Electrochemical pesticide detection with AutoDip--a portable platform for automation of crude sample analyses.

PubMed

Drechsel, Lisa; Schulz, Martin; von Stetten, Felix; Moldovan, Carmen; Zengerle, Roland; Paust, Nils

2015-02-07

Lab-on-a-chip devices hold promise for automation of complex workflows from sample to answer with minimal consumption of reagents in portable devices. However, complex, inhomogeneous samples as they occur in environmental or food analysis may block microchannels and thus often cause malfunction of the system. Here we present the novel AutoDip platform which is based on the movement of a solid phase through the reagents and sample instead of transporting a sequence of reagents through a fixed solid phase. A ball-pen mechanism operated by an external actuator automates unit operations such as incubation and washing by consecutively dipping the solid phase into the corresponding liquids. The platform is applied to electrochemical detection of organophosphorus pesticides in real food samples using an acetylcholinesterase (AChE) biosensor. Minimal sample preparation and an integrated reagent pre-storage module hold promise for easy handling of the assay. Detection of the pesticide chlorpyrifos-oxon (CPO) spiked into apple samples at concentrations of 10(-7) M has been demonstrated. This concentration is below the maximum residue level for chlorpyrifos in apples defined by the European Commission.

Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

NASA Astrophysics Data System (ADS)

Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

2017-09-01

The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

Embedding covalency into metal catalysts for efficient electrochemical conversion of CO2.

PubMed

Lim, Hyung-Kyu; Shin, Hyeyoung; Goddard, William A; Hwang, Yun Jeong; Min, Byoung Koun; Kim, Hyungjun

2014-08-13

CO2 conversion is an essential technology to develop a sustainable carbon economy for the present and the future. Many studies have focused extensively on the electrochemical conversion of CO2 into various useful chemicals. However, there is not yet a solution of sufficiently high enough efficiency and stability to demonstrate practical applicability. In this work, we use first-principles-based high-throughput screening to propose silver-based catalysts for efficient electrochemical reduction of CO2 to CO while decreasing the overpotential by 0.4-0.5 V. We discovered the covalency-aided electrochemical reaction (CAER) mechanism in which p-block dopants have a major effect on the modulating reaction energetics by imposing partial covalency into the metal catalysts, thereby enhancing their catalytic activity well beyond modulations arising from d-block dopants. In particular, sulfur or arsenic doping can effectively minimize the overpotential with good structural and electrochemical stability. We expect this work to provide useful insights to guide the development of a feasible strategy to overcome the limitations of current technology for electrochemical CO2 conversion.

Electrochemical Energy Storage for an Orbiting Space Station

NASA Technical Reports Server (NTRS)

Martin, R. E.

1981-01-01

The system weight of a multi hundred kilowatt fuel cell electrolysis cell energy storage system based upon alkaline electrochemical cell technology for use in a future orbiting space station in low Earth orbit (LEO) was studied. Preliminary system conceptual design, fuel cell module performance characteristics, subsystem and system weights, and overall system efficiency are identified. The impact of fuel cell module operating temperature and efficiency upon energy storage system weight is investigated. The weight of an advanced technology system featuring high strength filament wound reactant tanks and a fuel cell module employing lightweight graphite electrolyte reservoir plates is defined.

Electrochemical kinetics and dimensional considerations, at the nanoscale

NASA Astrophysics Data System (ADS)

Yamada, H.; Bandaru, P. R.

2016-06-01

It is shown that the consideration of the density of states variation in nanoscale electrochemical systems yields modulations in the rate constant and concomitant electrical currents. The proposed models extend the utility of Marcus-Hush-Chidsey (MHC) kinetics to a larger class of materials and could be used as a test of dimensional character. The implications of the study are of much significance to an understanding and modulation of charge transfer nanostructured electrodes.

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

Ultra-large optical modulation of electrochromic porous WO3 film and the local monitoring of redox activity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc03727a

PubMed Central

Cai, Guofa; Cui, Mengqi; Kumar, Vipin; Darmawan, Peter; Wang, Jiangxin; Wang, Xu; Lee-Sie Eh, Alice; Qian, Kai

2016-01-01

Porous WO3 films with ultra-high transmittance modulation were successfully fabricated on different substrates by a novel, facile and economical pulsed electrochemical deposited method with 1.1 s interval time between each pulse. The near ideal optical modulation (97.7% at 633 nm), fast switching speed (6 and 2.7 s), high coloration efficiency (118.3 cm2 C–1), and excellent cycling stability are achieved by the porous WO3 on ITO-coated glass. The outstanding electrochromic performances of the porous WO3 film were mainly attributed to the porous structure, which facilitates the charge-transfer, promotes the electrolyte infiltration and alleviates the expansion of the WO3 during H+ insertion compared to that of the compact structure. In addition, the relationships between the structural and electrochemical activity of the electrochromic WO3 films were further explored by the scanning electrochemical microscopy. These results testify that the porous structure can promote the infiltration of electrolyte and reduce the diffusion path, which consequently enhance the electrochemical activity. PMID:29910894

Low temperature thermally regenerative electrochemical system

DOEpatents

Loutfy, Raouf O.; Brown, Alan P.; Yao, Neng-Ping

1983-01-01

A thermally regenerative electrochemical system including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the complexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

Complex Exploration of Hydrocarbon Deposits on Arctic Shelf with Seismic, Electric Prospection and Electrochemical Methods

ERIC Educational Resources Information Center

Palamarchuk, Vasily; Holmyanskii, Mihail; Glinskaya, Nadezhda; Mishchenko, Oksana

2016-01-01

Article describes basic principles of seismic, electric prospection and electrochemical data complexation, received on the same research objects. The goal of our exploration works is complex exploration of hydrocarbon deposits on arctic shelf. Complex is based on ion-selective electrodes for detection of heavy metal complex anomalies in sea…

Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation†

PubMed Central

Lassalle-Kaiser, Benedikt; Hureau, Christelle; Pantazis, Dimitrios A.; Pushkar, Yulia; Guillot, Régis; Yachandra, Vittal K.; Yano, Junko; Neese, Frank; Anxolabéhère-Mallart, Elodie

2014-01-01

Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 × 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH2 complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH2 and Mn(III)OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn–O bond upon oxidation from Mn(II)OH2 to Mn(III)OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand. PMID:24772190

Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation.

PubMed

Lassalle-Kaiser, Benedikt; Hureau, Christelle; Pantazis, Dimitrios A; Pushkar, Yulia; Guillot, Régis; Yachandra, Vittal K; Yano, Junko; Neese, Frank; Anxolabéhère-Mallart, Elodie

2010-07-01

Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 × 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH 2 complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH 2 and Mn(III)OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn-O bond upon oxidation from Mn(II)OH 2 to Mn(III)OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand.

Optogenetic control of mitochondrial metabolism and Ca2+ signaling by mitochondria-targeted opsins.

PubMed

Tkatch, Tatiana; Greotti, Elisa; Baranauskas, Gytis; Pendin, Diana; Roy, Soumitra; Nita, Luliaoana I; Wettmarshausen, Jennifer; Prigge, Matthias; Yizhar, Ofer; Shirihai, Orian S; Fishman, Daniel; Hershfinkel, Michal; Fleidervish, Ilya A; Perocchi, Fabiana; Pozzan, Tullio; Sekler, Israel

2017-06-27

Key mitochondrial functions such as ATP production, Ca 2+ uptake and release, and substrate accumulation depend on the proton electrochemical gradient (ΔμH + ) across the inner membrane. Although several drugs can modulate ΔμH + , their effects are hardly reversible, and lack cellular specificity and spatial resolution. Although channelrhodopsins are widely used to modulate the plasma membrane potential of excitable cells, mitochondria have thus far eluded optogenetic control. Here we describe a toolkit of optometabolic constructs based on selective targeting of channelrhodopsins with distinct functional properties to the inner mitochondrial membrane of intact cells. We show that our strategy enables a light-dependent control of the mitochondrial membrane potential (Δψ m ) and coupled mitochondrial functions such as ATP synthesis by oxidative phosphorylation, Ca 2+ dynamics, and respiratory metabolism. By directly modulating Δψ m , the mitochondria-targeted opsins were used to control complex physiological processes such as spontaneous beats in cardiac myocytes and glucose-dependent ATP increase in pancreatic β-cells. Furthermore, our optometabolic tools allow modulation of mitochondrial functions in single cells and defined cell regions.

Compact electrochemical sensor system and method for field testing for metals in saliva or other fluids

DOEpatents

Lin, Yuehe; Bennett, Wendy D.; Timchalk, Charles; Thrall, Karla D.

2004-03-02

Microanalytical systems based on a microfluidics/electrochemical detection scheme are described. Individual modules, such as microfabricated piezoelectrically actuated pumps and a microelectrochemical cell were integrated onto portable platforms. This allowed rapid change-out and repair of individual components by incorporating "plug and play" concepts now standard in PC's. Different integration schemes were used for construction of the microanalytical systems based on microfluidics/electrochemical detection. In one scheme, all individual modules were integrated in the surface of the standard microfluidic platform based on a plug-and-play design. Microelectrochemical flow cell which integrated three electrodes based on a wall-jet design was fabricated on polymer substrate. The microelectrochemical flow cell was then plugged directly into the microfluidic platform. Another integration scheme was based on a multilayer lamination method utilizing stacking modules with different functionality to achieve a compact microanalytical device. Application of the microanalytical system for detection of lead in, for example, river water and saliva samples using stripping voltammetry is described.

Reliability and engineering sciences area. Materials research: Single junction thin film

NASA Technical Reports Server (NTRS)

1986-01-01

A test bench was designed and fabricated for the purpose of improving control of hot-spot test accuracy. Electrochemical corrosion research focused on corrosion mechanisms to which both crystalline and a-Si modules may be subjected in central station applications. A variety of cells and several designs were subjected to accelerated stress tests. Humiditiy degradation rates were determined and key electrochemical failure mechanisms were identified. Software was developed for the prediction of power loss resulting from open circuits in an array field of a-Si modules. Failure analysis was continued on the four ARCO Solar Genesis modules. The interactions of water on the silicon module was examined. An autocatalytic photooxidation model was proposed. The reliability and durability of bonding materials and electrical insulation were also studied.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2003-11-04

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electromechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Electrochemical carbon dioxide concentrator subsystem development

NASA Technical Reports Server (NTRS)

Koszenski, E. P.; Heppner, D. B.; Bunnell, C. T.

1986-01-01

The most promising concept for a regenerative CO2 removal system for long duration manned space flight is the Electrochemical CO2 Concentrator (EDC), which allows for the continuous, efficient removal of CO2 from the spacecraft cabin. This study addresses the advancement of the EDC system by generating subsystem and ancillary component reliability data through extensive endurance testing and developing related hardware components such as electrochemical module lightweight end plates, electrochemical module improved isolation valves, an improved air/liquid heat exchanger and a triple redundant relative humidity sensor. Efforts included fabrication and testing the EDC with a Sabatier CO2 Reduction Reactor and generation of data necessary for integration of the EDC into a space station air revitalization system. The results verified the high level of performance, reliability and durability of the EDC subsystem and ancillary hardware, verified the high efficiency of the Sabatier CO2 Reduction Reactor, and increased the overall EDC technology engineering data base. The study concluded that the EDC system is approaching the hardware maturity levels required for space station deployment.

Modulation of nitrogen vacancy charge state and fluorescence in nanodiamonds using electrochemical potential

PubMed Central

Karaveli, Sinan; Gaathon, Ophir; Wolcott, Abraham; Sakakibara, Reyu; Shemesh, Or A.; Peterka, Darcy S.; Boyden, Edward S.; Owen, Jonathan S.; Yuste, Rafael; Englund, Dirk

2016-01-01

The negatively charged nitrogen vacancy (NV−) center in diamond has attracted strong interest for a wide range of sensing and quantum information processing applications. To this end, recent work has focused on controlling the NV charge state, whose stability strongly depends on its electrostatic environment. Here, we demonstrate that the charge state and fluorescence dynamics of single NV centers in nanodiamonds with different surface terminations can be controlled by an externally applied potential difference in an electrochemical cell. The voltage dependence of the NV charge state can be used to stabilize the NV− state for spin-based sensing protocols and provides a method of charge state-dependent fluorescence sensing of electrochemical potentials. We detect clear NV fluorescence modulation for voltage changes down to 100 mV, with a single NV and down to 20 mV with multiple NV centers in a wide-field imaging mode. These results suggest that NV centers in nanodiamonds could enable parallel optical detection of biologically relevant electrochemical potentials. PMID:27035935

Modulation of nitrogen vacancy charge state and fluorescence in nanodiamonds using electrochemical potential.

PubMed

Karaveli, Sinan; Gaathon, Ophir; Wolcott, Abraham; Sakakibara, Reyu; Shemesh, Or A; Peterka, Darcy S; Boyden, Edward S; Owen, Jonathan S; Yuste, Rafael; Englund, Dirk

2016-04-12

The negatively charged nitrogen vacancy (NV(-)) center in diamond has attracted strong interest for a wide range of sensing and quantum information processing applications. To this end, recent work has focused on controlling the NV charge state, whose stability strongly depends on its electrostatic environment. Here, we demonstrate that the charge state and fluorescence dynamics of single NV centers in nanodiamonds with different surface terminations can be controlled by an externally applied potential difference in an electrochemical cell. The voltage dependence of the NV charge state can be used to stabilize the NV(-) state for spin-based sensing protocols and provides a method of charge state-dependent fluorescence sensing of electrochemical potentials. We detect clear NV fluorescence modulation for voltage changes down to 100 mV, with a single NV and down to 20 mV with multiple NV centers in a wide-field imaging mode. These results suggest that NV centers in nanodiamonds could enable parallel optical detection of biologically relevant electrochemical potentials.

Modulation of nitrogen vacancy charge state and fluorescence in nanodiamonds using electrochemical potential

NASA Astrophysics Data System (ADS)

Karaveli, Sinan; Gaathon, Ophir; Wolcott, Abraham; Sakakibara, Reyu; Shemesh, Or A.; Peterka, Darcy S.; Boyden, Edward S.; Owen, Jonathan S.; Yuste, Rafael; Englund, Dirk

2016-04-01

The negatively charged nitrogen vacancy (NV-) center in diamond has attracted strong interest for a wide range of sensing and quantum information processing applications. To this end, recent work has focused on controlling the NV charge state, whose stability strongly depends on its electrostatic environment. Here, we demonstrate that the charge state and fluorescence dynamics of single NV centers in nanodiamonds with different surface terminations can be controlled by an externally applied potential difference in an electrochemical cell. The voltage dependence of the NV charge state can be used to stabilize the NV- state for spin-based sensing protocols and provides a method of charge state-dependent fluorescence sensing of electrochemical potentials. We detect clear NV fluorescence modulation for voltage changes down to 100 mV, with a single NV and down to 20 mV with multiple NV centers in a wide-field imaging mode. These results suggest that NV centers in nanodiamonds could enable parallel optical detection of biologically relevant electrochemical potentials.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2004-09-28

An electrochemical energy storage device includes a number of solid-state thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

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

DOE PAGES

Martin, Daniel J.; McCarthy, Brian D.; Donley, Carrie L.; ...

2014-12-04

Here, a Ni(ii) complex with nitrogen and sulfur donor ligands degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen.

Reversibility of electrochemical reactions of sulfur supported on inverse opal carbon in glyme-Li salt molten complex electrolytes.

PubMed

Tachikawa, Naoki; Yamauchi, Kento; Takashima, Eriko; Park, Jun-Woo; Dokko, Kaoru; Watanabe, Masayoshi

2011-07-28

Electrochemical reactions of sulfur supported on three-dimensionally ordered macroporous carbon in glyme-Li salt molten complex electrolytes exhibit good reversibility and large capacity based on the mass of sulfur, which suggests that glyme-Li salt molten complexes are suitable electrolytes for Li-S batteries.

The possibility of multi-layer nanofabrication via atomic force microscope-based pulse electrochemical nanopatterning

NASA Astrophysics Data System (ADS)

Kim, Uk Su; Morita, Noboru; Lee, Deug Woo; Jun, Martin; Park, Jeong Woo

2017-05-01

Pulse electrochemical nanopatterning, a non-contact scanning probe lithography process using ultrashort voltage pulses, is based primarily on an electrochemical machining process using localized electrochemical oxidation between a sharp tool tip and the sample surface. In this study, nanoscale oxide patterns were formed on silicon Si (100) wafer surfaces via electrochemical surface nanopatterning, by supplying external pulsed currents through non-contact atomic force microscopy. Nanoscale oxide width and height were controlled by modulating the applied pulse duration. Additionally, protruding nanoscale oxides were removed completely by simple chemical etching, showing a depressed pattern on the sample substrate surface. Nanoscale two-dimensional oxides, prepared by a localized electrochemical reaction, can be defined easily by controlling physical and electrical variables, before proceeding further to a layer-by-layer nanofabrication process.

Best Practices for Operando Battery Experiments: Influences of X-ray Experiment Design on Observed Electrochemical Reactivity

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

Borkiewicz, O. J.; Wiaderek, Kamila M.; Chupas, Peter J.

Dynamic properties and multiscale complexities governing electrochemical energy storage in batteries are most ideally interrogated under simulated operating conditions within an electrochemical cell. We assess how electrochemical reactivity can be impacted by experiment design, including the X-ray measurements or by common features or adaptations of electrochemical cells that enable X-ray measurements.

Elaboration and use of nickel planar macrocyclic complex-based sensors for the direct electrochemical measurement of nitric oxide in biological media.

PubMed

Bedioui, F; Trevin, S; Devynck, J; Lantoine, F; Brunet, A; Devynck, M A

1997-01-01

We describe here the electrochemical detection of nitric oxide, NO, in biological systems by using chemically modified ultramicro carbon electrodes. In the first part of the paper, the different steps involved in the electrochemical preparation and characterization of the nickel-based sensor are described. This is illustrated by the use of nickel(II) tetrasulfonated phthalocyanine complex. The second part of the paper describes two examples of the direct electrochemical measurement of NO production in human blood platelets and endothelial cells from umbilical cord vein.

Low-temperature thermally regenerative electrochemical system

DOEpatents

Loutfy, R.O.; Brown, A.P.; Yao, N.P.

1982-04-21

A thermally regenerative electrochemical system is described including an electrochemical cell with two water-based electrolytes separated by an ion exchange membrane, at least one of the electrolytes containing a complexing agent and a salt of a multivalent metal whose respective order of potentials for a pair of its redox couples is reversible by a change in the amount of the ocmplexing agent in the electrolyte, the complexing agent being removable by distillation to cause the reversal.

Peptide Fragmentation by Corona Discharge Induced Electrochemical Ionization

PubMed Central

Lloyd, John R.; Hess, Sonja

2010-01-01

Fundamental studies have greatly improved our understanding of electrospray, including the underlying electrochemical reactions. Generally regarded as disadvantageous, we have recently shown that corona discharge (CD) can be used as an effective method to create a radical cation species [M]+•, thus optimizing the electrochemical reactions that occur on the surface of the stainless steel (SS) electrospray capillary tip. This technique is known as CD initiated electrochemical ionization (CD-ECI). Here, we report on the fundamental studies using CD-ECI to induce analytically useful in-source fragmentation of a range of molecules that complex transition metals. Compounds that have been selectively fragmented using CD-ECI include enolate forming phenylglycine containing peptides, glycopeptides, nucleosides and phosphopeptides. Collision induced dissociation (CID) or other activation techniques were not necessary for CD-ECI fragmentation. A four step mechanism was proposed: 1. Complexation using either Fe in the SS capillary tip material or Cu(II) as an offline complexation reagent; 2. Electrochemical oxidation of the complexed metal and thus formation of a radical cation (e.g.; Fe - e− → Fe +•); 3. Radical fragmentation of the complexed compound. 4. Electrospray ionization of the fragmented neutrals. Fragmentation patterns resembling b- and y-type ions were observed and allowed the localization of the phosphorylation sites. PMID:20869880

Technology advancement of the electrochemical CO2 concentrating process

NASA Technical Reports Server (NTRS)

Schubert, F. H.; Heppner, D. B.; Hallick, T. M.; Woods, R. R.

1979-01-01

Two multicell, liquid-cooled, advanced electrochemical depolarized carbon dioxide concentrator modules were fabricated. The cells utilized advanced, lightweight, plated anode current collectors, internal liquid cooling and lightweight cell frames. Both were designed to meet the carbon dioxide removal requirements of one-person, i.e., 1.0 kg/d (2.2 lb/d).

Electrochemical air revitalization system optimization investigation

NASA Technical Reports Server (NTRS)

Woods, R. R.; Schubert, F. H.; Hallick, T. M.

1975-01-01

A program to characterize a Breadboard of an Electrochemical Air Revitalization System (BEARS) was successfully completed. The BEARS is composed of three components: (1) a water vapor electrolysis module (WVEM) for O2 production and partial humidity control, (2) an electrochemical depolarized carbon dioxide concentrator module (EDCM) for CO2 control, and (3) a power-sharing controller, designed to utilize the power produced by the EDCM to partially offset the WVEM power requirements. It is concluded from the results of this work that the concept of electrochemical air revitalization with power-sharing is a viable solution to the problem of providing a localized topping force for O2 generation, CO2 removal and partial humidity control aboard manned spacecraft. Continued development of the EARS concept is recommended, applying the operational experience and limits identified during the BEARS program to testing of a one-man capacity system and toward the development of advanced system controls to optimize EARS operation for given interfaces and requirements. Successful completion of this development will produce timely technology necessary to plan future advanced environmental control and life support system programs and experiments.

A method for determining the actual rate of orientation switching of DNA self-assembled monolayers using optical and electrochemical frequency response analysis.

PubMed

Casanova-Moreno, J; Bizzotto, D

2015-02-17

Electrostatic control of the orientation of fluorophore-labeled DNA strands immobilized on an electrode surface has been shown to be an effective bioanalytical tool. Modulation techniques and later time-resolved measurements were used to evaluate the kinetics of the switching between lying and standing DNA conformations. These measurements, however, are the result of a convolution between the DNA "switching" response time and the other frequency limited responses in the measurement. In this work, a method for analyzing the response of a potential driven DNA sensor is presented by calculating the potential effectively dropped across the electrode interface (using electrochemical impedance spectroscopy) as opposed to the potential applied to the electrochemical cell. This effectively deconvolutes the effect of the charging time on the observed frequency response. The corrected response shows that DNA is able to switch conformation faster than previously reported using modulation techniques. This approach will ensure accurate measurements independent of the electrochemical system, removing the uncertainty in the analysis of the switching response, enabling comparison between samples and measurement systems.

Refurbishment of one-person regenerative air revitalization system

NASA Technical Reports Server (NTRS)

Powell, Ferolyn T.

1989-01-01

Regenerative processes for the revitalization of spacecraft atmospheres and reclamation of waste waters are essential for making long-term manned space missions a reality. Processes studied include: static feed water electrolysis for oxygen generation, Bosch carbon dioxide reduction, electrochemical carbon dioxide concentration, vapor compression distillation water recovery, and iodine monitoring. The objectives were to: provide engineering support to Marshall Space Flight Center personnel throughout all phases of the test program, e.g., planning through data analysis; fabricate, test, and deliver to Marshall Space Flight Center an electrochemical carbon dioxide module and test stand; fabricate and deliver an iodine monitor; evaluate the electrochemical carbon dioxide concentrator subsystem configuration and its ability to ensure safe utilization of hydrogen gas; evaluate techniques for recovering oxygen from a product oxygen and carbon dioxide stream; and evaluate the performance of an electrochemical carbon dioxide concentrator module to operate without hydrogen as a method of safe haven operation. Each of the tasks were related in that all focused on providing a better understanding of the function, operation, and performance of developmental pieces of environmental control and life support system hardware.

Effects of pH on the electrochemical behaviour of titanium alloys for implant applications.

PubMed

Souza, Maria E P; Lima, Lonetá; Lima, Carmo R P; Zavaglia, Cecília A C; Freire, Célia M A

2009-02-01

The electrochemical behaviour of two commercial titanium alloys Ti-6Al-4 V (ASTM F136) and Ti-13Nb-13Zr (ASTM F1713) was investigated in Ringer physiological solution at two pH values (5.5 and 7.0). The corrosion properties were examined by using electrochemical techniques: Potentiodynamic anodic polarization, cyclic polarization and electrochemical impedance spectroscopy (EIS). The electrochemical corrosion properties of both alloys at different conditions were measured in terms of corrosion potential (E (corr)), corrosion current density (i (corr)) and passivation current density (i (pass)). Equivalent electrical circuits were used to modulate EIS data, in order to characterize alloys surface and better understanding the pH effect on the interface alloy/solution.

Electrochemical activation and inhibition of neuromuscular systems through modulation of ion concentrations with ion-selective membranes

NASA Astrophysics Data System (ADS)

Song, Yong-Ak; Melik, Rohat; Rabie, Amr N.; Ibrahim, Ahmed M. S.; Moses, David; Tan, Ara; Han, Jongyoon; Lin, Samuel J.

2011-12-01

Conventional functional electrical stimulation aims to restore functional motor activity of patients with disabilities resulting from spinal cord injury or neurological disorders. However, intervention with functional electrical stimulation in neurological diseases lacks an effective implantable method that suppresses unwanted nerve signals. We have developed an electrochemical method to activate and inhibit a nerve by electrically modulating ion concentrations in situ along the nerve. Using ion-selective membranes to achieve different excitability states of the nerve, we observe either a reduction of the electrical threshold for stimulation by up to approximately 40%, or voluntary, reversible inhibition of nerve signal propagation. This low-threshold electrochemical stimulation method is applicable in current implantable neuroprosthetic devices, whereas the on-demand nerve-blocking mechanism could offer effective clinical intervention in disease states caused by uncontrolled nerve activation, such as epilepsy and chronic pain syndromes.

Electrochemical DNA biosensor for detection of porcine oligonucleotides using ruthenium(II) complex as intercalator label redox

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

Halid, Nurul Izni Abdullah; Hasbullah, Siti Aishah; Heng, Lee Yook

2014-09-03

A DNA biosensor detection of oligonucleotides via the interactions of porcine DNA with redox active complex based on the electrochemical transduction is described. A ruthenium(II) complex, [Ru(bpy){sub 2}(PIP)]{sup 2+}, (bpy = 2,2′bipyridine, PIP = 2-phenylimidazo[4,5-f[[1,10-phenanthroline]) as DNA label has been synthesized and characterized by 1H NMR and mass spectra. The study was carried out by covalent bonding immobilization of porcine aminated DNA probes sequences on screen printed electrode (SPE) modified with succinimide-acrylic microspheres and [Ru(bpy){sub 2}(PIP)]{sup 2+} was used as electrochemical redox intercalator label to detect DNA hybridization event. Electrochemical detection was performed by cyclic voltammetry (CV) and differential pulsemore » voltammetry (DPV) over the potential range where the ruthenium (II) complex was active. The results indicate that the interaction of [Ru(bpy){sub 2}(PIP)]{sup 2+} with hybridization complementary DNA has higher response compared to single-stranded and mismatch complementary DNA.« less

Smartphone-based cyclic voltammetry system with graphene modified screen printed electrodes for glucose detection.

PubMed

Ji, Daizong; Liu, Lei; Li, Shuang; Chen, Chen; Lu, Yanli; Wu, Jiajia; Liu, Qingjun

2017-12-15

Smartphone-based electrochemical devices have such advantages as the low price, miniaturization, and obtaining the real-time data. As a popular electrochemical method, cyclic voltammetry (CV) has shown its great practicability for quantitative detection and electrodes modification. In this study, a smartphone-based CV system with a simple method of electrode modification was constructed to perform electrochemical detections. The system was composed of these main portions: modified electrodes, portable electrochemical detector and smartphone. Among them, the detector was comprised of an energy transformation module applying the stimuli signals, and a low-cost potentiostat module for CV measurements with a Bluetooth module for transmitting data and commands. With an Application (App), the smartphone was used as the controller and displayer of the system. Through controlling of different scan rates, the smartphone-based system could perform CV detections for redox couples with test errors less than 3.8% compared to that of commercial electrochemical workstation. Also, the reduced graphene oxide (rGO) and sensitive substance could be modified by the system on the screen printed electrodes for detections. As a demonstration, 3-amino phenylboronic acid (APBA) was used as the sensitive substance to fabricate a glucose sensor. Finally, the experimental data of the system were shown the linear, sensitive, and specific responses to glucose at different doses, even in blood serum as low as about 0.026mM with 3δ/slope calculation. Thus, the system could show great potentials of detection and modification of electrodes in various fields, such as public health, water monitoring, and food quality. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and electrochemical studies of charge-transfer complexes of thiazolidine-2,4-dione with σ and π acceptors

NASA Astrophysics Data System (ADS)

Singh, Prashant; Kumar, Pradeep; Katyal, Anju; Kalra, Rashmi; Dass, Sujata K.; Prakash, Satya; Chandra, Ramesh

2010-03-01

In the present work, we report the synthesis and characterization of novel charge-transfer complexes of thiazolidine-2,4-dione (TZD) with sigma acceptor (iodine) and pi acceptors (chloranil, dichlorodicyanoquinone, picric acid and duraquinone). We also evaluated their thermal and electrochemical properties and we conclude that these complexes are frequency dependent. Charge-transfer complex between thiazolidine-2,4-dione and iodine give best conductivity. In conclusion, complex with sigma acceptors are more conducting than with pi acceptors.

Electrochemical sample matrix elimination for trace-level potentiometric detection with polymeric membrane ion-selective electrodes.

PubMed

Chumbimuni-Torres, Karin Y; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-08-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultratrace level (subnanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth-coated electrode, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte.

Electrochemical Sample Matrix Elimination for Trace Level Potentiometric Detection with Polymeric Membrane Ion-Selective Electrodes

PubMed Central

Chumbimuni-Torres, Karin Y.; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-01-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultra-trace level (sub-nanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination (EMPM) of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth coated electrodes, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte. PMID:18570385

Synthesis of hetero compounds using dialkylcarbonate quaternation

DOEpatents

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2017-10-17

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Synthesis of hetero ionic compounds using dialkylcarbonate quaternization

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

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2017-09-19

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Synthesis of hetero ionic compounds using dialkylcarbonate quaternization

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

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2018-04-03

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Separations of corticosteroids using electrochemically modulated liquid chromatography: Selectivity enhancements at a porous graphitic carbon stationary phase

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

Ting, E.Y.; Porter, M.D.

Electrochemically modulated liquid chromatography has been applied to the separation of a mixture of structurally similar corticosteroids (i.e., prednisone, prednisolone, cortisone, and hydrocortisone) using a porous graphitic carbon stationary phase. Changes in the voltage applied to the column markedly affected the efficiency as well as the elution order of the separation, with the mixture fully resolved at large negative values of applied potential. Mechanistic aspects in terms of the influence of changes in the applied voltage on the extent of the interactions between these analytes and the stationary phase are briefly discussed. 19 refs., 2 figs.

Library of electrocatalytic sites in nano-structured domains: electrocatalysis of hydrogen peroxide.

PubMed

Pandey, Prem C; Singh, Bhupendra

2008-12-01

Electrochemical detection of hydrogen peroxide at eight types of ormosil-modified electrodes, referred as hexacyanoferrate-system; Prussian blue systems (PB-1, PB-2, and PB-3), palladium (Pd-) system, graphite (Gr-) system, gold nanoparticle (AuNPs) system and palladium-gold nanoparticle (Pd-AuNPs) system were studied. The results on electrochemical detection suggested that hydrogen peroxide does not undergo homogeneous electrochemical mediation; however, the presence of redox mediator within nano-structured domains facilitates the electro-analysis of the same via redox electrocatalysis. Four approaches causing manipulation in nano-structured domains are described: (a) increase in the molecular size of the components generating nano-structured domains; (b) modulation via chemical reactivity; (c) modulation by non-reactive moieties and known nanoparticles; and (d) modulation by mixed approaches (a-c), all leading to decrease in a nano-structured domains. The results demonstrated that an increase in the size of nano-structured domains or decrease in micro-porous geometry increases the efficiency of electrocatalysis. The basic reaction protocol adopted in generating nano-structured domains, followed by manipulation protocols, supported the introduction of a library for creating electrocatalytic sites with varying electrocatalytic efficiency within the same basic nano-structured platform.

Characteristics for electrochemical machining with nanoscale voltage pulses.

PubMed

Lee, E S; Back, S Y; Lee, J T

2009-06-01

Electrochemical machining has traditionally been used in highly specialized fields, such as those of the aerospace and defense industries. It is now increasingly being applied in other industries, where parts with difficult-to-cut material, complex geometry and tribology, and devices of nanoscale and microscale are required. Electric characteristic plays a principal function role in and chemical characteristic plays an assistant function role in electrochemical machining. Therefore, essential parameters in electrochemical machining can be described current density, machining time, inter-electrode gap size, electrolyte, electrode shape etc. Electrochemical machining provides an economical and effective method for machining high strength, high tension and heat-resistant materials into complex shapes such as turbine blades of titanium and aluminum alloys. The application of nanoscale voltage pulses between a tool electrode and a workpiece in an electrochemical environment allows the three-dimensional machining of conducting materials with sub-micrometer precision. In this study, micro probe are developed by electrochemical etching and micro holes are manufactured using these micro probe as tool electrodes. Micro holes and microgroove can be accurately achieved by using nanoscale voltages pulses.

Electrochemical carbon dioxide concentrator subsystem math model. [for manned space station

NASA Technical Reports Server (NTRS)

Marshall, R. D.; Carlson, J. N.; Schubert, F. H.

1974-01-01

A steady state computer simulation model has been developed to describe the performance of a total six man, self-contained electrochemical carbon dioxide concentrator subsystem built for the space station prototype. The math model combines expressions describing the performance of the electrochemical depolarized carbon dioxide concentrator cells and modules previously developed with expressions describing the performance of the other major CS-6 components. The model is capable of accurately predicting CS-6 performance over EDC operating ranges and the computer simulation results agree with experimental data obtained over the prediction range.

Electrochemical carbon dioxide concentrator subsystem development

NASA Technical Reports Server (NTRS)

Heppner, D. B.; Dahlausen, M. J.; Schubert, F. H.

1983-01-01

The fabrication of a one-person Electrochemical Depolarized Carbon Dioxide Concentrator subsystem incorporating advanced electrochemical, mechanical, and control and monitor instrumentation concepts is discussed. This subsystem included an advanced liquid cooled unitized core composite cell module and integrated electromechanical components. Over 1800 hours with the subsystem with removal efficiencies between 90%. and 100%; endurance tests with a Fluid Control Assembly which integrates 11 gas handling components of the subsystem; and endurance testing of a coolant control assembly which integrates a coolant pump, diverter valve and a liquid accumulator were completed.

Spectroscopic, computational and electrochemical studies on the formation of the copper complex of 1-amino-4-hydroxy-9,10-anthraquinone and effect of it on superoxide formation by NADH dehydrogenase.

PubMed

Roy, Sanjay; Mondal, Palash; Sengupta, Partha Sarathi; Dhak, Debasis; Santra, Ramesh Chandra; Das, Saurabh; Guin, Partha Sarathi

2015-03-28

A 1 : 2 copper(II) complex of 1-amino-4-hydroxy-9,10-anthraquinone (QH) having the molecular formula CuQ2 was prepared and characterized by elemental analysis, NMR, FTIR, UV-vis and mass spectroscopy. The powder diffraction of the solid complex, magnetic susceptibility and ESR spectra were also recorded. The presence of the planar anthraquinone moiety in the complex makes it extremely difficult to obtain a single crystal suitable for X-ray diffraction studies. To overcome this problem, density functional theory (DFT) was used to evaluate an optimized structure of CuQ2. In the optimized structure, it was found that there is a tilt of the two planar aromatic anthraquinone rings of the complex with respect to each other in the two planes containing the O-Cu(II)-O plane. The present study is an important addition to the understanding of the structural aspects of metal-anthracyclines because there are only a few reports on the actual structures of metal-anthracyclines. The theoretical vibrational spectrum of the complex was assigned with the help of vibrational energy distribution analysis (VEDA) using potential energy distribution (PED) and compared with experimental results. Being important in producing the biochemical action of this class of molecules, the electrochemical behavior of the complex was studied in aqueous and non-aqueous solvents to find certain electrochemical parameters. In aqueous media, reduction involves a kinetic effect during electron transfer at an electrode surface, which was characterized very carefully using cyclic voltammetry. Electrochemical studies showed a significant modification in the electrochemical properties of 1-amino-4-hydroxy-9,10-anthraquinone (QH) when bound to Cu(II) in the complex compared to those observed for free QH. This suggests that the copper complex might be a good choice as a biologically active molecule, which was reflected in the lack of stimulated superoxide generation by the complex.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2000-01-01

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. In one embodiment, a sheet of conductive material is processed by employing a known milling, stamping, or chemical etching technique to include a connection pattern which provides for flexible and selective interconnecting of individual electrochemical cells within the housing, which may be a hermetically sealed housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Electrical research on solar cells and photovoltaic materials

NASA Technical Reports Server (NTRS)

Orehotsky, J.

1984-01-01

The flat-plate solar cell array program which increases the service lifetime of the photovoltaic modules used for terrestrial energy applications is discussed. The current-voltage response characteristics of the solar cells encapsulated in the modules degrade with service time and this degradation places a limitation on the useful lifetime of the modules. The most desirable flat-plate array system involves solar cells consisting of highly polarizable materials with similar electrochemical potentials where the cells are encapsulated in polymers in which ionic concentrations and mobilities are negligibly small. Another possible mechanism limiting the service lifetime of the photovoltaic modules is the gradual loss of the electrical insulation characteristics of the polymer pottant due to water absorption or due to polymer degradation from light or heat effects. The mechanical properties of various polymer pottant materials and of electrochemical corrosion mechanisms in solar cell material are as follows: (1) electrical and ionic resistivity; (2) water absorption kinetics and water solubility limits; and (3) corrosion characterization of various metallization systems used in solar cell construction.

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

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

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

Development of intraoperative electrochemical detection: wireless instantaneous neurochemical concentration sensor for deep brain stimulation feedback

PubMed Central

Van Gompel, Jamie J.; Chang, Su-Youne; Goerss, Stephan J.; Kim, In Yong; Kimble, Christopher; Bennet, Kevin E.; Lee, Kendall H.

2010-01-01

Deep brain stimulation (DBS) is effective when there appears to be a distortion in the complex neurochemical circuitry of the brain. Currently, the mechanism of DBS is incompletely understood; however, it has been hypothesized that DBS evokes release of neurochemicals. Well-established chemical detection systems such as microdialysis and mass spectrometry are impractical if one is assessing changes that are happening on a second-to-second time scale or for chronically used implanted recordings, as would be required for DBS feedback. Electrochemical detection techniques such as fast-scan cyclic voltammetry (FSCV) and amperometry have until recently remained in the realm of basic science; however, it is enticing to apply these powerful recording technologies to clinical and translational applications. The Wireless Instantaneous Neurochemical Concentration Sensor (WINCS) currently is a research device designed for human use capable of in vivo FSCV and amperometry, sampling at subsecond time resolution. In this paper, the authors review recent advances in this electrochemical application to DBS technologies. The WINCS can detect dopamine, adenosine, and serotonin by FSCV. For example, FSCV is capable of detecting dopamine in the caudate evoked by stimulation of the subthalamic nucleus/substantia nigra in pig and rat models of DBS. It is further capable of detecting dopamine by amperometry and, when used with enzyme linked sensors, both glutamate and adenosine. In conclusion, WINCS is a highly versatile instrument that allows near real-time (millisecond) detection of neurochemicals important to DBS research. In the future, the neurochemical changes detected using WINCS may be important as surrogate markers for proper DBS placement as well as the sensor component for a “smart” DBS system with electrochemical feedback that allows automatic modulation of stimulation parameters. Current work is under way to establish WINCS use in humans. PMID:20672923

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

NASA Astrophysics Data System (ADS)

Sulyma, Christopher Michael

This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail. In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated here in detail using the electrochemical techniques of cyclic voltammetry, open circuit potential analysis, polarization resistance measurements, and Fourier transform impedance spectroscopy. The results suggest that forming structurally weak oxide layers on the CMP samples is a key to achieving the goal of chemically controlled CMP of Ta/TaN at low down-pressures. (Abstract shortened by UMI.)

SERS- and Electrochemically Active 3D Plasmonic Liquid Marbles for Molecular-Level Spectroelectrochemical Investigation of Microliter Reactions.

PubMed

Koh, Charlynn Sher Lin; Lee, Hiang Kwee; Phan-Quang, Gia Chuong; Han, Xuemei; Lee, Mian Rong; Yang, Zhe; Ling, Xing Yi

2017-07-17

Liquid marbles are emergent microreactors owing to their isolated environment and the flexibility of materials used. Plasmonic liquid marbles (PLMs) are demonstrated as the smallest spectroelectrochemical microliter-scale reactor for concurrent spectro- and electrochemical analyses. The three-dimensional Ag shell of PLMs are exploited as a bifunctional surface-enhanced Raman scattering (SERS) platform and working electrode for redox process modulation. The combination of SERS and electrochemistry (EC) capabilities enables in situ molecular read-out of transient electrochemical species, and elucidate the potential-dependent and multi-step reaction dynamics. The 3D configuration of our PLM-based EC-SERS system exhibits 2-fold and 10-fold superior electrochemical and SERS performance than conventional 2D platforms. The rich molecular-level electrochemical insights and excellent EC-SERS capabilities offered by our 3D spectroelectrochemical system are pertinent in charge transfer processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of transition metal oxide/sulfide nanostructures for electrochemical applications

NASA Astrophysics Data System (ADS)

Yilmaz, Gamze

This thesis is essentially oriented to develop low-cost nanostructured transition metal (nickel and vanadium) oxides and sulfides with high energy density, power density and electrochemical stability via strategies of structural design, hybridization, functionalization and surface engineering. Metal oxide and metal oxide/sulfide hybrid nanostructures in several designs, including hierarchical porous nanostructures, hollow polyhedrons, nanocubes, nanoframes, octopod nanoframes, and nanocages, were synthesized to study the contribution of structural design, compositional engineering, functionalization and surface engineering to the electrochemical properties of the materials. Modulated compositional and structural features disclosed the opportunities of large accessible active sites, facile ion transport, robustness and enhanced electrical conductivity. The best electrochemical performance with merits of highest energy density (38.9 Wh kg-1), power density (7.4 kW kg-1) and electrochemical stability (90.9% after 10000 cycles) was obtained for nickel cobalt layered double hydroxide/cobalt sulfide (NiCo-LDH/Co9S8) hybrid hollow polyhedron structure.

Nanoscale Protection Layers To Mitigate Degradation in High-Energy Electrochemical Energy Storage Systems.

PubMed

Lin, Chuan-Fu; Qi, Yue; Gregorczyk, Keith; Lee, Sang Bok; Rubloff, Gary W

2018-01-16

In the pursuit of energy storage devices with higher energy and power, new ion storage materials and high-voltage battery chemistries are of paramount importance. However, they invite-and often enhance-degradation mechanisms, which are reflected in capacity loss with charge/discharge cycling and sometimes in safety problems. Degradation mechanisms are often driven by fundamentals such as chemical and electrochemical reactions at electrode-electrolyte interfaces, volume expansion and stress associated with ion insertion and extraction, and profound inhomogeneity of electrochemical behavior. While it is important to identify and understand these mechanisms at some reasonable level, it is even more critical to design strategies to mitigate these degradation pathways and to develop means to implement and validate the strategies. A growing set of research highlights the mitigation benefits achievable by forming thin protection layers (PLs) intentionally created as artificial interphase regions at the electrode-electrolyte interface. These advances illustrate a promising-perhaps even generic-pathway for enabling higher-energy and higher-voltage battery configurations. In this Account, we summarize examples of such PLs that serve as mitigation strategies to avoid degradation in lithium metal anodes, conversion-type electrode materials, and alloy-type electrodes. Examples are chosen from a larger body of electrochemical degradation research carried out in Nanostructures for Electrical Energy Storage (NEES), our DOE Energy Frontier Research Center. Overall, we argue on the basis of experimental and theoretical evidence that PLs effectively stabilize the electrochemical interfaces to prevent parasitic chemical and electrochemical reactions and mitigate the structural, mechanical, and compositional degradation of the electrode materials at the electrode-electrolyte interfaces. The evidenced improvement in performance metrics is accomplished by (1) establishing a homogeneous interface for ion insertion and extraction, (2) providing mechanical constraints to maintain structural integrity and robust electronic and ionic conduction pathways, and (3) introducing spatial confinements on the electrode material matrix to alter the phase transformation (delaying the occurrence of the conversion reaction) upon Li insertion, which results in superior electrode performance, excellent capacity retention, and improved reversibility. Taken together, these examples portray a valuable role for thin protection layers synthesized over electrode surfaces, both for their benefit to cycle stability and for revealing insights into degradation and mitigation mechanisms. Furthermore, they underscore the impact of complex electrochemical behavior at nanoscale materials and nanostructure interfaces in modulating the behavior of energy storage devices at the mesoscale and macroscale.

Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials.

PubMed

Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan

2011-12-23

Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-air cell comprising an electrolyte with a room temperature ionic liquid and hygroscopic additive

DOEpatents

Friesen, Cody A.; Krishnan, Ramkumar; Tang, Toni; Wolfe, Derek

2014-08-19

An electrochemical cell comprising an electrolyte comprising water and a hydrophobic ionic liquid comprising positive ions and negative ions. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. A hydrophilic or hygroscopic additive modulates the hydrophobicity of the ionic liquid to maintain a concentration of the water in the electrolyte is between 0.001 mol % and 25 mol %.

Complex Nanostructures from Materials based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion.

PubMed

Guan, Bu Yuan; Yu, Xin Yao; Wu, Hao Bin; Lou, Xiong Wen David

2017-12-01

Metal-organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF-based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy-related applications of complex nanostructures derived from MOF-based precursors is provided. After a brief summary of synthetic methods of MOF-based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single-shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium-ion batteries, hybrid supercapacitors, water-splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF-based-templates for electrochemical energy storage and conversion applications are outlined. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size and Electronic Modulation of Iridium Nanoparticles on Nitrogen Functionalized Carbon toward Advanced Electrocatalysts for Alkaline Water Splitting.

PubMed

Wang, Hua; Ming, Mei; Hu, Min; Xu, Caili; Wang, Yi; Zhang, Yun; Gao, Daojiang; Bi, Jian; Fan, Guangyin; Hu, Jin-Song

2018-06-14

Developing efficient catalytic materials for electrochemical water splitting is important. Herein, uniformly dispersed and size-controllable iridium (Ir) nanoparticles (NPs) were prepared using a nitrogen-functionalized carbon (Ir/CN) as the support. We found that nitrogen function can simultaneously modulate the size of Ir NPs to substantially enhance the catalytically active sites and adjust the electronic structure of Ir, thereby promoting electrocatalytic activity for water splitting. Consequently, the as-synthesized Ir/CN shows excellent electrocatalytic performance with overpotentials of 12 and 265 mV for hydrogen and oxygen evolution reactions in basic medium, respectively. These findings may pave a way for designing and synthesizing other similar materials as efficient catalysts for electrochemical water splitting.

CMOS Electrochemical Instrumentation for Biosensor Microsystems: A Review.

PubMed

Li, Haitao; Liu, Xiaowen; Li, Lin; Mu, Xiaoyi; Genov, Roman; Mason, Andrew J

2016-12-31

Modern biosensors play a critical role in healthcare and have a quickly growing commercial market. Compared to traditional optical-based sensing, electrochemical biosensors are attractive due to superior performance in response time, cost, complexity and potential for miniaturization. To address the shortcomings of traditional benchtop electrochemical instruments, in recent years, many complementary metal oxide semiconductor (CMOS) instrumentation circuits have been reported for electrochemical biosensors. This paper provides a review and analysis of CMOS electrochemical instrumentation circuits. First, important concepts in electrochemical sensing are presented from an instrumentation point of view. Then, electrochemical instrumentation circuits are organized into functional classes, and reported CMOS circuits are reviewed and analyzed to illuminate design options and performance tradeoffs. Finally, recent trends and challenges toward on-CMOS sensor integration that could enable highly miniaturized electrochemical biosensor microsystems are discussed. The information in the paper can guide next generation electrochemical sensor design.

CMOS Electrochemical Instrumentation for Biosensor Microsystems: A Review

PubMed Central

Li, Haitao; Liu, Xiaowen; Li, Lin; Mu, Xiaoyi; Genov, Roman; Mason, Andrew J.

2016-01-01

Modern biosensors play a critical role in healthcare and have a quickly growing commercial market. Compared to traditional optical-based sensing, electrochemical biosensors are attractive due to superior performance in response time, cost, complexity and potential for miniaturization. To address the shortcomings of traditional benchtop electrochemical instruments, in recent years, many complementary metal oxide semiconductor (CMOS) instrumentation circuits have been reported for electrochemical biosensors. This paper provides a review and analysis of CMOS electrochemical instrumentation circuits. First, important concepts in electrochemical sensing are presented from an instrumentation point of view. Then, electrochemical instrumentation circuits are organized into functional classes, and reported CMOS circuits are reviewed and analyzed to illuminate design options and performance tradeoffs. Finally, recent trends and challenges toward on-CMOS sensor integration that could enable highly miniaturized electrochemical biosensor microsystems are discussed. The information in the paper can guide next generation electrochemical sensor design. PMID:28042860

Synthesis, characterization and electrochemical investigations of mixed-ligand copper(II)-organic supramolecular frameworks

NASA Astrophysics Data System (ADS)

Singh, Sandeep K.; Srivastava, Ashish Kumar; Srivastava, Krishna; Banerjee, Rahul; Prasad, Jagdish

2017-11-01

Two mixed-ligand copper(II)-organic coordination compounds with 5,5‧-dimethyl-2,2‧-bipyridine (5,5‧-Me2bpy) as a primary ligand while aliphatic malonate (Hmal) and aromatic 2-hydroxynicotinate (2-OHNA) as secondary ligands, were synthesized. These complexes are formulated as: [Cu(Hmal)(5,5‧-Me2bpy)(H2O)](ClO4) 1 and [Cu2(2-OHNA)2(5,5‧-Me2bpy)2(NO3)](NO3) 2. These two complexes were structurally characterized by single crystal X-ray diffraction analysis. Characterization was further supported by powder X-ray diffraction analysis, elemental analyses, FT-IR, FAB-MASS and TGA, DSC studies. Cyclic voltammetric and UV-visible spectral studies of these two complexes have also been done. The electrochemical studies of complex 1 in DMSO and DMF have shown that this complex undergoes quasi-reversible diffusion-controlled one-electron transfer reaction without any chemical complication while complex 2 in DMSO undergoes quasi-reversible diffusion-controlled one electron transfer reaction, following EC mechanism. The electrochemical behaviour of complex 2 in DMF is complicated probably due to presence of more than one species in solution phase.

Neptunium carbonato complexes in aqueous solution: an electrochemical, spectroscopic, and quantum chemical study.

PubMed

Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro; Rossberg, André; Funke, Harald; Scheinost, Andreas C; Bernhard, Gert; Yaita, Tsuyoshi; Hennig, Christoph

2009-12-21

The electrochemical behavior and complex structure of Np carbonato complexes, which are of major concern for the geological disposal of radioactive wastes, have been investigated in aqueous Na(2)CO(3) and Na(2)CO(3)/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 1.5 M Na(2)CO(3) with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex, [NpO(2)(CO(3))(3)](n-) (n = 5 for Np(V), and 4 for Np(VI)). Hence, the electrochemical reaction of the Np(V/VI) redox couple merely results in the shortening/lengthening of bond distances mainly because of the change of the cationic charge of Np, without any structural rearrangement. This explains the observed reversible-like feature on their cyclic voltammograms. In contrast, the electrochemical oxidation of Np(V) in a highly basic carbonate solution of 2.0 M Na(2)CO(3)/1.0 M NaOH (pH > 13) yielded a stable heptavalent Np complex of [Np(VII)O(4)(OH)(2)](3-), indicating that the oxidation reaction from Np(V) to Np(VII) in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO(3)(2-)) to hydroxide ions (OH(-)).

Emission switching of ferrocenyl Schiff bases and a representative ruthenium complex in alkaline DMSO: Absorption, electrochemical and microstructural studies

NASA Astrophysics Data System (ADS)

Mishra, Lallan; Dubey, Santosh Kumar

2007-10-01

N,N'-Bis(4-ferrocenyl)- p-phenylene/octamethylene-diimines (L 1/L 2) and a representative Ru(II) complex [Ru(DMSO) 2Cl 2L 1]·2H 2O were prepared and characterized which showed many fold enhancement in their luminescence in alkaline dimethylsulfoxide (DMSO) solution. Spectral and electrochemical properties of these compounds have been studied. Microstructure (SEM) of L 1 and its complex showed single-phase porous material of crystal size ˜1 μm.

Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes.

PubMed

Asadi, Zahra; Shorkaei, Mohammad Ranjkesh

2013-03-15

Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible. Copyright © 2012 Elsevier B.V. All rights reserved.

Fractional capacity electrolyzer development for CO2 and H2O electrolysis

NASA Technical Reports Server (NTRS)

Wynveen, R. A.

1980-01-01

The electrolyzer module was designed to produce 0.24 kg/d (0.53 lb/d) of breathable oxygen from the electrolysis of metabolic carbon dioxide and water vapor. The fractional capacity electrolyzer module is constructed from three electrochemical tube cells and contains only three critical seals. The module design illustrated an 84 percent reduction in the total number of seals for a one person capacity oxygen generating system based on the solid electrolyte carbon dioxide and water vapor electrolysis concept. The electrolyzer module was successfully endurance tested for 71 days.

A review of iron and cobalt porphyrins, phthalocyanines, and related complexes for electrochemical and photochemical reduction of carbon dioxide

DOE PAGES

Manbeck, Gerald F.; Fujita, Etsuko

2015-03-30

This review summarizes research on the electrochemical and photochemical reduction of CO₂ using a variety of iron and cobalt porphyrins, phthalocyanines, and related complexes. Metalloporphyrins and metallophthalocyanines are visible light absorbers with extremely large extinction coefficients. However, yields of photochemically-generated active catalysts for CO₂ reduction are typically low owing to the requirement of a second photoinduced electron. This requirement is not relevant to the case of electrochemical CO₂ reduction. Recent progress on efficient and stable electrochemical systems includes the use of FeTPP catalysts that have prepositioned phenyl OH groups in their second coordination spheres. This has led to remarkable progressmore » in carrying out coupled proton-electron transfer reactions for CO₂ reduction. Such ground-breaking research has to be continued in order to produce renewable fuels in an economically feasible manner.« less

The Mathematical Modeling and Computer Simulation of Electrochemical Micromachining Using Ultrashort Pulses

NASA Astrophysics Data System (ADS)

Kozak, J.; Gulbinowicz, D.; Gulbinowicz, Z.

2009-05-01

The need for complex and accurate three dimensional (3-D) microcomponents is increasing rapidly for many industrial and consumer products. Electrochemical machining process (ECM) has the potential of generating desired crack-free and stress-free surfaces of microcomponents. This paper reports a study of pulse electrochemical micromachining (PECMM) using ultrashort (nanoseconds) pulses for generating complex 3-D microstructures of high accuracy. A mathematical model of the microshaping process with taking into consideration unsteady phenomena in electrical double layer has been developed. The software for computer simulation of PECM has been developed and the effects of machining parameters on anodic localization and final shape of machined surface are presented.

Enhanced lithium storage performance of hierarchical CuO nanomaterials with surface fractal characteristics

NASA Astrophysics Data System (ADS)

Li, Ang; He, Renyue; Bian, Zhuo; Song, Huaihe; Chen, Xiaohong; Zhou, Jisheng

2018-06-01

Self-assembled hierarchical CuO nanostructures with fractal structures were prepared by a mild method and exhibited excellent lithium storage properties, certain of which even demonstrated a high reversible capacity of 827 mAh g-1 at a rate of 0.1 C. An interesting phenomenon was observed that the electrochemical performance varies along with the structure complexity, and the products with higher surface factal dimensions exhibited larger capability and better cyclability. Structural and electrochemical analysis methods were used to explore the lithiation kinetics of the samples and the reasons for the outstanding electrochemical performances related to the complexities of hierarchical nanostructures and the irregularities of surface and mass distribution.

Construction and Characterization of a Chitosan-Immobilized-Enzyme and β-Cyclodextrin-Included-Ferrocene-Based Electrochemical Biosensor for H₂O₂ Detection.

PubMed

Dong, Wenbo; Wang, Kaiyin; Chen, Yu; Li, Weiping; Ye, Yanchun; Jin, Shaohua

2017-07-28

An electrochemical detection biosensor was prepared with the chitosan-immobilized-enzyme (CTS-CAT) and β-cyclodextrin-included-ferrocene (β-CD-FE) complex for the determination of H₂O₂. Ferrocene (FE) was included in β-cyclodextrin (β-CD) to increase its stability. The structure of the β-CD-FE was characterized. The inclusion amount, inclusion rate, and electrochemical properties of inclusion complexes were determined to optimize the reaction conditions for the inclusion. CTS-CAT was prepared by a step-by-step immobilization method, which overcame the disadvantages of the conventional preparation methods. The immobilization conditions were optimized to obtain the desired enzyme activity. CTS-CAT/β-CD-FE composite electrodes were prepared by compositing the CTS-CAT with the β-CD-FE complex on a glassy carbon electrode and used for the electrochemical detection of H₂O₂. It was found that the CTS-CAT could produce a strong reduction peak current in response to H₂O₂ and the β-CD-FE could amplify the current signal. The peak current exhibited a linear relationship with the H₂O₂ concentration in the range of 1.0 × 10 -7 -6.0 × 10 -3 mol/L. Our work provided a novel method for the construction of electrochemical biosensors with a fast response, good stability, high sensitivity, and a wide linear response range based on the composite of chitosan and cyclodextrin.

Intramolecular allyl transfer reaction from allyl ether to aldehyde groups: experimental and theoretical studies.

PubMed

Franco, Delphine; Wenger, Karine; Antonczak, Serge; Cabrol-Bass, Daniel; Duñach, Elisabet; Rocamora, Mercè; Gomez, Montserrat; Muller, Guillermo

2002-02-02

The intramolecular transfer of the allyl group of functionalized allyl aryl ethers to an aldehyde group in the presence of Ni0 complexes was studied from chemical, electrochemical and theoretical points of view. The chemical reaction involves the addition of Ni0 to the allyl ether followed by stoichiometric allylation. The electrochemical process is catalytic in nickel and involves the reduction of intermediate eta3-allylnickel(II) complexes.

Aerobic and Electrochemical Oxidations with N-Oxyl Reagents

NASA Astrophysics Data System (ADS)

Miles, Kelsey C.

Selective oxidation of organic compounds represents a significant challenge for chemical transformations. Oxidation methods that utilize nitroxyl catalysts have become increasingly attractive and include Cu/nitroxyl and nitroxyl/NO x co-catalyst systems. Electrochemical activation of nitroxyls is also well known and offers an appealing alternative to the use of chemical co-oxidants. However, academic and industrial organic synthetic communities have not widely adopted electrochemical methods. Nitroxyl catalysts facilitate effective and selective oxidation of alcohols and aldehydes to ketones and carboxylic acids. Selective benzylic, allylic, and alpha-heteroatom C-H abstraction can also be achieved with nitroxyls and provides access to oxygenated products when used in combination with molecular oxygen as a radical trap. This thesis reports various chemical and electrochemical oxidation methods that were developed using nitroxyl mediators. Chapter 1 provides a short review on practical aerobic alcohol oxidation with Cu/nitroxyl and nitroxyl/NO x systems and emphasizes the utility of bicyclic nitroxyls as co-catalysts. In Chapter 2, the combination of these bicyclic nitroxyls with NOx is explored for development of a mild oxidation of alpha-chiral aryl aldehydes and showcases a sequential asymmetric hydroformylation/oxidation method. Chapter 3 reports the synthesis and characterization of two novel Cu/bicyclic nitroxyl complexes and the electronic structure analysis of these complexes. Chapter 4 highlights the electrochemical activation of various nitroxyls and reports an in-depth study on electrochemical alcohol oxidation and compares the reactivity of nitroxyls under electrochemical or chemical activation. N-oxyls can also participate in selective C-H abstraction, and Chapter 5 reports the chemical and electrochemical activation of N-oxyls for radical-mediated C-H oxygenation of (hetero)arylmethanes. For these electrochemical transformations, the development of user-friendly methods and analysis techniques is emphasized.

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

Transparent Electrochemical Gratings from a Patterned Bistable Silver Mirror.

PubMed

Park, Chihyun; Na, Jongbeom; Han, Minsu; Kim, Eunkyoung

2017-07-25

Silver mirror patterns were formed reversibly on a polystyrene (PS)-patterned electrode to produce gratings through the electrochemical reduction of silver ions. The electrochemical gratings exhibited high transparency (T > 95%), similar to a see-through window, by matching the refractive index of the grating pattern with the surrounding medium. The gratings switch to a diffractive state upon the formation of a mirror pattern (T < 5%) with a high diffraction efficiency up to 40%, providing reversible diffractive gratings. The diffraction state was maintained in the voltage-off state (V-off) for 40 min, which demonstrated bistable reversible electrochemical grating (BREG) behavior. By carefully combining the BREGs through period matching, dual-color switching was achieved within the full color region, which exhibited three distinct optical switching states between -2.5, 0, and +2.5 V. The wide range of light tenability using the metallic BREGs developed herein enabled IR modulation, NIR light reflection, and on-demand heat transfer.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater.

PubMed

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-03-15

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO 2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

PubMed Central

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-01-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process. PMID:28294180

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

NASA Astrophysics Data System (ADS)

Gu, Di; Gao, Simeng; Jiang, Tingting; Wang, Baohui

2017-03-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

An unexpected Schiff base-type Ni(II) complex: Synthesis, crystal structures, fluorescence, electrochemical property and SOD-like activities

NASA Astrophysics Data System (ADS)

Chai, Lan-Qin; Zhang, Hong-Song; Huang, Jiao-Jiao; Zhang, Yu-Li

2015-02-01

An unexpected Schiff base-type Ni(II) complex, [Ni(L2)2]ṡCH3OH (HL2 = 1-(2-{[(E)-3, 5-dibromo-2-hydroxybenzylidene]amino}phenyl)ethanone oxime), has been synthesized via complexation of Ni(II) acetate tetrahydrate with HL1 (2-(3,5-dibromo-2-hydroxyphenyl)-4-methyl-1,2-dihydroquinazoline 3-oxide) originally. HL1 and its corresponding Ni(II) complex were characterized by IR, 1H NMR spectra, as well as by elemental analysis, UV-Vis and emission spectroscopy, respectively. Crystal structures of the ligand and complex have been determined by single-crystal X-ray diffraction. Each complex links two other molecules into an infinite 1-D chain via intermolecular hydrogen bonding interactions. Moreover, the electrochemical property of the nickle complex was studied by cyclic voltammetry. In addition, SOD-like activities of HL1 and Ni(II) complex were also investigated.

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond.

PubMed

Kaliginedi, Veerabhadrarao; Ozawa, Hiroaki; Kuzume, Akiyoshi; Maharajan, Sivarajakumar; Pobelov, Ilya V; Kwon, Nam Hee; Mohos, Miklos; Broekmann, Peter; Fromm, Katharina M; Haga, Masa-aki; Wandlowski, Thomas

2015-11-14

Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge-discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g(-1) at a current density of 10 μA cm(-2) and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.

An Efficient Power Harvesting Mobile Phone-Based Electrochemical Biosensor for Point-of-Care Health Monitoring

PubMed Central

Sun, Alexander C.; Yao, Chengyang; Venkatesh, A. G.; Hall, Drew A.

2016-01-01

Cellular phone penetration has grown continually over the past two decades with the number of connected devices rapidly approaching the total world population. Leveraging the worldwide ubiquity and connectivity of these devices, we developed a mobile phone-based electrochemical biosensor platform for point-of-care (POC) diagnostics and wellness tracking. The platform consists of an inexpensive electronic module (< $20) containing a low-power potentiostat that interfaces with and efficiently harvests power from a wide variety of phones through the audio jack. Active impedance matching improves the harvesting efficiency to 79%. Excluding loses from supply rectification and regulation, the module consumes 6.9 mW peak power and can measure < 1 nA bidirectional current. The prototype was shown to operate within the available power budget set by mobile devices and produce data that matches well with that of an expensive laboratory grade instrument. We demonstrate that the platform can be used to track the concentration of secretory leukocyte protease inhibitor (SLPI), a biomarker for monitoring lung infections in cystic fibrosis patients, in its physiological range via an electrochemical sandwich assay on disposable screen-printed electrodes with a 1 nM limit of detection. PMID:27725788

Electrochemical capacitance modulation in an interacting mesoscopic capacitor induced by internal charge transfer

NASA Astrophysics Data System (ADS)

Liu, Wei; He, Jianhong; Guo, Huazhong; Gao, Jie

2018-04-01

We report experiments on the dynamic response of an interacting mesoscopic capacitor consisting of a quantum dot with two confined spin-split levels of the lowest Landau level. In high magnetic fields, states inside the dot are regulated by a mixture of Coulomb interaction and Landau-level quantization, and electrons distribute on two spatially separated regions. Quantum point contact voltage and magnetic field are employed to manipulate the number and distribution of electrons inside the quantum dot. We find that the periodicity of the electrochemical capacitance oscillations is dominated by the charging energy, and their amplitudes, due to internal charge transfer and strong internal capacitive coupling, show rich variations of modulations. Magnetocapacitance displays a sawtoothlike manner and may differ in tooth directions for different voltages, which, we demonstrate, result from a sawtoothlike electrochemical potential change induced by internal charge transfer and field-sensitive electrostatic potential. We further build a charge stability diagram, which, together with all other capacitance properties, is consistently interpreted in terms of a double-dot model. The demonstrated technique is of interest as a tool for fast and sensitive charge state readout of a double-quantum-dot qubit in the gigahertz frequency quantum electronics.

Dioxythiophene-based polymer electrodes for supercapacitor modules.

PubMed

Liu, David Y; Reynolds, John R

2010-12-01

We report on the electrochemical and capacitive behaviors of poly(2,2-dimethyl-3,4-propylene-dioxythipohene) (PProDOT-Me2) films as polymeric electrodes in Type I electrochemical supercapacitors. The supercapacitor device displays robust capacitive charging/discharging behaviors with specific capacitance of 55 F/g, based on 60 μg of PProDOT-Me2 per electrode, that retains over 85% of its storage capacity after 32 000 redox cycles at 78% depth of discharge. Moreover, an appreciable average energy density of 6 Wh/kg has been calculated for the device, along with well-behaved and rapid capacitive responses to 1.0 V between 5 to 500 mV s(-1). Tandem electrochemical supercapacitors were assembled in series, in parallel, and in combinations of the two to widen the operating voltage window and to increase the capacitive currents. Four supercapacitors coupled in series exhibited a 4.0 V charging/discharging window, whereas assembly in parallel displayed a 4-fold increase in capacitance. Combinations of both serial and parallel assembly with six supercapacitors resulted in the extension of voltage to 3 V and a 2-fold increase in capacitive currents. Utilization of bipolar electrodes facilitated the encapsulation of tandem supercapacitors as individual, flexible, and lightweight supercapacitor modules.

Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

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

Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang

2016-03-31

Following the discovery of the redox-active 1,4- bis-BF 3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF 3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1Dmore » and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF 3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.« less

Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine.

PubMed

Bennett, Martin A; Bhargava, Suresh K; Bond, Alan M; Burgar, Iko M; Guo, Si-Xuan; Kar, Gopa; Privér, Steven H; Wagler, Jörg; Willis, Anthony C; Torriero, Angel A J

2010-10-14

Four new complexes, [PdX(κ(2)-2-C(6)R(4)PPh(2))(PPh(2)Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh(2)Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ(2)-2-C(6)F(4)PPh(2))(μ-I)(μ-2-C(6)F(4)PPh(2))PdI(PPh(2)Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected. The cis/trans ratio of 1-4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh(2)Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh(2)Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh(2)Fc(+), which undergoes further chemical and electrochemical reactions.

Construction and Characterization of a Chitosan-Immobilized-Enzyme and β-Cyclodextrin-Included-Ferrocene-Based Electrochemical Biosensor for H2O2 Detection

PubMed Central

Dong, Wenbo; Wang, Kaiyin; Chen, Yu; Li, Weiping; Ye, Yanchun; Jin, Shaohua

2017-01-01

An electrochemical detection biosensor was prepared with the chitosan-immobilized-enzyme (CTS-CAT) and β-cyclodextrin-included-ferrocene (β-CD-FE) complex for the determination of H2O2. Ferrocene (FE) was included in β-cyclodextrin (β-CD) to increase its stability. The structure of the β-CD-FE was characterized. The inclusion amount, inclusion rate, and electrochemical properties of inclusion complexes were determined to optimize the reaction conditions for the inclusion. CTS-CAT was prepared by a step-by-step immobilization method, which overcame the disadvantages of the conventional preparation methods. The immobilization conditions were optimized to obtain the desired enzyme activity. CTS-CAT/β-CD-FE composite electrodes were prepared by compositing the CTS-CAT with the β-CD-FE complex on a glassy carbon electrode and used for the electrochemical detection of H2O2. It was found that the CTS-CAT could produce a strong reduction peak current in response to H2O2 and the β-CD-FE could amplify the current signal. The peak current exhibited a linear relationship with the H2O2 concentration in the range of 1.0 × 10−7–6.0 × 10−3 mol/L. Our work provided a novel method for the construction of electrochemical biosensors with a fast response, good stability, high sensitivity, and a wide linear response range based on the composite of chitosan and cyclodextrin. PMID:28773229

An Experimental Approach to Controllably Vary Protein Oxidation While Minimizing Electrode Adsorption for Boron-Doped Diamond Electrochemical Surface Mapping Applications

PubMed Central

McClintock, Carlee S; Hettich, Robert L.

2012-01-01

Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent – hydroxyl radicals – for these measurements; however, these approaches range significantly in their complexity and expense of operation. This research expands upon earlier work to enhance the controllability of boron-doped diamond (BDD) electrochemistry as an easily accessible tool for producing hydroxyl radicals in order to oxidize a range of intact proteins. Efforts to modulate oxidation level while minimizing the adsorption of protein to the electrode involved the use of relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber. Additionally, a different cell activation approach using variable voltage to supply a controlled current allowed us to precisely tune the extent of oxidation in a protein-dependent manner. In order to gain perspective on the level of protein adsorption onto the electrode surface, studies were conducted to monitor protein concentration during electrolysis and gauge changes in the electrode surface between cell activation events. This report demonstrates the successful use of BDD electrochemistry for greater precision in generating a target number of oxidation events upon intact proteins. PMID:23210708

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.

A general electrochemical method for label-free screening of protein–small molecule interactions†

PubMed Central

Cash, Kevin J.; Ricci, Francesco

2010-01-01

Here we report a versatile method by which the interaction between a protein and a small molecule, and the disruption of that interaction by competition with other small molecules, can be monitored electrochemically directly in complex sample matrices. PMID:19826675

Estrone specific molecularly imprinted polymeric nanospheres: synthesis, characterization and applications for electrochemical sensor development.

PubMed

Congur, Gulsah; Senay, Hilal; Turkcan, Ceren; Canavar, Ece; Erdem, Arzum; Akgol, Sinan

2013-06-28

The aim of this study is (i) to prepare estrone-imprinted nanospheres (nano-EST-MIPs) and (ii) to integrate them into the electrochemical sensor as a recognition layer. N-methacryloyl-(l)-phenylalanine (MAPA) was chosen as the complexing monomer. Firstly, estrone (EST) was complexed with MAPA and the EST-imprinted poly(2-hyroxyethylmethacrylate-co-N-methacryloyl-(l)-phenylalanine) [EST-imprinted poly(HEMA-MAPA)] nanospheres were synthesized by surfactant- free emulsion polymerization method. The specific surface area of the EST-imprinted poly(HEMA-MAPA) nanospheres was found to be 1275 m2/g with a size of 163.2 nm in diameter. According to the elemental analysis results, the nanospheres contained 95.3 mmole MAPA/g nanosphere. The application of EST specific MIP nanospheres for the development of an electrochemical biosensor was introduced for the first time in our study by using electrochemical impedance spectroscopy (EIS) technique. This nano-MIP based sensor presented a great specificity and selectivity for EST.

Electrochemical and optical characterization of cobalt, copper and zinc phthalocyanine complexes.

PubMed

Lee, Jaehyun; Kim, Se Hun; Lee, Woosung; Lee, Jiwon; An, Byeong-Kwan; Oh, Se Young; Kim, Jae Pil; Park, Jongwook

2013-06-01

New phthalocyanine (Pc) derivatives that include the alkyl group in ligand were synthesized based on three core metals such as zinc (Zn), copper (Cu), and cobalt (Co). Electrochemical behaviors and optical properties of the new phthalocyanine derivatives with ligand and different core metal were investigated by using cyclic voltammetry, UV-Visible (UV-Vis) spectroscopy and photoluminescence (PL) spectroscopy. In UV-Vis data, maximum values of 2H, Co, Cu, and Zn complexes were 708 nm and 677 nm, 686 nm, 684 nm, respectively.

Metal-air cell with performance enhancing additive

DOEpatents

Friesen, Cody A; Buttry, Daniel

2015-11-10

Systems and methods drawn to an electrochemical cell comprising a low temperature ionic liquid comprising positive ions and negative ions and a performance enhancing additive added to the low temperature ionic liquid. The additive dissolves in the ionic liquid to form cations, which are coordinated with one or more negative ions forming ion complexes. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. The ion complexes improve oxygen reduction thermodynamics and/or kinetics relative to the ionic liquid without the additive.

An electrochemical model for hot-salt stress-corrosion of titanium alloys

NASA Technical Reports Server (NTRS)

Garfinkle, M.

1972-01-01

An electrochemical model of hot-salt stress-corrosion cracking of titanium alloys is proposed based on an oxygen-concentration cell. Hydrogen embrittlement is proposed as the direct cause of cracking, the hydrogen being generated as the results of the hydrolysis of complex halides formed at the shielded anode of the electrochemical cell. The model found to be consistent with the diverse observations made both in this study and by many investigators in this field.

Amorphous-silicon module intercell corrosion

NASA Astrophysics Data System (ADS)

Mon, G. R.; Ross, R. G.

1987-06-01

Three non-electrochemical, moisture-induced a-Si module degradation modes have been observed and their mechanisms studied: (1) the formation and growth of pinholes in the thin-film layers; (2) the directional interfusion of pinholes along process scribe lines to form metallization-free regions that tend to open-circuit the module; and (3) worm-like filiform corrosion in the aluminum layer. The dependency on time-of-exposure to moist environments of the amount of material erosion in the module intercell zone has been quantified by two methods—directly by EDS analysis, and indirectly by sheet resistivity measurements on fully aluminized back surface modules. In addition, changes in maximum power output, series resistance, and open circuit voltage have been documented. Consequences for fielded modules are discussed.

XPS study of ruthenium tris-bipyridine electrografted from diazonium salt derivative on microcrystalline boron doped diamond.

PubMed

Agnès, Charles; Arnault, Jean-Charles; Omnès, Franck; Jousselme, Bruno; Billon, Martial; Bidan, Gérard; Mailley, Pascal

2009-12-28

Boron doped diamond (BDD) functionalization has received an increasing interest during the last few years. Such an infatuation comes from the original properties of BDD, including chemical stability or an electrochemical window, that opens the way for the design of (bio)sensors or smart interfaces. In such a context, diazonium salts appear to be well suited for BDD functionalization as they enable covalent immobilization of functional entities such as enzymes or DNA. In this study we report microcrystalline BDD functionalization with a metallic complex, ruthenium tris(bipyridine), using the p-(tris(bipyridine)Ru(2+))phenyl diazonium salt. Electrografting using cyclic voltammetry (CV) allowed the formation of a ruthenium complex film that was finely characterized using electrochemistry and X-ray photoelectron spectroscopy (XPS). Moreover, we showed that chronopotentiometry (CP) is a convenient tool to monitor Ru complex film deposition through the control of the electrochemical pulse parameters (i.e. current density and pulse duration). Finally, such a control was demonstrated through the correlation between electrochemical and XPS characterizations.

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

PubMed

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

2012-08-01

Complexes of trimethoprim (TMP), with Cu(II), Zn(II), Pt(II), Ru(III) and Fe(III) have been synthesized. Then, these complexes have been characterized by spectroscopic techniques involving UV-vis, IR, mass and (1)H NMR. CHN elemental analysis, electrochemical and thermal behavior of complexes have also been investigated. The electrochemical properties of all complexes have been investigated by cyclic voltammetry (CV) using glassy carbon electrode. The biological activity of the complexes has been evaluated by examining their ability to bind to calf-thymus DNA (CT DNA) with UV spectroscopy and cyclic voltammetry. UV studies of the interaction of the complexes with DNA have shown that these compounds can bind to CT DNA. The binding constants of the complexes with CT DNA have also been calculated. The cyclic voltammograms of the complexes in the presence of CT DNA have shown that the complexes can bind to CT DNA by both the intercalative and the electrostatic binding mode. The antimicrobial activity of these complexes has been evaluated against three Gram-positive and four Gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with the reference drug TMP. Almost all types of complexes show excellent activity against all type of bacteria and fungi. The morphology of the CT DNA, TMP, metal ions and metal complexes has been investigated by scanning electron microscopy (SEM). To get the SEM images, the interaction of compounds with CT DNA has been studied by means of differential pulse voltammetry (DPV) at CT DNA modified pencil graphite electrode (PGE). The decrease in intensity of the guanine oxidation signals has been used as an indicator for the interaction mechanism. Copyright © 2012 Elsevier B.V. All rights reserved.

Moisture-temperature degradation in module encapsulants: The general problem of moisture in photovoltaic encapsulants

NASA Technical Reports Server (NTRS)

Mon, G. R.

1985-01-01

A general research approach was outlined toward understanding water-module interactions and the influence of temperature involving the need to: quantify module performance loss versus level of accumulated degradation, establish the dependence of the degradation reaction rate on module moisture and temperature levels, and determine module moisture and temperature levels in field environments. These elements were illustrated with examples drawn from studies of the now relatively well understood module electrochemical degradation process. Research data presented include temperature and humidity-dependent equilibrium leakage current values for multiparameter module material and design configurations. The contributions of surface, volume, and interfacial conductivities was demonstrated. Research directions were suggested to more fully understand the contributions to overall module conductivity of surface, volume, and interfacial conductivities over ranges of temperature and relative humidity characteristic of field environments.

Bio-inspired materials for electrochemical devices

NASA Astrophysics Data System (ADS)

Pawlicka, A.; Firmino, A.; Sentanin, F.; Sabadini, R. C.; Jimenez, D. E. Q.; Jayme, C. C.; Mindroiu, M.; Zgarian, R. G.; Tihan, G. T.; Rau, I.; Silva, M. M.; Nogueira, A. F.; Kanicki, J.; Kajzar, F.

2015-10-01

Natural macromolecules are very promising row materials to be used in modern technology including security and defense. They are abundant in nature, easy to extract and possess biocompatibility and biodegradability properties. These materials can be modified throughout chemical or physical processes, and can be doped with lithium and rare earth salts, ionic liquids, organic and inorganic acids. In this communication samples of DNA and modified DNA were doped with Prussian Blue (PB), poly(ethylene dioxythiophene) (PEDOT), europium and erbium triflate and organic dyes such as Nile Blue (NB), Disperse Red 1 (DR1) and Disperse Orange 3 (DO3). The colored or colorless membranes were characterized by electrochemical and spectroscopic measurements, and they were applied in electrochromic devices (ECDs) and dye sensitized solar cells (DSSC). ECDs change the color under applied potential, so they can modulate the intensity of transmitted light of 15 to 35%. As the electrochromic materials, WO3 or Prussian blue (PB), are usually blue colored, the color change is from transparent to blue. DNA, and the complexes: DNA-CTMA, DNA-DODA and DNAPEDOT: PSS were also investigated as either hole carrier material (HTM) or polymer electrolyte in dye-sensitized solar cells (DSSC). The DNA-based samples as HTM in small DSSCs revealed a solar energy conversion efficiency of 0.56%. Polymer electrolytes of DNA-CTMA and DNA-DODA, both with 10 wt% of LiI/I2, applied in small DSSC, exhibited the efficiencies of 0.18 and 0.66%, respectively. The obtained results show that natural macromolecules-based membranes are not only environmentally friendly but are also promising materials to be investigated for several electrochemical devices. However, to obtain better performances more research is still needed.

In-situ electrochemical transmission electron microscopy for battery research.

PubMed

Mehdi, B Layla; Gu, Meng; Parent, Lucas R; Xu, Wu; Nasybulin, Eduard N; Chen, Xilin; Unocic, Raymond R; Xu, Pinghong; Welch, David A; Abellan, Patricia; Zhang, Ji-Guang; Liu, Jun; Wang, Chong-Min; Arslan, Ilke; Evans, James; Browning, Nigel D

2014-04-01

The recent development of in-situ liquid stages for (scanning) transmission electron microscopes now makes it possible for us to study the details of electrochemical processes under operando conditions. As electrochemical processes are complex, care must be taken to calibrate the system before any in-situ/operando observations. In addition, as the electron beam can cause effects that look similar to electrochemical processes at the electrolyte/electrode interface, an understanding of the role of the electron beam in modifying the operando observations must also be understood. In this paper we describe the design, assembly, and operation of an in-situ electrochemical cell, paying particular attention to the method for controlling and quantifying the experimental parameters. The use of this system is then demonstrated for the lithiation/delithiation of silicon nanowires.

Force modulation and electrochemical gating of conductance in a cytochrome

NASA Astrophysics Data System (ADS)

Davis, Jason J.; Peters, Ben; Xi, Wang

2008-09-01

Scanning probe methods have been used to measure the effect of electrochemical potential and applied force on the tunnelling conductance of the redox metalloprotein yeast iso-1-cytochrome c (YCC) at a molecular level. The interaction of a proximal probe with any sample under test will, at this scale, be inherently perturbative. This is demonstrated with conductive probe atomic force microscopy (CP-AFM) current-voltage spectroscopy in which YCC, chemically adsorbed onto pristine Au(111) via its surface cysteine residue, is observed to become increasingly compressed as applied load is increased, with concomitant decrease in junction resistance. Electrical contact at minimal perturbation, where probe-molecule coupling is comparable to that in scanning tunnelling microscopy, brings with it the observation of negative differential resistance, assigned to redox-assisted probe-substrate tunnelling. The role of the redox centre in conductance is also resolved in electrochemical scanning tunnelling microscopy assays where molecular conductance is electrochemically gateable through more than an order of magnitude.

Long term stable deep red light-emitting electrochemical cells based on an emissive, rigid cationic Ir(iii) complex

DOE PAGES

Namanga, Jude E.; Ruhr-Univ. Bochum, Bochum; Gerlitzki, Niels; ...

2017-02-17

Here, the new cationic iridium complex [Ir(bzq) 2(biq)][PF 6] (bzq = benzo[ h]quinolinato and biq = 2,2'-biquinoline) has been synthesized for application as an emitter in light emitting electrochemical cells (LECs). The molecular structure and crystal packing of this complex were established by single X-ray diffraction (SXRD). The electrochemical and photophysical properties of the complex were examined to determine the frontier orbital energies as well as the optical transitions that led to photoemission. The complex was found to emit at 644 nm and 662 nm for powder and thin films, respectively. A high powder photoluminescence quantum yield of 25% wasmore » determined, which is attributed to a reduction in vibrational modes of the complex due to the use of the rigid cyclometalated (C^N) bzq ligand. A LEC with [Ir(bzq) 2(biq)][PF 6] as the emitter was fabricated which showed a deep red emission (662 nm) with a luminance of 33.65 cd m –2, yielding a current efficiency of 0.33 cd A –1 and a power efficiency of 0.2 lm W –1. Most importantly, the LEC based on [Ir(bzq) 2(biq)][PF 6] demonstrated a lifetime of 280 hours which is among the longest device lifetimes reported for any deep red light emitting LEC.« less

Long term stable deep red light-emitting electrochemical cells based on an emissive, rigid cationic Ir(iii) complex

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

Namanga, Jude E.; Ruhr-Univ. Bochum, Bochum; Gerlitzki, Niels

Here, the new cationic iridium complex [Ir(bzq) 2(biq)][PF 6] (bzq = benzo[ h]quinolinato and biq = 2,2'-biquinoline) has been synthesized for application as an emitter in light emitting electrochemical cells (LECs). The molecular structure and crystal packing of this complex were established by single X-ray diffraction (SXRD). The electrochemical and photophysical properties of the complex were examined to determine the frontier orbital energies as well as the optical transitions that led to photoemission. The complex was found to emit at 644 nm and 662 nm for powder and thin films, respectively. A high powder photoluminescence quantum yield of 25% wasmore » determined, which is attributed to a reduction in vibrational modes of the complex due to the use of the rigid cyclometalated (C^N) bzq ligand. A LEC with [Ir(bzq) 2(biq)][PF 6] as the emitter was fabricated which showed a deep red emission (662 nm) with a luminance of 33.65 cd m –2, yielding a current efficiency of 0.33 cd A –1 and a power efficiency of 0.2 lm W –1. Most importantly, the LEC based on [Ir(bzq) 2(biq)][PF 6] demonstrated a lifetime of 280 hours which is among the longest device lifetimes reported for any deep red light emitting LEC.« less

Interpreting the structural and electrochemical complexity of 0.5Li{sub 2}MnO{sub 3}{lg_bullet}.0.5LiMO{sub 2} electrodes for lithium batteries (M=Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x}, 0{le}x{le}0.5).

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

Kang, S. H.; Kempgens, P.; Greenbaum, S.

2007-01-01

The structural and electrochemical features of layered 0.5Li{sub 2}MnO{sub 3} {center_dot} 0.5LiMO{sub 2} electrodes, in which M = Mn{sub 0.5-x}Ni{sub 0.5-x}Co{sub 2x} (0{le} x {le} 0.5), have been studied by powder X-ray diffraction, electrochemical differential-capacity measurements, {sup 7}Li magic-angle-spinning nuclear magnetic resonance, and X-ray absorption near-edge spectroscopy. Li{sub 2}MnO{sub 3}-like regions in the as-prepared samples were observed for all values of x, with transition-metal cation disorder between the LiMO{sub 2} and Li{sub 2}MnO{sub 3} components increasing with cobalt content (i.e., the value of x). The structural disorder and complexity of the electrochemical redox reactions increase when the Li{sub 2}MnO{sub 3}-likemore » regions within the electrode are activated to 4.6 V in lithium cells; interpretations of structural and electrochemical phenomena are provided.« less

Bioelectrical coupling in multicellular domains regulated by gap junctions: A conceptual approach.

PubMed

Cervera, Javier; Pietak, Alexis; Levin, Michael; Mafe, Salvador

2018-04-21

We review the basic concepts involved in bioelectrically-coupled multicellular domains, focusing on the role of membrane potentials (V mem ). In the first model, single-cell V mem is modulated by two generic polarizing and depolarizing ion channels, while intercellular coupling is implemented via voltage-gated gap junctions. Biochemical and bioelectrical signals are integrated via a feedback loop between V mem and the transcription and translation of a protein forming an ion channel. The effective rate constants depend on the single-cell V mem because these potentials modulate the local concentrations of signaling molecules and ions. This electrochemically-based idealization of the complex biophysical problem suggests that the spatio-temporal map of single-cell potentials can influence downstream patterning processes by means of the voltage-gated gap junction interconnectivity, much as in the case of electronic devices where the control of electric potentials and currents allows the local modulation of the circuitry to achieve full functionality. An alternative theoretical approach, the BioElectrical Tissue Simulation Engine (BETSE), is also presented. The BETSE modeling environment utilizes finite volume techniques to simulate bioelectric states from the perspective of ion concentrations and fluxes. This model has been successfully applied to make predictions and explain experimental observations in a variety of embryonic, regenerative, and oncogenic contexts. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemical Control of Peptide Self-Organization on Atomically Flat Solid Surfaces: A Case Study with Graphite.

PubMed

Seki, Takakazu; So, Christopher R; Page, Tamon R; Starkebaum, David; Hayamizu, Yuhei; Sarikaya, Mehmet

2018-02-06

The nanoscale self-organization of biomolecules, such as proteins and peptides, on solid surfaces under controlled conditions is an important issue in establishing functional bio/solid soft interfaces for bioassays, biosensors, and biofuel cells. Electrostatic interaction between proteins and surfaces is one of the most essential parameters in the adsorption and self-assembly of proteins on solid surfaces. Although the adsorption of proteins has been studied with respect to the electrochemical surface potential, the self-assembly of proteins or peptides forming well-organized nanostructures templated by lattice structure of the solid surfaces has not been studied in the relation to the surface potential. In this work, we utilize graphite-binding peptides (GrBPs) selected by the phage display method to investigate the relationship between the electrochemical potential of the highly ordered pyrolytic graphite (HOPG) and peptide self-organization forming long-range-ordered structures. Under modulated electrical bias, graphite-binding peptides form various ordered structures, such as well-ordered nanowires, dendritic structures, wavy wires, amorphous (disordered) structures, and islands. A systematic investigation of the correlation between peptide sequence and self-organizational characteristics reveals that the presence of the bias-sensitive amino acid modules in the peptide sequence has a significant effect on not only surface coverage but also on the morphological features of self-assembled structures. Our results show a new method to control peptide self-assembly by means of applied electrochemical bias as well as peptide design-rules for the construction of functional soft bio/solid interfaces that could be integrated in a wide range of practical implementations.

Simultaneous Interfacial Reactivity and Topography Mapping with Scanning Ion Conductance Microscopy.

PubMed

Momotenko, Dmitry; McKelvey, Kim; Kang, Minkyung; Meloni, Gabriel N; Unwin, Patrick R

2016-03-01

Scanning ion conductance microscopy (SICM) is a powerful technique for imaging the topography of a wide range of materials and interfaces. In this report, we develop the use and scope of SICM, showing how it can be used for mapping spatial distributions of ionic fluxes due to (electro)chemical reactions occurring at interfaces. The basic idea is that there is a change of ion conductance inside a nanopipet probe when it approaches an active site, where the ionic composition is different to that in bulk solution, and this can be sensed via the current flow in the nanopipet with an applied bias. Careful tuning of the tip potential allows the current response to be sensitive to either topography or activity, if desired. Furthermore, the use of a distance modulation SICM scheme allows reasonably faithful probe positioning using the resulting ac response, irrespective of whether there is a reaction at the interface that changes the local ionic composition. Both strategies (distance modulation or tuned bias) allow simultaneous topography-activity mapping with a single channel probe. The application of SICM reaction imaging is demonstrated on several examples, including voltammetric mapping of electrocatalytic reactions on electrodes and high-speed electrochemical imaging at rates approaching 4 s per image frame. These two distinct approaches provide movies of electrochemical current as a function of potential with hundreds of frames (images) of surface reactivity, to reveal a wealth of spatially resolved information on potential- (and time) dependent electrochemical phenomena. The experimental studies are supported by detailed finite element method modeling that places the technique on a quantitative footing.

Field Effect Modulation of Heterogeneous Charge Transfer Kinetics at Back-Gated Two-Dimensional MoS2 Electrodes.

PubMed

Wang, Yan; Kim, Chang-Hyun; Yoo, Youngdong; Johns, James E; Frisbie, C Daniel

2017-12-13

The ability to improve and to modulate the heterogeneous charge transfer kinetics of two-dimensional (2D) semiconductors, such as MoS 2 , is a major challenge for electrochemical and photoelectrochemical applications of these materials. Here we report a continuous and reversible physical method for modulating the heterogeneous charge transfer kinetics at a monolayer MoS 2 working electrode supported on a SiO 2 /p-Si substrate. The heavily doped p-Si substrate serves as a back gate electrode; application of a gate voltage (V BG ) to p-Si tunes the electron occupation in the MoS 2 conduction band and shifts the conduction band edge position relative to redox species dissolved in electrolyte in contact with the front side of the MoS 2 . The gate modulation of both charge density and energy band alignment impacts charge transfer kinetics as measured by cyclic voltammetry (CV). Specifically, cyclic voltammograms combined with numerical simulations suggest that the standard heterogeneous charge transfer rate constant (k 0 ) for MoS 2 in contact with the ferrocene/ferrocenium (Fc 0/+ ) redox couple can be modulated by over 2 orders of magnitude from 4 × 10 -6 to 1 × 10 -3 cm/s, by varying V BG . In general, the field effect offers the potential to tune the electrochemical properties of 2D semiconductors, opening up new possibilities for fundamental studies of the relationship between charge transfer kinetics and independently controlled electronic band alignment and band occupation.

Synergy between tobramycin and trivalent chromium ion in electrochemical control of Pseudomonas aeruginosa.

PubMed

Niepa, Tagbo H R; Wang, Hao; Dabrowiak, James C; Gilbert, Jeremy L; Ren, Dacheng

2016-05-01

We recently demonstrated that the effectiveness of tobramycin (Tob), an aminoglycoside, against antibiotic-tolerant persister cells of Pseudomonas aeruginosa can be enhanced by electrochemical factors generated from direct currents (DC). Supplementation of Ni(II), Cr(III) and Fe(II) during carbon-mediated DC treatment revealed that these metal cations promote killing of persister cells in the presence of tobramycin, which led to our hypothesis that specific interactions between Tob and some metal ions contribute to the synergistic killing of persister cells. In this study, the interactions between selected metal cations and Tob were investigated using (1)H-(13)C HSQC NMR. Increase in the concentration of Cr(III) (in the form of [CrCl2(H2O)4](+)) in solutions containing Tob was found to shift the HSQC NMR peaks of Tob to new positions, suggesting the formation of a Cr(III)-Tob complex. Crystal field effects and electrochemical properties of the complex were further studied using UV-visible spectroscopy and cyclic voltammetry, which led to the finding that the Cr(III)-Tob complex has increased affinity with negatively charged nucleic acids. These findings are helpful for understanding the mechanism of electrochemical control of bacterial cells and for developing more effective antimicrobial therapies based on aminoglycosides and electrochemical species released from various metallic biomaterials. Medical device associated infections present a major challenge to healthcare and the quality of life of affected individuals. This problem is further exacerbated by the emergence of multidrug resistant pathogens. Thus, alternative methods for microbial control are urgently needed. Recently, we reported synergy between tobramycin and low-level electrochemical currents generated using stainless steel electrodes in killing bacterial persister cells, a dormant population with high-level intrinsic tolerance to antibiotics. In this article, we describe how electrically-induced interaction between aminoglycosides and certain metal cations enhance the potency of tobramycin in bacterial killing. The findings will help design new methods for controlling infections through electrochemical disruption of cellular function and associated drug resistance. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

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

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

DOE PAGES

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.; ...

2017-10-05

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

A Simple and Inexpensive Solar Energy Experiment.

ERIC Educational Resources Information Center

Evans, J. H.; Pedersen, L. G.

1979-01-01

An experiment is presented which utilizes the current solid state technology to demonstrate electrochemical generation of hydrogen gas, direct generation of electricity for pumping water, and energy conversion efficiency. The experimental module costs about $100 and can be used repeatedly. (BB)

Mass spectrometric methods for monitoring redox processes in electrochemical cells.

PubMed

Oberacher, Herbert; Pitterl, Florian; Erb, Robert; Plattner, Sabine

2015-01-01

Electrochemistry (EC) is a mature scientific discipline aimed to study the movement of electrons in an oxidation-reduction reaction. EC covers techniques that use a measurement of potential, charge, or current to determine the concentration or the chemical reactivity of analytes. The electrical signal is directly converted into chemical information. For in-depth characterization of complex electrochemical reactions involving the formation of diverse intermediates, products and byproducts, EC is usually combined with other analytical techniques, and particularly the hyphenation of EC with mass spectrometry (MS) has found broad applicability. The analysis of gases and volatile intermediates and products formed at electrode surfaces is enabled by differential electrochemical mass spectrometry (DEMS). In DEMS an electrochemical cell is sampled with a membrane interface for electron ionization (EI)-MS. The chemical space amenable to EC/MS (i.e., bioorganic molecules including proteins, peptides, nucleic acids, and drugs) was significantly increased by employing electrospray ionization (ESI)-MS. In the simplest setup, the EC of the ESI process is used to analytical advantage. A limitation of this approach is, however, its inability to precisely control the electrochemical potential at the emitter electrode. Thus, particularly for studying mechanistic aspects of electrochemical processes, the hyphenation of discrete electrochemical cells with ESI-MS was found to be more appropriate. The analytical power of EC/ESI-MS can further be increased by integrating liquid chromatography (LC) as an additional dimension of separation. Chromatographic separation was found to be particularly useful to reduce the complexity of the sample submitted either to the EC cell or to ESI-MS. Thus, both EC/LC/ESI-MS and LC/EC/ESI-MS are common. © 2013 The Authors. Mass Spectrometry Reviews published by Wiley Periodicals, Inc.

Highly labeled methylene blue-ds DNA silica nanoparticles for signal enhancement of immunoassays: application to the sensitive detection of bacteria in human platelet concentrates.

PubMed

Bonnet, Romaric; Farre, Carole; Valera, Lionel; Vossier, Ludivine; Léon, Fanny; Dagland, Typhaine; Pouzet, Agnès; Jaffrézic-Renault, Nicole; Fareh, Jeannette; Fournier-Wirth, Chantal; Chaix, Carole

2018-05-15

A nanoparticle-based electrochemical sandwich immunoassay was developed for bacteria detection in platelet concentrates. For the assay, magnetic beads were functionalized with antibodies to allow the specific capture of bacteria from the complex matrix, and innovative methylene blue-DNA/nanoparticle assemblies provided the electrochemical response for amplified detection. This nanoparticular system was designed as a temperature-sensitive nano-tool for electrochemical detection. First, oligonucleotide-functionalized nanoparticles were obtained by direct synthesis of the DNA strands on the nanoparticle surface using an automated oligonucleotide synthesizer. Densely packed DNA coverage was thus obtained. Then, DNA duplexes were constructed on the NP surface with a complementary strand bearing a 3 methylene blue tag. This strategy ultimately produced highly functionalized nanoparticles with electrochemical markers. These assemblies enabled amplification of the electrochemical signal, resulting in a very good sensitivity. A proof-of-concept was carried out for E. coli detection in human platelet concentrates. Bacterial contamination of this complex biological matrix is the highest residual infectious risk in blood transfusion. The development of a rapid assay that could reach 10-102 CFU mL-1 sensitivity is a great challenge. The nanoparticle-based electrochemical sandwich immunoassay carried out on a boron doped diamond electrode proved to be sensitive for E. coli detection in human platelets. Two antibody pairs were used to develop either a generic assay against certain Gram negative strains or a specific assay for E. coli. The methylene blue-DNA/nanoparticles amplify sensitivity ×1000 compared with the assay run without NPs for electrochemical detection. A limit of detection of 10 CFU mL-1 in a biological matrix was achieved for E. coli using the highly specific antibody pair.

Mass spectrometric methods for monitoring redox processes in electrochemical cells

PubMed Central

Oberacher, Herbert; Pitterl, Florian; Erb, Robert; Plattner, Sabine

2015-01-01

Electrochemistry (EC) is a mature scientific discipline aimed to study the movement of electrons in an oxidation–reduction reaction. EC covers techniques that use a measurement of potential, charge, or current to determine the concentration or the chemical reactivity of analytes. The electrical signal is directly converted into chemical information. For in-depth characterization of complex electrochemical reactions involving the formation of diverse intermediates, products and byproducts, EC is usually combined with other analytical techniques, and particularly the hyphenation of EC with mass spectrometry (MS) has found broad applicability. The analysis of gases and volatile intermediates and products formed at electrode surfaces is enabled by differential electrochemical mass spectrometry (DEMS). In DEMS an electrochemical cell is sampled with a membrane interface for electron ionization (EI)-MS. The chemical space amenable to EC/MS (i.e., bioorganic molecules including proteins, peptides, nucleic acids, and drugs) was significantly increased by employing electrospray ionization (ESI)-MS. In the simplest setup, the EC of the ESI process is used to analytical advantage. A limitation of this approach is, however, its inability to precisely control the electrochemical potential at the emitter electrode. Thus, particularly for studying mechanistic aspects of electrochemical processes, the hyphenation of discrete electrochemical cells with ESI-MS was found to be more appropriate. The analytical power of EC/ESI-MS can further be increased by integrating liquid chromatography (LC) as an additional dimension of separation. Chromatographic separation was found to be particularly useful to reduce the complexity of the sample submitted either to the EC cell or to ESI-MS. Thus, both EC/LC/ESI-MS and LC/EC/ESI-MS are common. PMID:24338642

Versatile and Programmable DNA Logic Gates on Universal and Label-Free Homogeneous Electrochemical Platform.

PubMed

Ge, Lei; Wang, Wenxiao; Sun, Ximei; Hou, Ting; Li, Feng

2016-10-04

Herein, a novel universal and label-free homogeneous electrochemical platform is demonstrated, on which a complete set of DNA-based two-input Boolean logic gates (OR, NAND, AND, NOR, INHIBIT, IMPLICATION, XOR, and XNOR) is constructed by simply and rationally deploying the designed DNA polymerization/nicking machines without complicated sequence modulation. Single-stranded DNA is employed as the proof-of-concept target/input to initiate or prevent the DNA polymerization/nicking cyclic reactions on these DNA machines to synthesize numerous intact G-quadruplex sequences or binary G-quadruplex subunits as the output. The generated output strands then self-assemble into G-quadruplexes that render remarkable decrease to the diffusion current response of methylene blue and, thus, provide the amplified homogeneous electrochemical readout signal not only for the logic gate operations but also for the ultrasensitive detection of the target/input. This system represents the first example of homogeneous electrochemical logic operation. Importantly, the proposed homogeneous electrochemical logic gates possess the input/output homogeneity and share a constant output threshold value. Moreover, the modular design of DNA polymerization/nicking machines enables the adaptation of these homogeneous electrochemical logic gates to various input and output sequences. The results of this study demonstrate the versatility and universality of the label-free homogeneous electrochemical platform in the design of biomolecular logic gates and provide a potential platform for the further development of large-scale DNA-based biocomputing circuits and advanced biosensors for multiple molecular targets.

Chemistry of vinylidene complexes. XXIV. A new μ-vinylidene complex containing RePt core, and platinum-bound carbonyl ligand. Spectroscopic, structural and electrochemical study

NASA Astrophysics Data System (ADS)

Verpekin, Victor V.; Vasiliev, Alexander D.; Kondrasenko, Alexander A.; Burmakina, Galina V.; Chudin, Oleg S.; Pavlenko, Nina I.; Zimonin, Dmitry V.; Rubaylo, Anatoly I.

2018-07-01

The novel heterobinuclear μ-vinylidene complex [Cp(CO)2Re(μ-C=CHPh)Pt(PPh3)(CO)] (1) was isolated from the reaction mixture of [Cp(CO)2Re(μ-C=CHPh)Fe(CO)4] and Pt(PPh3)4 for the first time. Alternative high-yield synthetic approaches to 1 were developed including the reactions of [Cp(CO)2Re(μ-C=CHPh)Pt(PPh3)2] (2) with Co2(CO)8 and Rh(acac)(CO)2. The complex was characterized by IR and 1H, 13C and 31P NMR spectroscopy, a molecular structure of 1 was determined by X-ray diffraction analysis. The electrochemical behavior of the new complex was studied by cyclic voltammetry at platinum or glassed carbon electrodes and by dc polarography at a dropping mercury electrode.

Fabrication of Compositionally and Topographically Complex Robust Tissue Forms by 3D-Electrochemical Compaction of Collagen

PubMed Central

Younesi, Mousa; Islam, Anowarul; Kishore, Vipuil; Panit, Stefi; Akkus, Ozan

2015-01-01

Collagen solutions are phase-transformed to mechanically robust shell structures with curviplanar topographies using electrochemically induced pH gradients. The process enables rapid layer-by-layer deposition of collagen-rich mixtures over the entire field simultaneously to obtain compositionally diverse multilayered structures. In-plane tensile strength and modulus of the electrocompacted collagen sheet samples were 5200 -fold and 2300 -fold greater than that of uncompacted collagen samples. Out of plane compression tests showed 27 -fold and fold increase in compressive stress and 46 -fold increase in compressive modulus compared to uncompacted collagen sheets. Cells proliferated 4.9 times faster, and cellular area spread was 2.7 times greater on compacted collagen sheets. Electrocompaction also resulted in 2.9 times greater focal adhesion area than on regular collagen hydrogel. The reported improvements in the cell-matrix interactions with electrocompaction would serve to expedite the population of electrocompacted collagen scaffolds by cells. The capacity of the method to fabricate nonlinear curved topographies with compositional heterogeneous layers is demonstrated by sequential deposition of collagenhydroxyapatite layer over a collagen layer. The complex curved topography of the nasal structure is replicated by the electrochemical compaction method. The presented electrochemical compaction process is an enabling modality which holds significant promise for reconstruction of a wide spectrum of topographically complex systems such as joint surfaces, craniofacial defects, ears, nose or urogenital forms. PMID:26069162

Electrochemical DNA probe for Hg(2+) detection based on a triple-helix DNA and Multistage Signal Amplification Strategy.

PubMed

Wang, Huan; Zhang, Yihe; Ma, Hongmin; Ren, Xiang; Wang, Yaoguang; Zhang, Yong; Wei, Qin

2016-12-15

In this work, an ultrasensitive electrochemical sensor was developed for detection of Hg(2+). Gold nanoparticles decorated bovine serum albumin reduction of graphene oxide (AuNP-BSA-rGO) were used as subsurface material for the immobilization of triple-helix DNA. The triple-helix DNA containing a thiol labelled single-stranded DNA (sDNA) and a thymine-rich DNA (T-rich DNA), which could be unwinded in the present of Hg(2+) to form more stable thymine-Hg(2+)-thymine (T-Hg(2+)-T) complex. T-Hg(2+)-T complex was then removed and the sDNA was left on the electrode. At this time, gold nanoparticle carrying thiol labelled cytosine-rich complementary DNA (cDNA-AuNP) could bind with the free sDNA. Meanwhile, the other free cDNA on AuNP could bind with each other in the present of Ag(+) to form the stable cytosine-Ag(+)-cytosine (C-Ag(+)-C) complex and circle amplification. Plenty of C-Ag(+)-C could form silver nanoclusters by electrochemical reduction and the striping signal of Ag could be measured for purpose of the final electrochemical detection of Hg(2+). This sensor could detect Hg(2+) over a wide concentration range from 0.1 to 130nM with a detection limit of 0.03nM. Copyright © 2016 Elsevier B.V. All rights reserved.

Long-Range Intramolecular Electronic Communication in a Trinuclear Ruthenium Tropolonate Complex.

PubMed

Yoshida, Jun; Kuwahara, Kyohei; Suzuki, Kota; Yuge, Hidetaka

2017-02-20

Dinuclear and trinuclear ruthenium complexes, [Ru(trop) 2 (C 2 trop)Ru(dppe)Cp] [2b; trop = tropolonato, C 2 trop = ethynyltropolonato, dppe = 1,2-bis(diphenylphosphino)ethane] and [Ru(trop){(C 2 trop)Ru(dppe)Cp} 2 ] (3), were synthesized, and their electronic and electrochemical properties were investigated in comparison with our previously reported complex [Ru(acac) 2 (C 2 trop)Ru(dppe)Cp] (2a). The electron-donating Ru II (dppe)Cp unit and electron-accepting Ru III O 6 unit are connected by C 2 trop in these complexes. 2a incorporates acetylacetonate as an ancillary ligand, while 2b and 3 incorporate tropolonate as an ancillary ligand. Every complex, 2a, 2b, and 3, exhibits similar UV-vis-near-IR (NIR) absorption spectra, demonstrating the lack of explicit intramolecular electronic communication between the units at least in the neutral state. The weak NIR absorption in 2a further diminished upon electrochemical oxidation, indicating almost no electronic communication between the units. In contrast, 2b and 3 exhibit broad NIR absorptions upon oxidation. Additionally, 3 exhibits four stepwise redox couples in the electrochemical study, which are formally attributed to [Ru II (trop) 3 ] - /[Ru III (trop) 3 ], two [Ru II (dppe)Cp]/[Ru III (dppe)Cp] + , and [Ru III (trop) 3 ]/[Ru IV (trop) 3 ] + couples. Clear separation of the redox couples attributed to the two terminal [Ru(dppe)Cp] units demonstrates the thermodynamic stability of the intermediate oxidation states with respect to disproportionation. Further electrochemical studies using an electrolyte including perfluorinated weakly coordinating anions and density functional theory/time-dependent density functional theory calculations confirmed the effect of ancillary ligands, acetylacetonate and tropolonate. In the case of 2a, electronic delocalization over the whole complex, especially over the [Ru(acac) 2 (trop)] unit, appears to be small. In contrast, the electronic communication between [Ru(dppe)Cp] and [Ru(trop) 3 ] units in 3 seems to be enhanced upon oxidation, resulting in the long-range intramolecular electronic communication.

Dual responsive supramolecular hydrogel with electrochemical activity.

PubMed

Du, Ping; Liu, Jianghua; Chen, Guosong; Jiang, Ming

2011-08-02

Supramolecular materials with reversible responsiveness to environmental changes are of particular research interest in recent years. Inclusion complexation between cyclodextrin (CD) and ferrocene (Fc) is well-known and extensively studied because of its reversible association-dissociation controlled by the redox state of Fc. Although there are quite a few reported nanoscale materials incorporating this host-guest pair, polymeric hydrogels with electrochemical activity based on this interactive pair are still rare. Taking advantage of our previous reported hybrid inclusion complex (HIC) hydrogel structure, a new Fc-HIC was designed and obtained with β-CD-modified quantum dots as the core and Fc-ended diblock co-polymer p(DMA-b-NIPAM) as the shell, to achieve an electrochemically active hydrogel at elevated temperatures. Considering the two independent cross-linking strategies in the network structure, i.e., the interchain aggregation of pNIPAM and inclusion complexation between CD and Fc on the surface of the quantum dots, the hydrogel was fully thermo-reversible and its gel-sol transition was achieved after the addition of either an oxidizing agent or a competitive guest to Fc.

Electrochemical process and production of novel complex hydrides

DOEpatents

Zidan, Ragaiy

2013-06-25

A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

Methylxanthine Drug Monitoring with Wearable Sweat Sensors.

PubMed

Tai, Li-Chia; Gao, Wei; Chao, Minghan; Bariya, Mallika; Ngo, Quynh P; Shahpar, Ziba; Nyein, Hnin Y Y; Park, Hyejin; Sun, Junfeng; Jung, Younsu; Wu, Eric; Fahad, Hossain M; Lien, Der-Hsien; Ota, Hiroki; Cho, Gyoujin; Javey, Ali

2018-06-01

Drug monitoring plays crucial roles in doping control and precision medicine. It helps physicians tailor drug dosage for optimal benefits, track patients' compliance to prescriptions, and understand the complex pharmacokinetics of drugs. Conventional drug tests rely on invasive blood draws. While urine and sweat are attractive alternative biofluids, the state-of-the-art methods require separate sample collection and processing steps and fail to provide real-time information. Here, a wearable platform equipped with an electrochemical differential pulse voltammetry sensing module for drug monitoring is presented. A methylxanthine drug, caffeine, is selected to demonstrate the platform's functionalities. Sweat caffeine levels are monitored under various conditions, such as drug doses and measurement time after drug intake. Elevated sweat caffeine levels upon increasing dosage and confirmable caffeine physiological trends are observed. This work leverages a wearable sweat sensing platform toward noninvasive and continuous point-of-care drug monitoring and management. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved Electrochemical Cycling Durability in a Nickel Oxide Double-Layered Film.

PubMed

Hou, Shuai; Zhang, Xiang; Tian, Yanlong; Zhao, Jiupeng; Geng, Hongbin; Qu, Huiying; Zhang, Hangchuan; Zhang, Kun; Wang, Binsheng; Gavrilyuk, Alexander; Li, Yao

2017-11-16

For the first time, a crystalline-amorphous double-layered NiO x film has been prepared by reactive radio frequency magnetron sputtering. This film has exhibited improved electrochemical cycling durability, whereas other electrochromic parameters have been maintained at the required level, namely, a short coloration/bleaching time (0.8 s/1.1 s) and an enhanced transmittance modulation range (62.2 %) at λ=550 nm. Additionally, the double-layered film has shown better reversibility than that of amorphous and crystalline single-layered films. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-Charge-Mediated Formation of H-TiO2 @Ni(OH)2 Heterostructures for High-Performance Supercapacitors.

PubMed

Ke, Qingqing; Guan, Cao; Zhang, Xiao; Zheng, Minrui; Zhang, Yong-Wei; Cai, Yongqing; Zhang, Hua; Wang, John

2017-02-01

An electrochemically favorable Ni(OH) 2 with porously hierarchical structure and ultrathin nanosheets in a core-shell structure H-TiO 2 @Ni(OH) 2 is achieved through modulating the surface chemical activity of TiO 2 by hydrogenation, which creates a defect-rich surface of TiO 2 , thereby facilitating the subsequent nucleation and growth of Ni(OH) 2 . These configuration-tailored H-TiO 2 @Ni(OH) 2 core-shell nanowires exhibit a superior electrochemical performance and good flexibility. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical gating-induced reversible and drastic resistance switching in VO2 nanowires

PubMed Central

Sasaki, Tsubasa; Ueda, Hiroki; Kanki, Teruo; Tanaka, Hidekazu

2015-01-01

Reversible and drastic modulation of the transport properties in vanadium dioxide (VO2) nanowires by electric field-induced hydrogenation at room temperature was demonstrated using the nanogaps separated by humid air in field-effect transistors with planer-type gates (PG-FET). These PG-FETs allowed us to investigate behavior of revealed hydrogen intercalation and diffusion aspects with time and spatial evolutions in nanowires. These results show that air nanogaps can operate as an electrochemical reaction field, even in a gaseous atmosphere, and offer new directions to explore emerging functions for electronic and energy devices in oxides. PMID:26584679

Ferrocene-oligonucleotide conjugates for electrochemical probing of DNA.

PubMed Central

Ihara, T; Maruo, Y; Takenaka, S; Takagi, M

1996-01-01

Toward the development of a universal, sensitive and convenient method of DNA (or RNA) detection, electrochemically active oligonucleotides were prepared by covalent linkage of a ferrocenyl group to the 5'-aminohexyl-terminated synthetic oligonucleotides. Using these electrochemically active probes, we have been able to demonstrate the detection of DNA and RNA at femtomole levels by HPLC equipped with an ordinary electrochemical detector (ECD) [Takenaka,S., Uto,Y., Kondo,H., Ihara,T. and Takagi,M. (1994) Anal. Biochem., 218, 436-443]. Thermodynamic and electrochemical studies of the interaction between the probes and the targets are presented here. The thermodynamics obtained revealed that the conjugation stabilizes the triple-helix complexes by 2-3 kcal mol-1 (1-2 orders increment in binding constant) at 298 K, which corresponds to the effect of elongation of additional several base triplets. The main cause of this thermodynamic stabilization by the conjugation is likely to be the overall conformational change of whole structure of the conjugate rather than the additional local interaction. The redox potential of the probe was independent of the target structure, which is either single- or double stranded. However, the potential is slightly dependent (with a 10-30 mV negative shift on complexation) on the extra sequence in the target, probably because the individual sequence is capable of contacting or interacting with the ferrocenyl group in a slightly different way from each other. This small potential shift itself, however, does not cause any inconvenience on practical applications in detecting the probes by using ECD. These results lead to the conclusion that the redox-active probes are very useful for the microanalysis of nucleic acids due to the stability of the complexes, high detection sensitivity and wide applicability to the target structures (DNA and RNA; single- and double strands) and the sequences. PMID:8932383

Using Organic Light-Emitting Electrochemical Thin-Film Devices to Teach Materials Science

ERIC Educational Resources Information Center

Sevian, Hannah; Muller, Sean; Rudmann, Hartmut; Rubner, Michael F.

2004-01-01

Materials science can be taught by applying organic light-emitting electrochemical thin-film devices and in this method students were allowed to make a light-emitting device by spin coating a thin film containing ruthenium (II) complex ions onto a glass slide. Through this laboratory method students are provided with the opportunity to learn about…

New luminescent bioprobes Eu(lll)-phloroglucinol derivatives and their spectrofluorimetric, electrochemical interactions with nucleotides and DNA.

PubMed

Azab, Hassan Ahmed; Anwar, Zeinab M; Abdel-Salam, Enas T; el-Sayed-Sebak, Mahmoud

2012-01-01

Two new ligands derived from phloroglucinol 2-{[(4-methoxy benzoyl)oxy]} methyl benzoic acid[L1] and 2-{[(4-methyl benzoyl)oxy] methyl} benzoic acid[L2] were synthesized. The solid complex Eu(III)-L2 has been synthesised and characterized by elemental analysis, UV and IR spectra. The reaction of Eu(III) with the two synthesized ligands has been investigated in I = 0.1 mol dm(-3) p-toluene sulfonate by cyclic voltammetry and square wave voltammetry. The reaction of Eu (III)-L1 and Eu (III)-L2 binary complexes with nucleotide 5'-AMP, 5'-ADP, 5'-ATP, 5'- GMP, 5'-IMP, and 5'-CMP has been investigated using UV, fluorescence and electrochemical methods. The experimental conditions were selected such that self-association of the nucleotides and their complexes was negligibly small, that is, the monomeric complexes were studied. The interaction of the Eu(III)-L1 or L2 solid complexes with calf-thymus DNA has been investigated by fluorescence and electrochemical methods including cyclic voltammetery(CV), differential pulse polarography (DPP) and square wave voltammetry (SWV) on a glassy carbon electrode. The fluorescence intensity of Eu(III)-L2 complex was enhanced with the addition of DNA. Under optimal conditions in phosphate buffer pH 7.0 at 25 °C the linear range is 3-20 μM for calf thymus DNA (CT-DNA) and the corresponding determination limit is 1.8 μM.

Polymers containing nickel(II) complexes of Goedken's macrocycle: optimized synthesis and electrochemical characterization.

PubMed

Paquette, Joseph A; Sauvé, Ethan R; Gilroy, Joe B

2015-04-01

The synthesis and characterization of a new class of nickel-containing polymers is described. The optimized copolymerization of alkyne-bearing nickel(II) complexes of Goedken's macrocycle (4,11-dihydro-5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) and brominated 9,9-dihexylfluorene produced polymers with potential application as functional redox-active materials. The title polymers exhibit electrochemically reversible, ligand-centered oxidation events at 0.24 and 0.73 V versus the ferrocene/ferrocenium redox couple. They also display exceptional thermal stability and interesting absorption properties due to the presence of the macrocyclic nickel(II) complexes and π-conjugated units incorporated in their backbones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal regeneration of an electrochemical concentration cell

DOEpatents

Krumpelt, Michael; Bates, John K.

1981-01-01

A system and method for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 Kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.

Metal-metal interactions in tetrakis(diphenylphosphino)benzene-bridged dimetallic complexes and their related coordination polymers

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

Wang, Pei-Wei; Fox, M.A.

1994-06-22

Electrochemical, EPR, and spectroelectrochemical methods have been used to probe electronic coupling through a 1,2,4,5-tetrakis(diphenylphosphino)benzene bridging ligand connecting metal centers in several Ni-, Pd-, and Pt-containing dimetallic complexes. These dimetalated complexes showed weak intervalence charge transfer (IT) bands and slightly shifted redox potentials in comparison with their monometallic models. A Marcus-Hush analysis of the energies of the IT bands for the electrochemically generated mixed-valence heterodimetallic complexes (Ni{sup o}-Pd{sup II} and Ni{sup o}-Pt{sup II}, respectively) established the magnitude of intermetallic electronic coupling. The weak thermal coupling observed in these dimetalated complexes is consistent with the very low conductivities (10{sup {minus}8}-10{sup {minus}10}{omega}{supmore » -1} cm{sup {minus}1}) observed in the polymeric analogs of these complexes, namely, the newly prepared metal coordination polymers (M = Ni{sup II}, Pd{sup II}, Pt{sup II}) with 1,2,4,5-tetrakis(diphenylphosphino)benzene.« less

Humic acids as pseudocapacitive electrolyte additive for electrochemical double layer capacitors

NASA Astrophysics Data System (ADS)

Wasiński, Krzysztof; Walkowiak, Mariusz; Lota, Grzegorz

2014-06-01

Novel electrolyte additive for electrochemical capacitors has been reported. It has been demonstrated for the first time that addition of humic acids (HA) to KOH-based electrolyte significantly increases capacitance of symmetrical capacitors with electrodes made of activated carbon. Specific capacitances determined by means of galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy consistently showed increases for HA concentrations ranging from 2% w/w up to saturated solution with maximum positive effect observed for 5% w/w of the additive. The capacitance increase has been attributed to complex faradaic processes involving oxygen-containing groups of HA molecules. Due to abundant resources, low cost and easy processability the reported solution can find application in electrochemical capacitor technologies.

Soft plasma electrolysis with complex ions for optimizing electrochemical performance

NASA Astrophysics Data System (ADS)

Kamil, Muhammad Prisla; Kaseem, Mosab; Ko, Young Gun

2017-03-01

Plasma electrolytic oxidation (PEO) was a promising surface treatment for light metals to tailor an oxide layer with excellent properties. However, porous coating structure was generally exhibited due to excessive plasma discharges, restraining its performance. The present work utilized ethylenediaminetetraacetic acid (EDTA) and Cu-EDTA complexing agents as electrolyte additives that alter the plasma discharges to improve the electrochemical properties of Al-1.1Mg alloy coated by PEO. To achieve this purpose, PEO coatings were fabricated under an alternating current in silicate electrolytes containing EDTA and Cu-EDTA. EDTA complexes were found to modify the plasma discharging behaviour during PEO that led to a lower porosity than that without additives. This was attributed to a more homogeneous electrical field throughout the PEO process while the coating growth would be maintained by an excess of dissolved Al due to the EDTA complexes. When Cu-EDTA was used, the number of discharge channels in the coating layer was lower than that with EDTA due to the incorporation of Cu2O and CuO altering the dielectric behaviour. Accordingly, the sample in the electrolyte containing Cu-EDTA constituted superior corrosion resistance to that with EDTA. The electrochemical mechanism for excellent corrosion protection was elucidated in the context of equivalent circuit model.

Soft plasma electrolysis with complex ions for optimizing electrochemical performance

PubMed Central

Kamil, Muhammad Prisla; Kaseem, Mosab; Ko, Young Gun

2017-01-01

Plasma electrolytic oxidation (PEO) was a promising surface treatment for light metals to tailor an oxide layer with excellent properties. However, porous coating structure was generally exhibited due to excessive plasma discharges, restraining its performance. The present work utilized ethylenediaminetetraacetic acid (EDTA) and Cu-EDTA complexing agents as electrolyte additives that alter the plasma discharges to improve the electrochemical properties of Al-1.1Mg alloy coated by PEO. To achieve this purpose, PEO coatings were fabricated under an alternating current in silicate electrolytes containing EDTA and Cu-EDTA. EDTA complexes were found to modify the plasma discharging behaviour during PEO that led to a lower porosity than that without additives. This was attributed to a more homogeneous electrical field throughout the PEO process while the coating growth would be maintained by an excess of dissolved Al due to the EDTA complexes. When Cu-EDTA was used, the number of discharge channels in the coating layer was lower than that with EDTA due to the incorporation of Cu2O and CuO altering the dielectric behaviour. Accordingly, the sample in the electrolyte containing Cu-EDTA constituted superior corrosion resistance to that with EDTA. The electrochemical mechanism for excellent corrosion protection was elucidated in the context of equivalent circuit model. PMID:28281672

Synthesis, characterization, single crystal X-ray determination, fluorescence and electrochemical studies of new dinuclear nickel(II) and oxovanadium(IV) complexes containing double Schiff base ligands

NASA Astrophysics Data System (ADS)

Shafaatian, Bita; Ozbakzaei, Zahra; Notash, Behrouz; Rezvani, S. Ahmad

2015-04-01

A series of new bimetallic complexes of nickel(II) and vanadium(IV) have been synthesized by the reaction of the new double bidentate Schiff base ligands with nickel acetate and vanadyl acetylacetonate in 1:1 M ratio. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metals to ligands stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The nickel and vanadyl complexes exhibited distorted square planar and square pyramidal coordination geometries, respectively. The emission spectra of the ligands and their complexes were studied in methanol. Electrochemical properties of the ligands and their metal complexes were also investigated in DMSO solvent at 150 mV s-1 scan rate. The ligands and metal complexes showed both quasi-reversible and irreversible processes at this scan rate. The Schiff bases and their complexes have been characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis and conductometry. The crystal structure of the nickel complex has been determined by single crystal X-ray diffraction.

Production of Titanium Metal by an Electrochemical Molten Salt Process

NASA Astrophysics Data System (ADS)

Fatollahi-Fard, Farzin

Titanium production is a long and complicated process. What we often consider to be the standard method of primary titanium production (the Kroll process), involves many complex steps both before and after to make a useful product from titanium ore. Thus new methods of titanium production, especially electrochemical processes, which can utilize less-processed feedstocks have the potential to be both cheaper and less energy intensive than current titanium production processes. This project is investigating the use of lower-grade titanium ores with the electrochemical MER process for making titanium via a molten salt process. The experimental work carried out has investigated making the MER process feedstock (titanium oxycarbide) with natural titanium ores--such as rutile and ilmenite--and new ways of using the MER electrochemical reactor to "upgrade" titanium ores or the titanium oxycarbide feedstock. It is feasible to use the existing MER electrochemical reactor to both purify the titanium oxycarbide feedstock and produce titanium metal.

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media

PubMed Central

Al-Harbi, Albandaree K.

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution. PMID:29337992

Outstanding resistance and passivation behaviour of new Fe-Co metal-metal glassy alloys in alkaline media.

PubMed

Emran, Khadijah M; Al-Harbi, Albandaree K

2018-01-01

The electrochemical behavior of the oxide layers on two metal-metal glassy alloys, Fe78Co9Cr10Mo2Al1 (VX9)and Fe49Co49V2 (VX50) (at.%), were studied using electrochemical techniques including electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) measurements. The morphology and composition of the alloy surfaces were investigated using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion rate and surface roughness of both alloys increased as the concentration of NaOH in aqueous solution was raised. The presence of some protective elements in the composition of the alloys led to the formation of a spontaneous passive layer on the alloy surface. The higher resistance values of both alloys were associated with the magnitude of the dielectric properties of the passive films formed on their surfaces. Both alloys are classified as having outstanding resistance to corrosion, which results from the formation of a passive film that acts as an efficient barrier to corrosion in alkaline solution.

Issues on the production and electrochemical separation of oxygen from carbon dioxide

NASA Technical Reports Server (NTRS)

Kaloupis, P.; Sridhar, K. R.

1991-01-01

There is considerable interest in in-situ propellant manufacturing on the moon and Mars. One of the concepts of oxygen production that is being actively pursued is the processing of atmospheric carbon dioxide on Mars to produce oxygen by means of thermal decomposition and electrochemical separation. The key component of such a production facility is the electrochemical separation cell that filters out the oxygen from the gas mixture of carbon dioxide, carbon monoxide, and oxygen. Efficient design of the separation cell and the selection of electrolyte and electrode materials of superior performance for the cell would translate to significant reduction in the power requirement and the mass of the production facility. The objective is to develop the technology required to produce the cells in-house and test various electrolyte and electrode materials systematically until the optimal combination is found. An effective technique was developed for the fabrication of disk shaped cells. Zirconia and Ceria cells were made in-house. Complete modules of the electrochemical cell and housings were designed, fabricated, and tested.

Review-Physicochemical hydrodynamics of gas bubbles in two phase electrochemical systems.

PubMed

Taqieddin, Amir; Nazari, Roya; Rajic, Ljiljana; Alshawabkeh, Akram

2017-01-01

Electrochemical systems suffer from poor management of evolving gas bubbles. Improved understanding of bubbles behavior helps to reduce overpotential, save energy and enhance the mass transfer during chemical reactions. This work investigates and reviews the gas bubbles hydrodynamics, behavior, and management in electrochemical cells. Although the rate of bubble growth over the electrode surface is well understood, there is no reliable prediction of bubbles break-off diameter from the electrode surface because of the complexity of bubbles motion near the electrode surface. Particle Image Velocimetry (PIV) and Laser Doppler Anemometry (LDA) are the most common experimental techniques to measure bubble dynamics. Although the PIV is faster than LDA, both techniques are considered expensive and time-consuming. This encourages adapting Computational Fluid Dynamics (CFD) methods as an alternative to study bubbles behavior. However, further development of CFD methods is required to include coalescence and break-up of bubbles for better understanding and accuracy. The disadvantages of CFD methods can be overcome by using hybrid methods. The behavior of bubbles in electrochemical systems is still a complex challenging topic which requires a better understanding of the gas bubbles hydrodynamics and their interactions with the electrode surface and bulk liquid, as well as between the bubbles itself.

[Tissue-specific nucleoprotein complexes].

PubMed

Riadnova, I Iu; Shataeva, L K; Khavinson, V Kh

2000-01-01

A method of isolation of native nucleorprotein complexes from cattle cerebral cortex, thymus, and liver was developed. Compositions of these complexes were studied by means of gel-chromatography and ion-exchange chromatography. These preparations were shown to consist of several fractions of proteins and their complexes differ by molecular mass and electro-chemical properties. Native nucleoprotein complexes revealed high tissue specific activity, which was not species-specific.

Light-emitting properties of cationic iridium complexes containing phenanthroline based ancillary ligand with blue-green and green emission colors

NASA Astrophysics Data System (ADS)

Kwon, Yiseul; Sunesh, Chozhidakath Damodharan; Choe, Youngson

2015-01-01

We report here two new cationic iridium(III) complexes with phenanthroline-based ancillary ligands, [Ir(dfppy)2(dibutyl-phen)]PF6 (Complex 1) and [Ir(ppz)2(dibutyl-phen)]PF6 (Complex 2) and their uses in light-emitting electrochemical cells (LECs). The design is based on 2-(2,4-difluorophenyl)pyridine (dfppy) and 1-phenylpyrazole (ppz) as the cyclometalating ligands and 2,9-dibutyl-1,10-phenanthroline (dibutyl-phen) as the ancillary ligand. The photophysical and electrochemical properties of the complexes were studied and the results obtained were corroborated with theoretical density functional theory (DFT) calculations. LECs were fabricated incorporating each complexes which resulted in blue-green light emission (502 nm) with Commission Internationale de l'Eclairage (CIE) coordinates of (0.26, 0.49) for Complex 1 and green (530 nm) electroluminescence with CIE coordinates of (0.33, 0.54) for Complex 2. The luminance and the current efficiency of the LECs based on Complex 1 are 947 cd m-2 and 0.25 cd A-1, respectively, which are relatively higher than that of Complex 2 with a maximum luminance of 773 cd m-2 and an efficiency of 0.16 cd A-1.

In situ study of Li-ions diffusion and deformation in Li-rich cathode materials by using scanning probe microscopy techniques

NASA Astrophysics Data System (ADS)

Zeng, Kaiyang; Li, Tao; Tian, Tian

2017-08-01

In this paper, the scanning probe microscopy (SPM) based techniques, namely, conductive-AFM, electrochemical strain microscopy (ESM) and AM-FM (amplitude modulation-frequency modulation) techniques, are used to in situ characterize the changes in topography, conductivity and elastic properties of Li-rich layered oxide cathode (Li1.2Mn0.54Ni0.13Co0.13O2) materials, in the form of nanoparticles, when subject to the external electric field. Nanoparticles are the basic building blocks for composite cathode in a Li-ion rechargeable battery. Characterization of the structure and electrochemical properties of the nanoparticles is very important to understand the performance and reliability of the battery materials and devices. In this study, the conductivity, deformation and mechanical properties of the Li-rich oxide nanoparticles under different polarities of biases are studied using the above-mentioned SPM techniques. This information can be correlated with the Li+-ion diffusion and migration in the particles under external electrical field. The results also confirm that the SPM techniques are ideal tools to study the changes in various properties of electrode materials at nano- to micro-scales during or after the ‘simulated’ battery operation conditions. These techniques can also be used to in situ characterize the electrochemical performances of other energy storage materials, especially in the form of the nanoparticles.

β-cyclodextrin-ferrocene host-guest complex multifunctional labeling triple amplification strategy for electrochemical immunoassay of subgroup J of avian leukosis viruses.

PubMed

Shang, Kun; Wang, Xindong; Sun, Bing; Cheng, Ziqiang; Ai, Shiyun

2013-07-15

A novel sandwich-type electrochemical immunosensor was fabricated for ultrasensitive detection of subgroup J of avian leukosis virus (ALVs-J) by employing β-cyclodextrin-ferrocene (CD-Fc) host-guest complex multifunctional Fe3O4 nanospheres as labels and β-cyclodextrin functional graphene sheets (CD-GS) nanocomposite as sensor platform. The sensitivity was greatly improved based on the triple amplification strategy. Firstly, the CD-GS improved the electron transfer rate as well as increasing the surface area to capture a large amount of primary antibodies (Ab1). Secondly, the CD on the Fe3O4 surface with strong recognition capability could form stable CD-Fc host-guest inclusion complex and provided larger free room for the conjugation of secondary antibodies (Ab2) and glucose oxidase (GOD). Finally, the conjugated GOD exhibited extraordinary electrochemical biocatalysis towards the reduction reaction of Fc(+) by glucose. Under the optimized conditions, the electrochemical immunosensor exhibited a wide working range from 10(2.27)-10(3.50) TCID50/mL (TCID50: 50% tissue culture infective dose) with a low detection limit of 10(2.19) TCID50/mL (S/N=3). The selectivity, reproducibility, and stability are acceptable. The assay was evaluated for real avian serum sample, receiving satisfactory results. This new type of triple amplification strategy may provide potential applications for the clinic application. Copyright © 2013 Elsevier B.V. All rights reserved.

Coupled Mechanical-Electrochemical-Thermal Modeling for Accelerated Design of EV Batteries

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

Santhanagopalan, Shriram; Zhang, Chao; Kim, Gi-Heon

2015-05-03

This presentation provides an overview of the mechanical electrochemical-thermal (M-ECT) modeling efforts. The physical phenomena occurring in a battery are many and complex and operate at different scales (particle, electrodes, cell, and pack). A better understanding of the interplay between different physics occurring at different scales through modeling could provide insight to design improved batteries for electric vehicles. Work funded by the U.S. DOE has resulted in development of computer-aided engineering (CAE) tools to accelerate electrochemical and thermal design of batteries; mechanical modeling is under way. Three competitive CAE tools are now commercially available.

Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor

NASA Astrophysics Data System (ADS)

Pech, David; Brunet, Magali; Taberna, Pierre-Louis; Simon, Patrice; Fabre, Norbert; Mesnilgrente, Fabien; Conédéra, Véronique; Durou, Hugo

Carbon-based micro-supercapacitors dedicated to energy storage in self-powered modules were fabricated with inkjet printing technology on silicon substrate. An ink was first prepared by mixing an activated carbon powder with a PTFE polymer binder in ethylene glycol stabilized with a surfactant then deposited by inkjet on patterned gold current collectors with the substrate heated at 140 °C in order to assure a good homogeneity. Electrochemical micro-capacitors with electrodes in an interdigital configuration were fabricated, and characterized using electrochemical techniques in 1 M Et 4NBF 4 propylene carbonate electrolyte. These micro-devices show an excellent capacitive behavior over a wide potential range of 2.5 V for a cell capacitance of 2.1 mF cm -2. The newly developed technology will allow the integration of the storage device as close as possible to the MEMS-based energy harvesting device, minimizing power losses through connections.

Electrocatalysis-induced elasticity modulation in a superionic proton conductor probed by band-excitation atomic force microscopy.

PubMed

Papandrew, A B; Li, Q; Okatan, M B; Jesse, S; Hartnett, C; Kalinin, S V; Vasudevan, R K

2015-12-21

Variable temperature band-excitation atomic force microscopy in conjunction with I-V spectroscopy was used to investigate the crystalline superionic proton conductor CsHSO4 during proton exchange induced by a Pt-coated conductive scanning probe. At a sample temperature of 150 °C and under an applied bias <1 V, reduction currents of up to 1 nA were observed. Simultaneously, we show that the electrochemical reactions are accompanied by a reversible decrease in the elastic modulus of CsHSO4, as seen by a contact resonance shift, and find evidence for superplasticity during scanning. These effects were not observed in the room-temperature phase of CsHSO4 or in the case of catalytically inactive conductive probes, proving the utility of this technique for monitoring electrochemical processes on the nanoscale, as well as the use of local contact stiffness as a sensitive indicator of electrochemical reactions.

Computational analysis of species transport and electrochemical characteristics of a MOLB-type SOFC

NASA Astrophysics Data System (ADS)

Hwang, J. J.; Chen, C. K.; Lai, D. Y.

A multi-physics model coupling electrochemical kinetics with fluid dynamics has been developed to simulate the transport phenomena in mono-block-layer built (MOLB) solid oxide fuel cells (SOFC). A typical MOLB module is composed of trapezoidal flow channels, corrugated positive electrode-electrolyte-negative electrode (PEN) plates, and planar inter-connecters. The control volume-based finite difference method is employed for calculation, which is based on the conservation of mass, momentum, energy, species, and electric charge. In the porous electrodes, the flow momentum is governed by a Darcy model with constant porosity and permeability. The diffusion of reactants follows the Bruggman model. The chemistry within the plates is described via surface reactions with a fixed surface-to-volume ratio, tortuosity and average pore size. Species transports as well as the local variations of electrochemical characteristics, such as overpotential and current density distributions in the electrodes of an MOLB SOFC, are discussed in detail.

Real space mapping of ionic diffusion and electrochemical activity in energy storage and conversion materials

DOEpatents

Kalinin, Sergei V; Balke, Nina; Kumar, Amit; Dudney, Nancy J; Jesse, Stephen

2014-05-06

A method and system for probing mobile ion diffusivity and electrochemical reactivity on a nanometer length scale of a free electrochemically active surface includes a control module that biases the surface of the material. An electrical excitation signal is applied to the material and induces the movement of mobile ions. An SPM probe in contact with the surface of the material detects the displacement of mobile ions at the surface of the material. A detector measures an electromechanical strain response at the surface of the material based on the movement and reactions of the mobile ions. The use of an SPM tip to detect local deformations allows highly reproducible measurements in an ambient environment without visible changes in surface structure. The measurements illustrate effective spatial resolution comparable with defect spacing and well below characteristic grain sizes of the material.

Toxicity, Spectroscopic Characterization and Electrochemical Behaviour of New Macrocclic Complexes of Lead(II) and Palladium(II) Metals

PubMed Central

Bansal, Anil; Singh, Randhir

2000-01-01

Tetraazamacrocyclie complexes of lead and palladium have been synthesized by the template process using the bis(benzil)ethylenediamine precursor. The tetradentate macrocycle (maL) reacts with PbCl2, PdCl2 and different diamines in a 1:1:1 molar ratio in methanol to give several solid complexes of the types [Pb(maL)(R)Cl2] and [Pd(maL)(R)]Cl2 (where R = 2,6-diaminopyridine or 1,2-phenylenediamine). The macrocycle and its metal complexes have been characterized by elemental analysis, molecular weight determinations, molar conductivity, IR, 1H NMR, 13C NMR, electronic, mass and electrochemical studies. The macrocyclic ligand coordinates through the four azomethine nitrogen atoms which are bridged by benzil moieties. IR spectra suggest that the pyridine nitrogen is not coordinating. The palladium complexes exhibit tetracoordinated square-planar geometry, whereas a hexacoordinated octahedral geometry is suggested for lead complexes. The macrocycle along with its complexes have been screened in vitro against a number of pathogenic fungi and bacteria to assess their growth inhibiting potential. PMID:18475947

Lattice-cell orientation disorder in complex spinel oxides

DOE PAGES

Chen, Yan; Cheng, Yongqiang; Li, Juchuan; ...

2016-11-07

Transition metal (TM) substitution has been widely applied to change complex oxides crystal structures to create high energy density electrodes materials in high performance rechargeable lithium-ion batteries. The complex local structure in the oxides imparted by the TM arrangement often impacts their electrochemical behaviors by influencing the diffusion and intercalation of lithium. Here, a major discrepancy is demonstrated between the global and local structures of the promising high energy density and high voltage LiNi 0.5Mn 1.5O 4 spinel cathode material that contradicts the existing structural models. A new single-phase lattice-cell orientation disorder model is proposed as the mechanism for themore » local ordering that explains how the inhomogeneous local distortions and the coherent connection give rise to the global structure in the complex oxide. As a result, the single-phase model is consistent with the electrochemical behavior observation of the materials.« less

Thermal regeneration of an electrochemical concentration cell

DOEpatents

Krumpelt, M.; Bates, J.K.

1980-05-09

A system and method are described for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.

Potential-Induced Degradation-Delamination Mode in Crystalline Silicon Modules: Preprint

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

Hacke, Peter L; Kempe, Michael D; Wohlgemuth, John

A test sequence producing potential-induced degradation-delamination (PID-d) in crystalline silicon modules has been tested and found comparable under visual inspection to cell/encapsulant delamination seen in some fielded modules. Four commercial modules were put through this sequence, 85 degrees C, 85%, 1000 h damp heat, followed by an intensive PID stress sequence of 72 degrees C, 95% RH, and -1000 V, with the module face grounded using a metal foil. The 60 cell c-Si modules exhibiting the highest current transfer (4.4 center dot 10-4 A) exhibited PID-d at the first inspection after 156 h of PID stress. Effects promoting PID-d aremore » reduced adhesion caused by damp heat, sodium migration further reducing adhesion to the cells, and gaseous products of electrochemical reactions driven by the applied system voltage. A new work item proposal for an IEC test standard to evaluate for PID-d is anticipated.« less

Electrochemical fabrication of SrTiO3 nanowires with nanoporous alumina template.

PubMed

Kang, Jinwook; Ryu, Jaemin; Ko, Eunseong; Tak, Yongsug

2007-11-01

Strontium titanate nanowires were electrochemically synthesized with nanoporous alumina template. Both chemical and electrical variables such as electrolyte pH, temperature, and current waveform were modulated to investigate the synthesis process of SrTiO3 nanowires. Superimposed cathodic pulse and diffusion time accelerated the growth of SrTiO3 nanowires, which suggested that the concentration of H+ and Sr2+ ion inside alumina template had a strong influence on the formation of SrTiO3 nanowires. Morphology and crystallinity of SrTiO3 nanowires were investigated with scanning electron microscope, X-ray diffractometer and energy dispersive X-ray spectroscopy.

Spectro- and electrochemical studies of some ruthenium and osmium complexes of 2-(2'-pyridyl)benzimidazole; complexes with intra-molecular charge transfer.

PubMed

Khalil, M M; Ali, S A; Ramadan, R M

2001-04-01

Reaction of Ru3(CO)12, with 2-(2'-pyridyl)benzimidazole (HPBI) resulted in the formation of Ru(CO)3(HPBI) (I) complex. In presence of pyridine or dipyridine, the two derivatives [Ru(CO)3(HPBI)].Py (II) and [Ru(CO)3(HPBI)].dpy (III) were isolated. The corresponding reactions of Os3(CO)12 yielded only one single product; Os(CO)2(HPBI)2 (IV). Spectroscopic studies of these complexes revealed intramolecular metal to ligand CT interactions. Reactions of RuCl3 with HPBI gave three distinct products; [Ru(HPBI)2Cl2]Cl (V), [Ru(HPBI)(dipy)Cl2]C1 (VI) and [Ru(PBI)2(py)2]Cl (VII). The UV-vis studies indicated the presence of intramolecular ligand to metal CT interactions. Electrochemical investigation of the complexes showed some irreversible, reversible and quasi-reversible redox reactions due to tautomeric interconversions through electron transfer.

Bimetallic ruthenium complexes bridged by divinylphenylene bearing oligo(ethylene glycol)methylether: synthesis, (spectro)electrochemistry and the lithium cation effect.

PubMed

Tian, Li Yan; Liu, Yuan Mei; Tian, Guang-Xuan; Wu, Xiang Hua; Li, Zhen; Kou, Jun-Feng; Ou, Ya-Ping; Liu, Sheng Hua; Fu, Wen-Fu

2014-03-14

A series of 1,4-disubstituted ruthenium-vinyl complexes, (E,E)-[{(PMe3)3(CO)ClRu}2(μ-HC=CH-Ar-CH=CH)], in which the 1,4-diethenylphenylene bridge bears two oligo(ethylene glycol)methyl ether side chains at different positions (2,5- and 2,3-positions), were prepared. The respective products were characterized by elemental analyses and NMR spectroscopy. The structures of complexes 1b and 1e were established by X-ray crystallography. The electronic properties of the complexes were investigated by cyclic voltammetry, and IR and UV-vis/NIR spectroscopies. Electrochemical studies showed that the 2,5-substituents better stabilized the mixed-valence states; the electrochemical behavior was greatly affected by lithium cations, especially complex 1g with 2,3-substituents, which was further supported by IR and UV-vis/NIR spectra changes. Spectroelectrochemical studies showed that the redox chemistry was dominated by the non-innocent character of the bridging fragment.

Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

NASA Astrophysics Data System (ADS)

Weitzner, Stephen E.; Dabo, Ismaila

2017-11-01

The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

Synthesis, pH dependent photometric and electrochemical investigation, redox mechanism and biological applications of novel Schiff base and its metallic derivatives

NASA Astrophysics Data System (ADS)

Rauf, Abdur; Shah, Afzal; Khan, Abdul Aziz; Shah, Aamir Hassan; Abbasi, Rashda; Qureshi, Irfan Zia; Ali, Saqib

2017-04-01

A novel Schiff base, 1-((2, 4-dimethylphenylimino)methyl)naphthalen-2-ol abbreviated as (HL) and its four metallic complexes were synthesized and confirmed by 1H and 13C NMR, FTIR, TGA and UV-Visible spectroscopy. Schiff base was also characterized by X-ray analysis. The photometric and electrochemical responses of all the synthesized compounds were investigated in a wide pH range. Structures of the compounds were optimized computationally for the evaluation of different physico-chemical parameters. On the basis of electrochemical results the redox mechanistic pathways of the compounds were proposed. The cytotoxicity analysis on Hela cells revealed that HL and its complexes inhibit cell growth as revealed from their IC50 values (HL):106.7 μM, (L2VO): 40.66 μM, (L2Sn): 5.92 μM, (L2Zn): 42.82 and (L2Co): 107.68 μM. The compounds were tested for anti-diabetic, triglyceride, cholesterol, anti-microbial, anti-fungal and enzyme inhibition activities. The results revealed that HL and its complexes are promising new therapeutic options as these compounds exhibit strong activity against cancer cells, diabetics, fungal and microbial inhibition.

PEGylated Polyaniline Nanofibers: Antifouling and Conducting Biomaterial for Electrochemical DNA Sensing.

PubMed

Hui, Ni; Sun, Xiaotian; Niu, Shuyan; Luo, Xiliang

2017-01-25

Biofouling arising from nonspecific adsorption is a substantial outstanding challenge in diagnostics and disease monitoring, and antifouling sensing interfaces capable of reducing the nonspecific adsorption of proteins from biological complex samples are highly desirable. We present herein the preparation of novel composite nanofibers through the grafting of polyethylene glycol (PEG) polymer onto polyaniline (PANI) nanofibers and their application in the development of antifouling electrochemical biosensors. The PEGylated PANI (PANI/PEG) nanofibers possessed large surface area and remained conductive and at the same time demonstrated excellent antifouling performances in single protein solutions as well as complex human serum samples. Sensitive and low fouling electrochemical biosensors for the breast cancer susceptibility gene (BRCA1) can be easily fabricated through the attachment of DNA probes to the PANI/PEG nanofibers. The biosensor showed a very high sensitivity to target BRCA1 with a linear range from 0.01 pM to 1 nM and was also efficient enough to detect DNA mismatches with satisfactory selectivity. Moreover, the DNA biosensor based on the PEGylated PANI nanofibers supported the quantification of BRCA1 in complex human serum, indicating great potential of this novel biomaterial for application in biosensors and bioelectronics.

[(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2″-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltametry

PubMed Central

Cady, Clyde W.; Shinopoulos, Katherine E.; Crabtree, Robert H.; Brudvig, Gary W.

2010-01-01

Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO3)3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. PMID:20372724

Analytical methods for determination of free metal ion concentration, labile species fraction and metal complexation capacity of environmental waters: a review.

PubMed

Pesavento, Maria; Alberti, Giancarla; Biesuz, Raffaela

2009-01-12

Different experimental approaches have been suggested in the last few decades to determine metal species in complex matrices of unknown composition as environmental waters. The methods are mainly focused on the determination of single species or groups of species. The more recent developments in trace elements speciation are reviewed focusing on methods for labile and free metal determination. Electrochemical procedures with low detection limit as anodic stripping voltammetry (ASV) and the competing ligand exchange with adsorption cathodic stripping voltammetry (CLE-AdCSV) have been widely employed in metal distribution studies in natural waters. Other electrochemical methods such as stripping chronopotentiometry and AGNES seem to be promising to evaluate the free metal concentration at the low levels of environmental samples. Separation techniques based on ion exchange (IE) and complexing resins (CR), and micro separation methods as the Donnan membrane technique (DMT), diffusive gradients in thin-film gels (DGT) and the permeation liquid membrane (PLM), are among the non-electrochemical methods largely used in this field and reviewed in the text. Under appropriate conditions such techniques make possible the evaluation of free metal ion concentration.

Nanostructured core-shell electrode materials for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Jiang, Long-bo; Yuan, Xing-zhong; Liang, Jie; Zhang, Jin; Wang, Hou; Zeng, Guang-ming

2016-11-01

Core-shell nanostructure represents a unique system for applications in electrochemical energy storage devices. Owing to the unique characteristics featuring high power delivery and long-term cycling stability, electrochemical capacitors (ECs) have emerged as one of the most attractive electrochemical storage systems since they can complement or even replace batteries in the energy storage field, especially when high power delivery or uptake is needed. This review aims to summarize recent progress on core-shell nanostructures for advanced supercapacitor applications in view of their hierarchical architecture which not only create the desired hierarchical porous channels, but also possess higher electrical conductivity and better structural mechanical stability. The core-shell nanostructures include carbon/carbon, carbon/metal oxide, carbon/conducting polymer, metal oxide/metal oxide, metal oxide/conducting polymer, conducting polymer/conducting polymer, and even more complex ternary core-shell nanoparticles. The preparation strategies, electrochemical performances, and structural stabilities of core-shell materials for ECs are summarized. The relationship between core-shell nanostructure and electrochemical performance is discussed in detail. In addition, the challenges and new trends in core-shell nanomaterials development have also been proposed.

Strategic modulation of the photonic properties of conjugated organometallic Pt-Ir polymers exhibiting hybrid CT-excited states.

PubMed

Soliman, Ahmed M; Zysman-Colman, Eli; Harvey, Pierre D

2015-04-01

Polymer 6, ([trans-Pt(PBu3 )2 (C≡C)2 ]-[Ir(dFMeppy)2 (N^N)](PF6 ))n , (([Pt]-[Ir](PF6 ))n ; N^N = 5,5'-disubstituted-2,2'-bipyridyl; dFMeppy = 2-(2,4-difluoro-phenyl)-5-methylpyridine) is prepared along with model compounds. These complexes are investigated by absorption and emission spectroscopy and their photophysical and electrochemical properties are measured and compared with their corresponding non fluorinated complexes. Density functional theory (DFT) and time-dependent DFT computations corroborate the nature of the excited state as being a hybrid between the metal-to-ligand charge transfer ((1,3) MLCT) for the trans-Pt(PBu3 )2 (C≡CAr)2 unit, [Pt] and the metal-to-ligand/ligand-to-ligand' charge transfer ((1,3) ML'CT/LL'CT) for [Ir] with L = dFMeppy. Overall, the fluorination of the phenylpyridine group expectedly does not change the nature of the excited state but desirably induces a small blue shift of the absorption and emission bands along a slight decrease in emission quantum yields and lifetimes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

2013-09-03

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

2014-10-28

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Controlling Complex Systems and Developing Dynamic Technology

NASA Astrophysics Data System (ADS)

Avizienis, Audrius Victor

In complex systems, control and understanding become intertwined. Following Ilya Prigogine, we define complex systems as having control parameters which mediate transitions between distinct modes of dynamical behavior. From this perspective, determining the nature of control parameters and demonstrating the associated dynamical phase transitions are practically equivalent and fundamental to engaging with complexity. In the first part of this work, a control parameter is determined for a non-equilibrium electrochemical system by studying a transition in the morphology of structures produced by an electroless deposition reaction. Specifically, changing the size of copper posts used as the substrate for growing metallic silver structures by the reduction of Ag+ from solution under diffusion-limited reaction conditions causes a dynamical phase transition in the crystal growth process. For Cu posts with edge lengths on the order of one micron, local forces promoting anisotropic growth predominate, and the reaction produces interconnected networks of Ag nanowires. As the post size is increased above 10 microns, the local interfacial growth reaction dynamics couple with the macroscopic diffusion field, leading to spatially propagating instabilities in the electrochemical potential which induce periodic branching during crystal growth, producing dendritic deposits. This result is interesting both as an example of control and understanding in a complex system, and as a useful combination of top-down lithography with bottom-up electrochemical self-assembly. The second part of this work focuses on the technological development of devices fabricated using this non-equilibrium electrochemical process, towards a goal of integrating a complex network as a dynamic functional component in a neuromorphic computing device. Self-assembled networks of silver nanowires were reacted with sulfur to produce interfacial "atomic switches": silver-silver sulfide junctions, which exhibit complex dynamics (e.g. both short- and long-term changes in conductivity) in response to applied voltage signals. Characterization of these atomic switch networks (ASNs) brought out interesting parallels to biological neural networks, including power-law scaling in the statistics of electrical signal propagation and dynamic self-organization of differentiated subnetworks. A reservoir computing (RC) strategy was employed to utilize measurements of electrical signals dynamically generated in ASNs to perform time-series memory and manipulation tasks including a parity test and arbitrary waveform generation. These results represent the useful integration of a complex network into a dynamic physical RC device.

Structured Nanowires for Spectra-Tuned and Spectra-Multiplexed Sensing THZ Generation

DTIC Science & Technology

2015-04-08

anodic aluminum oxide membranes ( AAO ) as templates. We...nanowires were fabricated by direct current electrochemical deposition technique using diameter-modulated anodic aluminum oxide membranes ( AAO ) as...throughout this project was the technique of atomic layer deposition (ALD) into anodized alumina oxide ( AAO ) templates. Aluminum , when

Synthesis, crystal structure, fluorescence and electrochemical studies of a new tridentate Schiff base ligand and its nickel(II) and palladium(II) complexes

NASA Astrophysics Data System (ADS)

Shafaatian, Bita; Soleymanpour, Ahmad; Kholghi Oskouei, Nasim; Notash, Behrouz; Rezvani, Seyyed Ahmad

2014-07-01

A new unsymmetrical tridentate Schiff base ligand was derived from the 1:1 M condensation of ortho-vanillin with 2-mercaptoethylamine. Nickel and palladium complexes were obtained by the reaction of the tridentate Schiff base ligand with nickel(II) acetate tetrahydrate and palladium(II) acetate in 2:1 M ratio. In nickel and palladium complexes the ligand was coordinated to metals via the imine N and enolic O atoms. The S groups of Schiff bases were not coordinated to the metals and S-S coupling was occured. The complexes have been found to possess 1:2 Metal:Ligand stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The complexes exhibited octahedral coordination geometry. The emission spectra of the ligand and its complexes were studied in methanol. Electrochemical properties of the ligand and its metal complexes were investigated in the CH3CN solvent at the 100 mV s-1 scan rate. The ligand and metal complexes showed both reversible and quasi-reversible processes at this scan rate. The Schiff base and its complexes have been characterized by IR, 1H NMR, UV/Vis, elemental analyses and conductometry. The crystal structure of nickel complex has been determined by single crystal X-ray diffraction.

Deprotonation/protonation of coordinated secondary thioamide units of pincer ruthenium complexes: modulation of voltammetric and spectroscopic characterization of the pincer complexes.

PubMed

Teratani, Takuya; Koizumi, Take-aki; Yamamoto, Takakazu; Tanaka, Koji; Kanbara, Takaki

2011-09-21

New pincer ruthenium complexes, [Ru(SCS)(tpy)]PF(6) (1) (SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl), tpy = 2,2':6',2''-terpyridyl) and [Ru(SNS)(tpy)]PF(6) (2) (SNS = 2,5-bis(benzylaminothiocarbonyl)pyrrolyl), having κ(3)SCS and κ(3)SNS pincer ligands with two secondary thioamide units were synthesized by the reactions of [RuCl(3)(tpy)] with N,N'-dibenzyl-1,3-benzenedicarbothioamide (L1) and N,N'-dibenzyl-2,5-1H-pyrroledicarbothioamide (L2), respectively, and their chemical and electrochemical properties were elucidated. The structure of 1 was determined by X-ray crystallography. The complexes 1 and 2 showed a two-step deprotonation reaction by treatment with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), and the addition of DBU led to a shift of the metal-centered redox couples to a lower potential by 720 and 550 mV, respectively. The di-deprotonated complexes were also studied by (1)H-NMR and UV-vis spectroscopy. The addition of methanesulfonic acid (MSA) to the di-deprotonated complexes enabled the recovery of 1 and 2, indicating that the thioamide moiety underwent a reversible deprotonation-protonation process, which resulted in regulating the redox potentials of the metal center. The Pourbaix diagram of 1 revealed that 1 underwent a one-proton/one-electron transfer process in the pH range of 5.83-10.35, and a two-proton/one-electron process at a pH of over 10.35, indicating that the deprotonation/protonation process of the complexes is related to proton-coupled electron transfer (PCET). This journal is © The Royal Society of Chemistry 2011

Regeneration of anion exchange resins by catalyzed electrochemical reduction

DOEpatents

Gu, Baohua; Brown, Gilbert M.

2002-01-01

Anion exchange resins sorbed with perchlorate may be regenerated by a combination of chemical reduction of perchlorate to chloride using a reducing agent and an electrochemical reduction of the oxidized reducing agent. Transitional metals including Ti, Re, and V are preferred chemical reagents for the reduction of perchlorate to chloride. Complexing agents such as oxalate are used to prevent the precipitation of the oxidized Ti(IV) species, and ethyl alcohol may be added to accelerate the reduction kinetics of perchlorate. The regeneration may be performed by continuously recycling the regenerating solution through the resin bed and an electrochemical cell so that the secondary waste generation is minimized.

Magnetic separation of antibiotics by electrochemical magnetic seeding

NASA Astrophysics Data System (ADS)

Ihara, I.; Toyoda, K.; Beneragama, N.; Umetsu, K.

2009-03-01

Magnetic separation of several classes of antibiotics was investigated using electrochemical magnetic seeding. Electrocoagulation with a sacrificial anode followed by addition of magnetite particles was applied for the magnetic seeding of antibiotics. With electrochemical magnetic seeding using an iron anode, tetracycline antibiotics (oxytetracycline, chlortetracycline, doxycycline and tetracycline) and cephalosporin antibiotic (cefdinir) were rapidly removed from synthetic wastewater by magnetic separation using a neodymium magnet. Iron and aluminium anodes were suitable for magnetic seeding of the antibiotics. The results indicated that the ability of antibiotics to form strong complex with iron and aluminium allowed the higher removal by magnetic separation. This method would be appropriate for rapid treatment of antibiotics in wastewater.

Zinc-chlorine battery plant system and method

DOEpatents

Whittlesey, Curtis C.; Mashikian, Matthew S.

1981-01-01

A zinc-chlorine battery plant system and method of redirecting the electrical current around a failed battery module. The battery plant includes a power conditioning unit, a plurality of battery modules connected electrically in series to form battery strings, a plurality of battery strings electrically connected in parallel to the power conditioning unit, and a bypass switch for each battery module in the battery plant. The bypass switch includes a normally open main contact across the power terminals of the battery module, and a set of normally closed auxiliary contacts for controlling the supply of reactants electrochemically transformed in the cells of the battery module. Upon the determination of a failure condition, the bypass switch for the failed battery module is energized to close the main contact and open the auxiliary contacts. Within a short time, the electrical current through the battery module will substantially decrease due to the cutoff of the supply of reactants, and the electrical current flow through the battery string will be redirected through the main contact of the bypass switch.

Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes

DOE PAGES

Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won; ...

2016-01-08

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag +/Ag redox reaction to Ag +-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

Laboratory Experiments on the Electrochemical Remediation of the Environment. Part 9: Microscale Recovery of a Soil Metal Pollutant and Its Extractant

ERIC Educational Resources Information Center

Ibanez, Jorge G.; Balderas-Hernandez, Patricia; Garcia-Pintor, Elizabeth; Barba-Gonzalez, Sandy Nohemi; Doria-Serrano, Ma. del Carmen; Hernaiz-Arce, Lorena; Diaz-Perez, Armando; Lozano-Cusi, Ana

2011-01-01

Many soils throughout the world are contaminated with metal salts of diverse toxicity. We have developed an experiment to demonstrate the removal of a metal from an insoluble surrogate soil pollutant, CuCO[subscript 3] multiplied by Cu(OH)[subscript 2], by complexation followed by the simultaneous electrochemical recovery of the ligand (i.e.,…

Aptamer-based detection of plasma proteins by an electrochemical assay coupled to magnetic beads.

PubMed

Centi, Sonia; Tombelli, Sara; Minunni, Maria; Mascini, Marco

2007-02-15

The DNA thrombin aptamer has been extensively investigated, and the coupling of this aptamer to different transduction principles has demonstrated the wide applicability of aptamers as bioreceptors in bioanalytical assays. The goal of this work was to design an aptamer-based sandwich assay with electrochemical detection for thrombin analysis in complex matrixes, using a simple target capturing step by aptamer-functionalized magnetic beads. The conditions for the aptamer immobilization and for the protein binding have been first optimized by surface plasmon resonance, and then transferred to the electrochemical-based assay performed onto screen-printed electrodes. The assay was then applied to the analysis of thrombin in buffer, spiked serum, and plasma and high sensitivity and specificity were found. Moreover, thrombin was generated in situ in plasma by the conversion of its precursor prothrombin, and the formation of thrombin was followed at different times. The concentrations detected by the electrochemical assay were in agreement with a simulation software that mimics the formation of thrombin over time (thrombogram). The proposed work demonstrates that the high specificity of aptamers together with the use of magnetic beads are the key features for aptamer-based analysis in complex matrixes, opening the possibility of a real application to diagnostics or medical investigation.

Comparing the Properties of Electrochemical-Based DNA Sensors Employing Different Redox Tags

PubMed Central

Kang, Di; Zuo, Xiaolei; Yang, Renqiang; Xia, Fan; Plaxco, Kevin W.; White, Ryan J.

2009-01-01

Many electrochemical biosensor approaches developed in recent years utilize redox labeled (most commonly methylene blue or ferrocene) oligonucleotide probes site-specifically attached to an interrogating electrode. Sensors in this class have been reported employing a range of probe architectures, including single- and double-stranded DNA, more complex DNA structures, DNA and RNA aptamers and, most recently, DNA-small molecule chimeras. Signaling in this class of sensors is generally predicated on binding-induced changes in the efficiency with which the covalently attached redox label transfers electrons with the interrogating electrode. Here we have investigated how the properties of the redox tag affect the performance of such sensors. Specifically, we compare the differences in signaling and stability of electrochemical DNA sensors (E-DNA sensors) fabricated using either ferrocene or methylene blue as the signaling redox moiety. We find that while both tags support efficient E-DNA signaling, ferrocene produces slightly improved signal gain and target affinity. These small advantages, however, come at a potentially significant price: the ferrocene-based sensors are far less stable than their methylene blue counterparts, particularly with regards to stability to long-term storage, repeated electrochemical interrogations, repeated sensing/regeneration iterations, and employment in complex sample matrices such as blood serum. PMID:19810694

Review—Physicochemical hydrodynamics of gas bubbles in two phase electrochemical systems

PubMed Central

Taqieddin, Amir; Nazari, Roya; Rajic, Ljiljana; Alshawabkeh, Akram

2018-01-01

Electrochemical systems suffer from poor management of evolving gas bubbles. Improved understanding of bubbles behavior helps to reduce overpotential, save energy and enhance the mass transfer during chemical reactions. This work investigates and reviews the gas bubbles hydrodynamics, behavior, and management in electrochemical cells. Although the rate of bubble growth over the electrode surface is well understood, there is no reliable prediction of bubbles break-off diameter from the electrode surface because of the complexity of bubbles motion near the electrode surface. Particle Image Velocimetry (PIV) and Laser Doppler Anemometry (LDA) are the most common experimental techniques to measure bubble dynamics. Although the PIV is faster than LDA, both techniques are considered expensive and time-consuming. This encourages adapting Computational Fluid Dynamics (CFD) methods as an alternative to study bubbles behavior. However, further development of CFD methods is required to include coalescence and break-up of bubbles for better understanding and accuracy. The disadvantages of CFD methods can be overcome by using hybrid methods. The behavior of bubbles in electrochemical systems is still a complex challenging topic which requires a better understanding of the gas bubbles hydrodynamics and their interactions with the electrode surface and bulk liquid, as well as between the bubbles itself. PMID:29731515

Synthesis, characterization, redox behavior, DNA and protein binding and antibacterial activity studies of ruthenium(II) complexes of bidentate schiff bases.

PubMed

Paul, Hena; Sen, Buddhadeb; Mondal, Tapan Kumar; Chattopadhyay, Pabitra

2017-08-03

Two new ruthenium(II) complexes of Schiff base ligands (L) derived from cinnamaldehyde and ethylenediamine formulated as [Ru(L)(bpy) 2 ](ClO 4 ) 2 , where L 1 = N,N'-bis(4-nitrocinnamald-ehyde)ethylenediamine and L 2 = N,N'-bis(2-nitrocinnamaldehyde)-ethylenediamine for complex 1 and 2, respectively, were isolated in pure form. The complexes were characterized by physicochemical and spectroscopic methods. The electrochemical behavior of the complexes showed the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of the complexes with calf thymus DNA (CT-DNA) using absorption, emission spectral studies and electrochemical techniques have been used to determine the binding constant, K b and the linear Stern-Volmer quenching constant, K SV . The results indicate that the ruthenium(II) complexes interact with CT-DNA strongly in a groove binding mode. The interactions of bovine serum albumin (BSA) with the complexes were also investigated with the help of absorption and fluorescence spectroscopy tools. Absorption spectroscopy proved the formation of a ground state BSA-[Ru(L)(bpy) 2 ](ClO 4 ) 2 complex. The antibacterial study showed that the Ru(II) complexes (1 and 2) have better activity than the standard antibiotics but weak activity than the ligands.

Nanoscale visualization of redox activity at lithium-ion battery cathodes.

PubMed

Takahashi, Yasufumi; Kumatani, Akichika; Munakata, Hirokazu; Inomata, Hirotaka; Ito, Komachi; Ino, Kosuke; Shiku, Hitoshi; Unwin, Patrick R; Korchev, Yuri E; Kanamura, Kiyoshi; Matsue, Tomokazu

2014-11-17

Intercalation and deintercalation of lithium ions at electrode surfaces are central to the operation of lithium-ion batteries. Yet, on the most important composite cathode surfaces, this is a rather complex process involving spatially heterogeneous reactions that have proved difficult to resolve with existing techniques. Here we report a scanning electrochemical cell microscope based approach to define a mobile electrochemical cell that is used to quantitatively visualize electrochemical phenomena at the battery cathode material LiFePO4, with resolution of ~100 nm. The technique measures electrode topography and different electrochemical properties simultaneously, and the information can be combined with complementary microscopic techniques to reveal new perspectives on structure and activity. These electrodes exhibit highly spatially heterogeneous electrochemistry at the nanoscale, both within secondary particles and at individual primary nanoparticles, which is highly dependent on the local structure and composition.

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

Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag +/Ag redox reaction to Ag +-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

Reactive Oxygen Species Production by Forward and Reverse Electron Fluxes in the Mitochondrial Respiratory Chain

PubMed Central

Selivanov, Vitaly A.; Votyakova, Tatyana V.; Pivtoraiko, Violetta N.; Zeak, Jennifer; Sukhomlin, Tatiana; Trucco, Massimo; Roca, Josep; Cascante, Marta

2011-01-01

Reactive oxygen species (ROS) produced in the mitochondrial respiratory chain (RC) are primary signals that modulate cellular adaptation to environment, and are also destructive factors that damage cells under the conditions of hypoxia/reoxygenation relevant for various systemic diseases or transplantation. The important role of ROS in cell survival requires detailed investigation of mechanism and determinants of ROS production. To perform such an investigation we extended our rule-based model of complex III in order to account for electron transport in the whole RC coupled to proton translocation, transmembrane electrochemical potential generation, TCA cycle reactions, and substrate transport to mitochondria. It fits respiratory electron fluxes measured in rat brain mitochondria fueled by succinate or pyruvate and malate, and the dynamics of NAD+ reduction by reverse electron transport from succinate through complex I. The fitting of measured characteristics gave an insight into the mechanism of underlying processes governing the formation of free radicals that can transfer an unpaired electron to oxygen-producing superoxide and thus can initiate the generation of ROS. Our analysis revealed an association of ROS production with levels of specific radicals of individual electron transporters and their combinations in species of complexes I and III. It was found that the phenomenon of bistability, revealed previously as a property of complex III, remains valid for the whole RC. The conditions for switching to a state with a high content of free radicals in complex III were predicted based on theoretical analysis and were confirmed experimentally. These findings provide a new insight into the mechanisms of ROS production in RC. PMID:21483483

Reliability and Engineering of Thin-Film Photovoltaic Modules. Research forum proceedings

NASA Technical Reports Server (NTRS)

Ross, R. G., Jr. (Editor); Royal, E. L. (Editor)

1985-01-01

A Research Forum on Reliability and Engineering of Thin Film Photovoltaic Modules, under sponsorship of the Jet Propulsion Laboratory's Flat Plate Solar Array (FSA) Project and the U.S. Department of Energy, was held in Washington, D.C., on March 20, 1985. Reliability attribute investigations of amorphous silicon cells, submodules, and modules were the subjects addressed by most of the Forum presentations. Included among the reliability research investigations reported were: Arrhenius-modeled accelerated stress tests on a Si cells, electrochemical corrosion, light induced effects and their potential effects on stability and reliability measurement methods, laser scribing considerations, and determination of degradation rates and mechanisms from both laboratory and outdoor exposure tests.

Regulating the electrical behaviors of 2D inorganic nanomaterials for energy applications.

PubMed

Feng, Feng; Wu, Junchi; Wu, Changzheng; Xie, Yi

2015-02-11

Recent years have witnessed great developments in inorganic 2D nanomaterials for their unique dimensional confinement and diverse electronic energy bands. Precisely regulating their intrinsic electrical behaviors would bring superior electrical conductivity, rendering 2D nanomaterials ideal candidates for active materials in electrochemical applications when combined with the excellent reaction activity from the inorganic lattice. This Concept focuses on highly conducting inorganic 2D nanomaterials, including intrinsic metallic 2D nanomaterials and artificial highly conductive 2D nanomaterials. The intrinsic metallicity of 2D nanomaterials is derived from their closely packed atomic structures that ensure maximum overlapping of electron orbitals, while artificial highly conductive 2D nanomaterials could be achieved by designed methodologies of surface modification, intralayer ion doping, and lattice strain, in which atomic-scale structural modulation plays a vital role in realizing conducting behaviors. Benefiting from fast electron transfer, high reaction activity, as well as large surface areas arising from the 2D inorganic lattice, highly conducting 2D nanomaterials open up prospects for enhancing performance in electrochemical catalysis and electrochemical capacitors. Conductive 2D inorganic nanomaterials promise higher efficiency for electrochemical applications of energy conversion and storage. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical wastewater treatment directly powered by photovoltaic panels: electrooxidation of a dye-containing wastewater.

PubMed

Valero, David; Ortiz, Juan M; Expósito, Eduardo; Montiel, Vicente; Aldaz, Antonio

2010-07-01

Electrochemical technologies have proved to be useful for the treatment of wastewater, but to enhance their green characteristics it seems interesting to use a green electric energy such as that provided by photovoltaic (PV) cells, which are actually under active research to decrease the economic cost of solar kW. The aim of this work is to demonstrate the feasibility and utility of using an electrooxidation system directly powered by a photovoltaic array for the treatment of a wastewater. The experimental system used was an industrial electrochemical filter press reactor and a 40-module PV array. The influence on the degradation of a dye-containing solution (Remazol RB 133) of different experimental parameters such as the PV array and electrochemical reactor configurations has been studied. It has been demonstrated that the electrical configuration of the PV array has a strong influence on the optimal use of the electric energy generated. The optimum PV array configuration changes with the intensity of the solar irradiation, the conductivity of the solution, and the concentration of pollutant in the wastewater. A useful and effective methodology to adjust the EO-PV system operation conditions to the wastewater treatment is proposed.

Dual-responsive immunosensor that combines colorimetric recognition and electrochemical response for ultrasensitive detection of cancer biomarkers.

PubMed

Hong, Wooyoung; Lee, Sooyeon; Cho, Youngnam

2016-12-15

We developed a nanoroughened, biotin-doped polypyrrole immunosensor for the detection of tumor markers through dual-signal (electrochemical and colorimetric) channels, electrochemical and colorimetric, that demonstrates remarkable analytical performance. A rapid, one-step electric field-mediated method was employed to fabricate the immunosensor with nanoscale roughness by simply modulating the applied electrical potential. We demonstrated the successful detection of three tumor markers (CA125, CEA, and PSA) via the double enzymatic signal amplifications in the presence of a target antigen, ultimately leading to desired diagnostic accuracy and reliability. The addition of multiple horseradish peroxidase (HRP)- and antibody-labeled nanoparticles greatly amplified the signal and simplified the measurement of cancer biomarker proteins by sequentially magnifying electrochemical and colorimetric signals in a single platform. The two parallel assays performed using the proposed immunosensor have yielded highly consistent and reproducible results. Additionally, for the analysis of plasma samples in a clinical setting, the values obtained with our immunosensor were validated by correlating the results with those of a standard radioimmunoassay (RIA), which obtained very similar clinically valid responses. Copyright © 2016 Elsevier B.V. All rights reserved.

Corrosion Behavior of Carbon Steel in Concrete Material Composed of Tin Slag Waste in Aqueous Chloride Solution

NASA Astrophysics Data System (ADS)

Rustandi, Andi; Cahyadi, Agung; Taruli Siallagan, Sonia; Wafa' Nawawi, Fuad; Pratesa, Yudha

2018-01-01

Tin slag is a byproduct of tin ore smelting process which is rarely utilized. The main purpose of this work is to investigate the use of tin slag for concrete cement material application compared to the industrial Ordinary Portland Cement (OPC). Tin slag composition was characterized by XRD and XRF analysis. The characterization results showed the similar chemical composition of tin slag and OPC. It also revealed the semi crystalline structure of tin slag sample. Several electrochemical tests were performed to evaluate corrosion behavior of tin slag, OPC and various mixed composition of both materials and the addition of CaO. The corrosion behavior of OPC and tin slag were evaluated by using Cyclic Polarization, Electrochemical Impedance Spectroscopy (EIS) and Electrochemical Frequency Modulation (EFM) methods. Aqueous sodium chloride (NaCl) solution with 3.5% w.t concentration which similar to seawater was used as the electrolyte in this work. The steel specimen used as the reinforce bar (rebar) material of the concrete was carbon steel AISI 1045. The rebar was embedded in the concrete cement which composed of OPC and the various composition of tin slag including slag without addition of CaO and slag mixed with addition of 50 % CaO. The electrochemical tests results revealed that tin slag affected its corrosion behavior which becoming more active and increasing the corrosion rate as well as decreasing the electrochemical impedance.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Crystalline-silicon reliability lessons for thin-film modules

NASA Technical Reports Server (NTRS)

Ross, R. G., Jr.

1985-01-01

The reliability of crystalline silicon modules has been brought to a high level with lifetimes approaching 20 years, and excellent industry credibility and user satisfaction. The transition from crystalline modules to thin film modules is comparable to the transition from discrete transistors to integrated circuits. New cell materials and monolithic structures will require new device processing techniques, but the package function and design will evolve to a lesser extent. Although there will be new encapsulants optimized to take advantage of the mechanical flexibility and low temperature processing features of thin films, the reliability and life degradation stresses and mechanisms will remain mostly unchanged. Key reliability technologies in common between crystalline and thin film modules include hot spot heating, galvanic and electrochemical corrosion, hail impact stresses, glass breakage, mechanical fatigue, photothermal degradation of encapsulants, operating temperature, moisture sorption, circuit design strategies, product safety issues, and the process required to achieve a reliable product from a laboratory prototype.

Solar-Electrochemical Power System for a Mars Mission

NASA Technical Reports Server (NTRS)

Withrow, Colleen A.; Morales, Nelson

1994-01-01

This report documents a sizing study of a variety of solar electrochemical power systems for the intercenter NASA study known as 'Mars Exploration Reference Mission'. Power systems are characterized for a variety of rovers, habitation modules, and space transport vehicles based on requirements derived from the reference mission. The mission features a six-person crew living on Mars for 500 days. Mission power requirements range from 4 kWe to 120 kWe. Primary hydrogen and oxygen fuel cells, regenerative hydrogen and oxygen fuel cells, sodium sulfur batteries advanced photovoltaic solar arrays of gallium arsenide on germanium with tracking and nontracking mechanisms, and tent solar arrays of gallium arsenide on germanium are evaluated and compared.

Electrochemically modulated liquid chromatography using a boron-doped diamond particle stationary phase

PubMed Central

Muna, Grace W.; Swope, Vernon M.; Swain, Greg M.; Porter, Marc D.

2011-01-01

This paper reports on preliminary tests of the performance of boron-doped diamond powder (BDDP) as a stationary phase in electrochemically modulated liquid chromatography (EMLC). EMLC manipulates retention through changes in the potential applied (Eappl) to a conductive packing. Porous graphitic carbon (PGC) has routinely been utilized as a material in EMLC separations. Herein the utility of BDDP as a stationary phase in EMLC was investigated and its stability, both compositionally and microstructurally, relative to PGC was compared. The results show that BDDP is stable over a wide range of Eappl values (i.e., −1.2 to +1.2 V vs. Ag/AgCl, sat’d NaCl). The data also reveal that electrostatics play a key role in the adsorption of the aromatic sulfonates on the BDDP stationary phase, and that these analytes are more weakly retained in comparison to the PGC support. The potential for this methodology to provide a means to advance the understanding of molecular adsorption and retention mechanisms on carbonaceous materials is briefly discussed. PMID:18922535

Simultaneous noncontact topography and electrochemical imaging by SECM/SICM featuring ion current feedback regulation.

PubMed

Takahashi, Yasufumi; Shevchuk, Andrew I; Novak, Pavel; Murakami, Yumi; Shiku, Hitoshi; Korchev, Yuri E; Matsue, Tomokazu

2010-07-28

We described a hybrid system of scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM) with ion current feedback nanopositioning control for simultaneous imaging of noncontact topography and spatial distribution of electrochemical species. A nanopipette/nanoring electrode probe provided submicrometer resolution of the electrochemical measurement on surfaces with complex topology. The SECM/SICM probe had an aperture radius of 220 nm. The inner and outer radii of the SECM Au nanoring electrode were 330 and 550 nm, respectively. Characterization of the probe was performed with scanning electron microscopy (SEM), cyclic voltammetry (CV), and approach curve measurements. SECM/SICM was applied to simultaneous imaging of topography and electrochemical responses of enzymes (horse radish peroxidase (HRP) and glucose oxidase (GOD)) and single live cells (A6 cells, superior cervical ganglion (SCG) cells, and cardiac myocytes). The measurements revealed the distribution of activity of the enzyme spots on uneven surfaces with submicrometer resolution. SECM/SICM acquired high resolution topographic images of cells together with the map of electrochemical signals. This combined technique was also applied to the evaluation of the permeation property of electroactive species through cellular membranes.

One-step electrochemical deposition of Schiff base cobalt complex as effective water oxidation catalyst

NASA Astrophysics Data System (ADS)

Huang, Binbin; Wang, Yan; Zhan, Shuzhong; Ye, Jianshan

2017-02-01

Schiff base metal complexes have been applied in many fields, especially, a potential homogeneous catalyst for water splitting. However, the high overpotential, time consumed synthesis process and complicated working condition largely limit their application. In the present work, a one-step approach to fabricate Schiff base cobalt complex modified electrode is developed. Microrod clusters (MRC) and rough spherical particles (RSP) can be obtained on the ITO electrode through different electrochemical deposition condition. Both of the MRC and RSP present favorable activity for oxygen evolution reaction (OER) compared to the commercial Co3O4, taking an overpotential of 650 mV and 450 mV to drive appreciable catalytic current respectively. The highly active and stable RSP shows a Tafel plot of 84 mV dec-1 and negligible decrease of the current density for 12 h bulk electrolysis. The synthesis strategy of effective and stable catalyst in this work provide a simple method to fabricate heterogeneous OER catalyst with Schiff base metal complex.

Characterization of surface complexes in enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Roy, D.; Furtak, T. E.

1984-11-01

An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl- ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl- ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl+ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl-/Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes.

PubMed

Berardi, Serena; Francàs, Laia; Neudeck, Sven; Maji, Somnath; Benet-Buchholz, Jordi; Meyer, Franc; Llobet, Antoni

2015-11-01

Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes

NASA Astrophysics Data System (ADS)

Ceyhan, Gökhan; Çelik, Cumali; Uruş, Serhan; Demirtaş, İbrahim; Elmastaş, Mahfuz; Tümer, Mehmet

2011-10-01

In this study, two Schiff base ligands (HL 1 and HL 2) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as Gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as Gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH rad ) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.

Electrochemical and Spectroscopic Investigation of Molten Chloroaluminates and Related Solvents

DTIC Science & Technology

1988-11-07

chemistry of iridium carbonyl complexes known to be active Fischer-Tropsch catalysts (described below). These studies represent the first successful in...electrochemical studies, e. g., doole potential step chronocoulometry, of this system are in progress. 3: hemistry of iridium carbonyls in sodium...chloroaluminates’/The iridium carbonyl species 1r4(CO)12 and IrCl(CO)3 have previously been shown to serve as Fischer-Tropsch catalysts in acidic sodium

Investigation of bio polymer electrolyte based on cellulose acetate-ammonium nitrate for potential use in electrochemical devices.

PubMed

Monisha, S; Mathavan, T; Selvasekarapandian, S; Milton Franklin Benial, A; Aristatil, G; Mani, N; Premalatha, M; Vinoth Pandi, D

2017-02-10

Proton conducting materials create prime interest in electro chemical device development. Present work has been carried out to design environment friendly new biopolymer electrolytes (BPEs) using cellulose acetate (CA) complex with different concentrations of ammonium nitrate (NH 4 NO 3 ), which have been prepared as film and characterized. The 50mol% CA and 50mol% NH 4 NO 3 complex has highest ionic conductivity (1.02×10 -3 Scm -1 ). Differential scanning calorimetry shows the changes in glass transition temperature depends on salt concentration. Structural analysis indicates that the highest ionic conductivity complex exhibits more amorphous nature. Vibrational analysis confirms the complex formation, which has been validated theoretically by Gaussian 09 software. Conducting element in the BPEs has been predicted. Primary proton battery and proton exchange membrane fuel cell have been developed for highest ionic conductivity complex. Output voltage and power performance has been compared for single fuel cell application, which manifests the present BPE holds promise application in electrochemical devices. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of complexing agents on electrochemical deposition of FeS x O y in ZnO/FeS x O y heterostructures

NASA Astrophysics Data System (ADS)

Supee, A.; Ichimura, M.

2017-12-01

Heterostructures which consist of ZnO and FeS x O y were deposited via electrochemical deposition (ECD) for application to solar cells. Galvanostatic ECD was used in FeS x O y deposition with a solution containing 100 mM Na2S2O3 and 30 mM FeSO4. To alter the film properties, L(+)-tartaric acid (C4H6O6) and lactic acid [CH3CH(OH)COOH] were introduced as the complexing agents into the FeS x O y deposition solution. Larger film thickness and smaller oxygen content were obtained for the films deposited with the complexing agents. ZnO was deposited on FeS x O y by two-step pulse ECD from a solution containing Zn(NO3)2. For the ZnO/FeS x O y heterostructures fabricated with/without complexing agents, rectifying properties were confirmed in the current density-voltage ( J- V) characteristics. However, photovoltaic properties were not improved with addition of both complexing agents.

Behaviour of Zinc Complexes and Zinc Sulphide Nanoparticles Revealed by Using Screen Printed Electrodes and Spectrometry

PubMed Central

Nejdl, Lukas; Ruttkay-Nedecky, Branislav; Kudr, Jiří; Kremplova, Monika; Cernei, Natalia; Prasek, Jan; Konecna, Marie; Hubalek, Jaromir; Zitka, Ondrej; Kynicky, Jindrich; Kopel, Pavel; Kizek, Rene; Adam, Vojtech

2013-01-01

In this study, we focused on microfluidic electrochemical analysis of zinc complexes (Zn(phen)(his)Cl2, Zn(his)Cl2) and ZnS quantum dots (QDs) using printed electrodes. This method was chosen due to the simple (easy to use) instrumentation and variable setting of flows. Reduction signals of zinc under the strictly defined and controlled conditions (pH, temperature, flow rate, accumulation time and applied potential) were studied. We showed that the increasing concentration of the complexes (Zn(phen)(his)Cl2, Zn(his)Cl2) led to a decrease in the electrochemical signal and a significant shift of the potential to more positive values. The most likely explanation of this result is that zinc is strongly bound in the complex and its distribution on the electrode is very limited. Changing the pH from 3.5 to 5.5 resulted in a significant intensification of the Zn(II) reduction signal. The complexes were also characterized by UV/VIS spectrophotometry, chromatography, and ESI-QTOF mass spectrometry. PMID:24233071

Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator

PubMed Central

Wu, Guan; Hu, Ying; Liu, Yang; Zhao, Jingjing; Chen, Xueli; Whoehling, Vincent; Plesse, Cédric; Nguyen, Giao T. M.; Vidal, Frédéric; Chen, Wei

2015-01-01

Ionic actuators have attracted attention due to their remarkably large strain under low-voltage stimulation. Because actuation performance is mainly dominated by the electrochemical and electromechanical processes of the electrode layer, the electrode material and structure are crucial. Here, we report a graphitic carbon nitride nanosheet electrode-based ionic actuator that displays high electrochemical activity and electromechanical conversion abilities, including large specific capacitance (259.4 F g−1) with ionic liquid as the electrolyte, fast actuation response (0.5±0.03% in 300 ms), large electromechanical strain (0.93±0.03%) and high actuation stability (100,000 cycles) under 3 V. The key to the high performance lies in the hierarchical pore structure with dominant size <2 nm, optimal pyridinic nitrogen active sites (6.78%) and effective conductivity (382 S m−1) of the electrode. Our study represents an important step towards artificial muscle technology in which heteroatom modulation in electrodes plays an important role in promoting electrochemical actuation performance. PMID:26028354

Bedside arterial blood gas monitoring system using fluorescent optical sensors

NASA Astrophysics Data System (ADS)

Bartnik, Daniel J.; Rymut, Russell A.

1995-05-01

We describe a bedside arterial blood gas (ABG) monitoring system which uses fluorescent optical sensors in the measurement of blood pH, PCO2 and PO2. The Point-of-Care Arterial Blood Gas Monitoring System consists of the SensiCathTM optical sensor unit manufactured by Optical Sensors Incorporated and the TramTM Critical Care Monitoring System with ABG Module manufactured by Marquette Electronics Incorporated. Current blood gas measurement techniques require a blood sample to be removed from the patient and transported to an electrochemical analyzer for analysis. The ABG system does not require removal of blood from the patient or transport of the sample. The sensor is added to the patient's existing arterial line. ABG measurements are made by drawing a small blood sample from the arterial line in sufficient quantity to ensure an undiluted sample at the sensor. Measurements of pH, PCO2 and PO2 are made within 60 seconds. The blood is then returned to the patient, the line flushed and results appear on the bedside monitor. The ABG system offers several advantages over traditional electrochemical analyzers. Since the arterial line remains closed during the blood sampling procedure the patient's risk of infection is reduced and the caregiver's exposure to blood is eliminated. The single-use, disposable sensor can be measure 100 blood samples over 72 hours after a single two-point calibration. Quality Assurance checks are also available and provide the caregiver the ability to assess system performance even after the sensor is patient attached. The ABG module integrates with an existing bedside monitoring system. This allows ABG results to appear on the same display as ECG, respiration, blood pressure, cardiac output, SpO2, and other clinical information. The small module takes up little space in the crowded intensive care unit. Performance studies compare the ABG system with an electrochemical blood gas analyzer. Study results demonstrated accurate and precise blood gas measurement of 100 samples and 72 hour performance without need for re-calibration.

Efficient and Extensible Quasi-Explicit Modular Nonlinear Multiscale Battery Model: GH-MSMD

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

Kim, Gi-Heon; Smith, Kandler; Lawrence-Simon, Jake

Complex physics and long computation time hinder the adoption of computer aided engineering models in the design of large-format battery cells and systems. A modular, efficient battery simulation model -- the multiscale multidomain (MSMD) model -- was previously introduced to aid the scale-up of Li-ion material and electrode designs to complete cell and pack designs, capturing electrochemical interplay with 3-D electronic current pathways and thermal response. Here, this paper enhances the computational efficiency of the MSMD model using a separation of time-scales principle to decompose model field variables. The decomposition provides a quasi-explicit linkage between the multiple length-scale domains andmore » thus reduces time-consuming nested iteration when solving model equations across multiple domains. In addition to particle-, electrode- and cell-length scales treated in the previous work, the present formulation extends to bus bar- and multi-cell module-length scales. We provide example simulations for several variants of GH electrode-domain models.« less

Efficient and Extensible Quasi-Explicit Modular Nonlinear Multiscale Battery Model: GH-MSMD

DOE PAGES

Kim, Gi-Heon; Smith, Kandler; Lawrence-Simon, Jake; ...

2017-03-24

Complex physics and long computation time hinder the adoption of computer aided engineering models in the design of large-format battery cells and systems. A modular, efficient battery simulation model -- the multiscale multidomain (MSMD) model -- was previously introduced to aid the scale-up of Li-ion material and electrode designs to complete cell and pack designs, capturing electrochemical interplay with 3-D electronic current pathways and thermal response. Here, this paper enhances the computational efficiency of the MSMD model using a separation of time-scales principle to decompose model field variables. The decomposition provides a quasi-explicit linkage between the multiple length-scale domains andmore » thus reduces time-consuming nested iteration when solving model equations across multiple domains. In addition to particle-, electrode- and cell-length scales treated in the previous work, the present formulation extends to bus bar- and multi-cell module-length scales. We provide example simulations for several variants of GH electrode-domain models.« less

System-based approach for an advanced drug delivery platform

NASA Astrophysics Data System (ADS)

Kulinsky, Lawrence; Xu, Han; Tsai, Han-Kuan A.; Madou, Marc

2006-03-01

Present study is looking at the problem of integrating drug delivery microcapsule, a bio-sensor, and a control mechanism into a biomedical drug delivery system. A wide range of medical practices from cancer therapy to gastroenterological treatments can benefit from such novel bio-system. Drug release in our drug delivery system is achieved by electrochemically actuating an array of polymeric valves on a set of drug reservoirs. The valves are bi-layer structures, made in the shape of a flap hinged on one side to a valve seat, and consisting of thin films of evaporated gold and electrochemically deposited polypyrrole (PPy). These thin PPy(DBS) bi-layer flaps cover access holes of underlying chambers micromachined in a silicon substrate. Chromium and polyimide layers are applied to implement "differential adhesion" to obtain a voltage induced deflection of the bilayer away from the drug reservoir. The Cr is an adhesion-promoting layer, which is used to strongly bind the gold layer down to the substrate, whereas the gold adheres weakly to polyimide. Drug actives (dry or wet) were pre-stored in the chambers and their release is achieved upon the application of a small bias (~ 1V). Negative voltage causes cation adsorption and volume change in PPy film. This translates into the bending of the PPy/Au bi-layer actuator and release of the drug from reservoirs. This design of the drug delivery module is miniaturized to the dimensions of 200μm valve diameter. Galvanostatic and potentiostatic PPy deposition methods were compared, and potentiostatic deposition method yields film of more uniform thickness. PPy deposition experiments with various pyrrole and NaDBS concentrations were also performed. Glucose biosensor based on glucose oxidase (GOx) embedded in the PPy matrix during elechtrochemical deposition was manufactured and successfully tested. Multiple-drug pulsatile release and continuous linear release patterns can be implemented by controlling the operation of an array of valves. Varying amounts of drugs, together with more complex controlling strategies would allow creation of more complex drug delivery patterns.

Electrochemical investigations of advanced materials for microelectronic and energy storage devices

NASA Astrophysics Data System (ADS)

Goonetilleke, Pubudu Chaminda

A broad range of electrochemical techniques are employed in this work to study a selected set of advanced materials for applications in microelectronics and energy storage devices. The primary motivation of this study has been to explore the capabilities of certain modern electrochemical techniques in a number of emerging areas of material processing and characterization. The work includes both aqueous and non-aqueous systems, with applications in two rather general areas of technology, namely microelectronics and energy storage. The sub-systems selected for investigation are: (i) Electrochemical mechanical and chemical mechanical planarization (ECMP and CMP, respectively), (ii) Carbon nanotubes in combination with room temperature ionic liquids (ILs), and (iii) Cathode materials for high-performance Li ion batteries. The first group of systems represents an important building block in the fabrication of microelectronic devices. The second and third groups of systems are relevant for new energy storage technologies, and have generated immense interests in recent years. A common feature of these different systems is that they all are associated with complex surface reactions that dictate the performance of the devices based on them. Fundamental understanding of these reactions is crucial to further development and expansion of their associated technologies. It is the complex mechanistic details of these surface reactions that we address using a judicious combination of a number of state of the art electrochemical techniques. The main electrochemical techniques used in this work include: (i) Cyclic voltammetry (CV) and slow scan cyclic voltammetry (SSCV, a special case of CV); (ii) Galvanostatic (or current-controlled) measurements; (iii) Electrochemical impedance spectroscopy (EIS), based on two different methodologies, namely, Fourier transform EIS (FT-EIS, capable of studying fast reaction kinetics in a time-resolved mode), and EIS using frequency response analysis (employed to study slow reactions such as solid state diffusion of Li). The designs of both the experimental equipment and the control variables change for studying the different aqueous and non-aqueous systems. The protocols for data analysis also change depending on the systems. In addition, it often becomes necessary to combine different aspects of the different experimental methods to obtain the necessary information about the system(s) under study. The experimental strategies and the associated theoretical considerations for developing these strategies are discussed in appropriate contexts of this work. CNT electrodes in combination with IL electrolytes are potentially important for electrochemical super-capacitors. We have carried out electrochemical investigation of such a system involving a paper-electrode of multiwall CNT in the IL of 1-Ethyl-3-methyl imidazolium ethylsulfate (EMIM-EtSO4). Our study concentrated on the analytical aspects of cyclic voltammetry (CV) to probe the double layer capacitance of these relatively unconventional systems. (that involve rather large charge-discharge time constants). Both theoretical and experimental aspects of CV for such systems have been discussed, focusing in particular, on the effects of faradaic side-reactions, electrolyte resistance and voltage scan speeds. The results have been analyzed using an electrode equivalent circuit model, demonstrating a method to account for the typical artifacts expected in CV of CNT-IL interfaces. Chemical-mechanical planarization (CMP) of copper has now become an integral part of modern semiconductor fabrication technology. Recently, electrochemical-mechanical planarization (ECMP) has emerged as a possible extension of CMP, where through voltage-activated removal of Cu surface layers, one can substantially minimize the down-force necessary for mechanical polishing However, the detailed electrochemical factors that are central to designing efficient abrasive-free electrolytes for ECMP are not clearly understood at the present time. The present work has addressed this issue by studying the relative electrochemical effects of selected different chemical additives. Controlling the surface reactions (that is controlling the voltage-induced material removal) in ECMP requires a carefully designed combination of a number of electrochemical input variables (voltage activation program and electrolyte composition). We have studied the main experimental factors for designing these parameters, using triangular and rectangular-voltage-pulse modulated dissolution of Cu in electrolytes of different chemical compositions. Applications of rechargeable Li ion batteries have considerably expanded in recent years. As a result, research activities involving material-fabrication and characterization for these batteries also have expanded during this period. The importance of studying these specific materials lies in the fact that the cathode plays a major role in its contribution to the battery performance LiMn2O4 cathodes are being considered for next generation of Li ion batteries. The current work focuses on a specific problem commonly associated with Li cathode systems, namely surface film formation on the cathodes. LiMn2O4 cathodes tend to develop native surface films in carbonate electrolytes. By combining D.C. SSCV with A.C. EIS, we have studied how these films would react with an electrolyte of LiBF4 in ethylene and diethyl carbonates. We have demonstrated that such reactions could affect the measurement of the characteristic electrochemical parameters of the cathode, namely the intercalation capacitance, initial capacity-loss, coulometric titration profiles, and the solid state diffusion coefficient of Li+. A generalized framework for data analysis, based on the considerations of electrode equivalent circuits, has been used to combine the results of the D.C. and A.C. measurements.

Magnetic field effects on electrochemical metal depositions.

PubMed

Bund, Andreas; Ispas, Adriana; Mutschke, Gerd

2008-04-01

This paper discusses recent experimental and numerical results from the authors' labs on the effects of moderate magnetic (B) fields in electrochemical reactions. The probably best understood effect of B fields during electrochemical reactions is the magnetohydrodynamic (MHD) effect. In the majority of cases it manifests itself in increased mass transport rates which are a direct consequence of Lorentz forces in the bulk of the electrolyte. This enhanced mass transport can directly affect the electrocrystallization. The partial currents for the nucleation of nickel in magnetic fields were determined using an in situ micro-gravimetric technique and are discussed on the basis of the nucleation model of Heerman and Tarallo. Another focus of the paper is the numerical simulation of MHD effects on electrochemical metal depositions. A careful analysis of the governing equations shows that many MHD problems must be treated in a 3D geometry. In most cases there is a complex interplay of natural and magnetically driven convection.

An Electrochemical Impedimetric Aptasensing Platform for Sensitive and Selective Detection of Small Molecules Such as Chloramphenicol

PubMed Central

Pilehvar, Sanaz; Dierckx, Tarryn; Blust, Ronny; Breugelmans, Tom; De Wael, Karolien

2014-01-01

We report on the aptadetection of chloramphenicol (CAP) using electrochemical impedance spectroscopy. The detection principle is based on the changes of the interfacial properties of the electrode after the interaction of the ssDNA aptamers with the target molecules. The electrode surface is partially blocked due to the formation of the aptamer-CAP complex, resulting in an increase of the interfacial electron-transfer resistance of the redox probe detected by electrochemical impedance spectroscopy or cyclic voltammetry. We observed that the ratio of polarization resistance had a linear relationship with the concentrations of CAP in the range of 1.76–127 nM, and a detection limit of 1.76 nM was obtained. The covalent binding of CAP-aptamer on the electrode surface combined with the unique properties of aptamers and impedimetric transduction leads to the development of a stable and sensitive electrochemical aptasensor for CAP. PMID:25004156

Investigating Li 2NiO 2–Li 2CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

DOE PAGES

Xu, Jing; Renfrew, Sara; Marcus, Matthew A.; ...

2017-05-11

Li 2Ni 1–xCu xO 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2Ni 1–xCu xO 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, andmore » charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.« less

Electrochemical and spectroelectrochemical study on novel non-peripherally tetra 1,2,4-triazole substituted phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Koca, Atıf; Bekircan, Olcay; Kantekin, Halit

2018-03-01

In the present study novel tetra 4-(4-fluorophenyl)-5-(4-methoxyphenyl)-4H-1,2,4-triazole-3-thio substituted non-peripherally metal free (4), zinc(II) (5), lead (II) (6) and copper(II) (7) phthalocyanines were synthesized. The obtained novel compounds were characterized by a combination of FT-IR, 1H NMR, UV-Vis and MALDI-TOF techniques. The redox properties of the complexes have been investigated via cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemistry. The compounds displayed ring-based, reversible and/or quasi-reversible reduction and oxidation processes and aggregation of the complexes influenced the redox character of the processes. The color changes during the redox processes of metallo phthalocyanine were recorded by in-situ spectroelectrochemical measurements. In situ UV-vis spectroelectrochemical measurements, which was associated with color change of the complexes, showed their applicability in the fields of the electrochemical technologies.

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

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

Chen, Yan; Cheng, Yongqiang; Li, Juchuan

Transition metal (TM) substitution has been widely applied to change complex oxides crystal structures to create high energy density electrodes materials in high performance rechargeable lithium-ion batteries. The complex local structure in the oxides imparted by the TM arrangement often impacts their electrochemical behaviors by influencing the diffusion and intercalation of lithium. Here, a major discrepancy is demonstrated between the global and local structures of the promising high energy density and high voltage LiNi 0.5Mn 1.5O 4 spinel cathode material that contradicts the existing structural models. A new single-phase lattice-cell orientation disorder model is proposed as the mechanism for themore » local ordering that explains how the inhomogeneous local distortions and the coherent connection give rise to the global structure in the complex oxide. As a result, the single-phase model is consistent with the electrochemical behavior observation of the materials.« less

Characterization of Screen-Printed Organic Electrochemical Transistors to Detect Cations of Different Sizes.

PubMed

Contat-Rodrigo, Laura; Pérez-Fuster, Clara; Lidón-Roger, José Vicente; Bonfiglio, Annalisa; García-Breijo, Eduardo

2016-09-28

A novel screen-printing fabrication method was used to prepare organic electrochemical transistors (OECTs) based on poly(3,4-ethylenedioxythiophene) doped with polysterene sulfonate (PEDOT:PSS). Initially, three types of these screen-printed OECTs with a different channel and gate areas ratio were compared in terms of output characteristics, transfer characteristics, and current modulation in a phosphate buffered saline (PBS) solution. Results confirm that transistors with a gate electrode larger than the channel exhibit higher modulation. OECTs with this geometry were therefore chosen to investigate their ion-sensitive properties in aqueous solutions of cations of different sizes (sodium and rhodamine B). The effect of the gate electrode was additionally studied by comparing these all-PEDOT:PSS transistors with OECTs with the same geometry but with a non-polarizable metal gate (Ag). The operation of the all-PEDOT:PSS OECTs yields a response that is not dependent on a Na⁺ or rhodamine concentration. The weak modulation of these transistors can be explained assuming that PEDOT:PSS behaves like a supercapacitor. In contrast, the operation of Ag-Gate OECTs yields a response that is dependent on ion concentration due to the redox reaction taking place at the gate electrode with Cl - counter-ions. This indicates that, for cation detection, the response is maximized in OECTs with non-polarizable gate electrodes.

Synthesis, crystal structure, photoluminescence and electrochemical properties of a sandwiched Ni2Ce complex

NASA Astrophysics Data System (ADS)

Güngör, Seyit Ali; Kose, Muhammet

2017-12-01

In this study, a Ni2Ce complex [(NiL)2Ce(NO3)2](NO3) was synthesized and characterized by spectroscopic and analytical methods. The structure of the complex was determined by single crystal X-ray diffraction study. In the structure of the complex, a Ce(III) ion is sandwiched between the two NiL units, which are virtually parallel to each other. The Ce(III) center is 12-coordinate, surrounded by 12 oxygen atoms; four are from phenolic groups, four from methoxy groups, and four from two bidentate nitrate ligands. Hirshfeld surface analysis was used to evaluate the inter-molecular interactions within the crystal packing. The complex molecules are linked by H⋯ONO2 interactions. The largest contribution is H⋯O/O⋯H with 41.6% contribution and followed by H⋯H contacts with 39.1%. The complex showed an excitation band in the range of 510-580 nm. A band in the range of 520-580 nm observed in the emission spectrum almost completely overlapped. This suggests that the band in the emission spectrum of the complex is not the actual fluorescence emission and is assigned to the Rayleigh scattering band. Electrochemical and thermal behaviours of the complex were also investigated.

Mononuclear zinc(II) complexes of 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols: Synthesis, structural characterization, DNA binding and cheminuclease activities

NASA Astrophysics Data System (ADS)

Ravichandran, J.; Gurumoorthy, P.; Karthick, C.; Kalilur Rahiman, A.

2014-03-01

Four new zinc(II) complexes [Zn(HL1-4)Cl2] (1-4), where HL1-4 = 2-((2-(piperazin-1-yl)ethylimino)methyl)-4-substituted phenols, have been isolated and fully characterized using various spectro-analytical techniques. The X-ray crystal structure of complex 4 shows the distorted trigonal-bipyramidal coordination geometry around zinc(II) ion. The crystal packing is stabilized by intermolecular NH⋯O hydrogen bonding interaction. The complexes display no d-d electronic band in the visible region due to d10 electronic configuration of zinc(II) ion. The electrochemical properties of the synthesized ligands and their complexes exhibit similar voltammogram at reduction potential due to electrochemically innocent Zn(II) ion, which evidenced that the electron transfer is due to the nature of the ligand. Binding interaction of complexes with calf thymus DNA was studied by UV-Vis absorption titration, viscometric titration and cyclic voltammetry. All complexes bind with CT DNA by intercalation, giving the binding affinity in the order of 2 > 1 ≫ 3 > 4. The prominent cheminuclease activity of complexes on plasmid DNA (pBR322 DNA) was observed in the absence and presence of H2O2. Oxidative pathway reveals that the underlying mechanism involves hydroxyl radical.

Heterobimetallic complexes with redox-active mesoionic carbenes as metalloligands: electrochemical properties, electronic structures and catalysis.

PubMed

Hettmanczyk, Lara; Manck, Sinja; Hoyer, Carolin; Hohloch, Stephan; Sarkar, Biprajit

2015-07-11

A mesoionic carbene with a ferrocene backbone is used as a metalloligand to generate the first example of their Fe-Au heterobimetallic complexes. The details of geometric and electronic structures in different redox states and preliminary catalytic results are presented.

Impedance spectroscopy study of a catechol-modified activated carbon electrode as active material in electrochemical capacitor

NASA Astrophysics Data System (ADS)

Cougnon, C.; Lebègue, E.; Pognon, G.

2015-01-01

Modified activated carbon (Norit S-50) electrodes with electrochemical double layer (EDL) capacitance and redox capacitance contributions to the electric charge storage were tested in 1 M H2SO4 to quantify the benefit and the limitation of the surface redox reactions on the electrochemical performances of the resulting pseudo-capacitive materials. The electrochemical performances of an electrochemically anodized carbon electrode and a catechol-modified carbon electrode, which make use both EDL capacitance of the porous structure of the carbon and redox capacitance, were compared to the performances obtained for the pristine carbon. Nitrogen gas adsorption measurements have been used for studying the impact of the grafting on the BET surface area, pore size distribution, pore volume and average pore diameter. The electrochemical behavior of carbon materials was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The EIS data were discussed by using a complex capacitance model that allows defining the characteristic time constant, the global capacitance and the frequency at which the maximum charge stored is reached. The EIS measurements were achieved at different dc potential values where a redox activity occurs and the evolution of the capacitance and the capacitive relaxation time with the electrode potential are presented. Realistic galvanostatic charge/discharge measurements performed at different current rates corroborate the results obtained by impedance.

Nucleic acid-based electrochemical nanobiosensors.

PubMed

Abi, Alireza; Mohammadpour, Zahra; Zuo, Xiaolei; Safavi, Afsaneh

2018-04-15

The detection of biomarkers using sensitive and selective analytical devices is critically important for the early stage diagnosis and treatment of diseases. The synergy between the high specificity of nucleic acid recognition units and the great sensitivity of electrochemical signal transductions has already shown promise for the development of efficient biosensing platforms. Yet nucleic-acid based electrochemical biosensors often rely on target amplification strategies (e.g., polymerase chain reactions) to detect analytes at clinically relevant concentration ranges. The complexity and time-consuming nature of these amplification methods impede moving nucleic acid-based electrochemical biosensors from laboratory-based to point-of-care test settings. Fortunately, advancements in nanotechnology have provided growing evidence that the recruitment of nanoscaled materials and structures can enhance the biosensing performance (particularly in terms of sensitivity and response time) to the level suitable for use in point-of-care diagnostic tools. This Review highlights the significant progress in the field of nucleic acid-based electrochemical nanobiosensing with the focus on the works published during the last five years. Copyright © 2017. Published by Elsevier B.V.

Ultrasensitive one-step rapid detection of ochratoxin A by the folding-based electrochemical aptasensor.

PubMed

Wu, Jingjing; Chu, Huaqin; Mei, Zhanlong; Deng, Yi; Xue, Feng; Zheng, Lei; Chen, Wei

2012-11-13

A one-step electrochemical aptasensor using the thiol- and methylene blue- (MB-) dual-labeled aptamer modified gold electrode for determination of ochratoxin A (OTA) was presented in this research. The aptamer against OTA was covalently immobilized on the surface of the electrode by the self-assembly effect and used as recognition probes for OTA detection by the binding induced folding of the aptamer. Under the optimal conditions, the developed electrochemical aptasensor demonstrated a wide linear range from 0.1 pg mL(-1) to 1000 pg mL(-1) with the limit of detection (LOD) of 0.095 pg mL(-1), which was an extraordinary sensitivity compared with other common methods for OTA detection. Moreover, as a practical application, this proposed electrochemical aptasensor was used to monitor the OTA level in red wine samples without any special pretreatment and with satisfactory results obtained. Study results showed that this electrochemical aptasensor could be a potential useful platform for on-site OTA measurement in real complex samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Heterogeneous Electrochemical Immunoassay of Hippuric Acid on the Electrodeposited Organic Films

PubMed Central

Choi, Young-Bong; Kim, Nam-Hyuk; Kim, Seung-Hoi; Tae, Gun-Sik; Kim, Hyug-Han

2014-01-01

By directly coordinating hippuric acid (HA) to the ferrate (Fe) as an electron transfer mediator, we synthesized a Fe-HA complex, which shows a good electrochemical signal and thus enables the electrochemical immunoanalysis for HA. We electrodeposited organic films containing imidazole groups on the electrode surface and then bonded Ni ion (positive charge) to induce immobilization of Fe-HA (negative charge) through the electrostatic interaction. The heterogeneous competitive immunoassay system relies on the interaction between immobilized Fe-HA antigen conjugate and free HA antigen to its antibody (anti-HA). The electric signal becomes weaker due to the hindered electron transfer reaction when a large-sized HA antibody is bound onto the Fe-HA. However, in the presence of HA, the electric signal increases because free HA competitively reacts with the HA antibody prior to actual reaction and thus prevents the HA antibody from interacting with Fe-HA at the electrode surface. This competition reaction enabled an electrochemical quantitative analysis of HA concentration with a detection limit of 0.5 μg mL−1, and thus allowed us to develop a simple and rapid electrochemical immunosensor. PMID:25313491

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

PubMed

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Electrochemical biosensor based on enzyme substrate as a linker: Application for aldolase activity with pectin-thionine complex as recognization element and signal amplification probe.

PubMed

Wang, Xiaonan; Wang, Meiwen; Zhang, Yuanyuan; Miao, Xiaocao; Huang, Yuanyuan; Zhang, Juan; Sun, Lizhou

2016-09-15

A new strategy to fabricate electrochemical biosensor is reported based on the linkage of enzyme substrate, thereby an electrochemical method to detect aldolase activity is established using pectin-thionine complex (PTC) as recognization element and signal probe. The linkage effect of fructose-1,6-bisphosphate (FBP), the substrate of aldolase, can be achieved via its strong binding to magnetic nanoparticles (MNPs)/aminophenylboronic acid (APBA) and the formation of phosphoramidate bond derived from its reaction with p-phenylenediamine (PDA) on the surface of electrode. Aldolase can reversibly catalyze the substrates into the products which have no binding capacity with MNPs/APBA, resulting in the exposure of the corresponding binding sites and its subsequent recognization on signal probe. Meanwhile, signal amplification can be accomplished by using the firstly prepared PTC which can bind with MNPs/APBA, and accuracy can be strengthened through magnetic separation. With good precision and accuracy, the established sensor may be extended to other proteins with reversible catalyzed ability. Copyright © 2016 Elsevier B.V. All rights reserved.

Organic, Organometallic and Bioorganic Catalysts for Electrochemical Reduction of CO2

PubMed Central

Schlager, Stefanie; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

2017-01-01

Abstract A broad review of homogeneous and heterogeneous catalytic approaches toward CO2 reduction using organic, organometallic, and bioorganic systems is provided. Electrochemical, bioelectrochemical and photoelectrochemical approaches are discussed in terms of their faradaic efficiencies, overpotentials and reaction mechanisms. Organometallic complexes as well as semiconductors and their homogeneous and heterogeneous catalytic activities are compared to enzymes. In both cases, their immobilization on electrodes is discussed and compared to homogeneous catalysts in solution. PMID:28383174

Electrochemically Protected Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

PubMed Central

Hong, Vu; Udit, Andrew K.; Evans, Richard A.; Finn, M.G.

2012-01-01

The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has found broad application in myriad fields. For the most demanding applications requiring high yields at low substrate concentrations, highly active but air-sensitive copper complexes must be used. We describe here the use of an electrochemical potential to maintain catalysts in the active Cu(I) oxidation state in the presence of air. The simple procedure efficiently achieves excellent yields of CuAAC products involving both small molecule and protein substrates without the use of potentially damaging chemical reducing agents. A new water-soluble carboxylated version of the popular tris(benzyltriazolylmethyl)amine (TBTA) ligand is described. Cyclic voltammetry revealed reversible or quasi-reversible electrochemical redox behavior of copper complexes of the TBTA derivative (2; E1/2 = 60 mV vs. Ag/AgCl), sulfonated bathophenanthroline (3; E1/2 = -60 mV), and sulfonated tris(benzimidazoylmethyl)amine (4; E1/2 ~ -70 mV), and showed catalytic turnover to be rapid relative to the voltammetry time scale. Under the influence of a -200 mV potential established using a reticulated vitreous carbon working electrode, CuSO4 and 3 formed a superior catalyst. Electrochemically-protected bioconjugations in air were performed using bacteriophage Qβ derivatized with azide moieties at surface lysine residues. The complete addressing of more than 600 reactive sites per particle was demonstrated within 12 hours of electrolysis with sub-stoichiometric quantities of Cu•3. PMID:18504727

Ammonia release method for depositing metal oxides

DOEpatents

Silver, Gary L.; Martin, Frank S.

1994-12-13

A method of depositing metal oxides on substrates which is indifferent to the electrochemical properties of the substrates and which comprises forming ammine complexes containing metal ions and thereafter effecting removal of ammonia from the ammine complexes so as to permit slow precipitation and deposition of metal oxide on the substrates.

Electrode with transparent series resistance for uniform switching of optical modulation devices

DOEpatents

Tench, D Morgan [Camarillo, CA; Cunningham, Michael A [Thousand Oaks, CA; Kobrin, Paul H [Newbury Park, CA

2008-01-08

Switching uniformity of an optical modulation device for controlling the propagation of electromagnetic radiation is improved by use of an electrode comprising an electrically resistive layer that is transparent to the radiation. The resistive layer is preferably an innerlayer of a wide-bandgap oxide sandwiched between layers of indium tin oxide or another transparent conductor, and may be of uniform thickness, or may be graded so as to provide further improvement in the switching uniformity. The electrode may be used with electrochromic and reversible electrochemical mirror (REM) smart window devices, as well as display devices based on various technologies.

Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes

DOE PAGES

Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.; ...

2017-03-09

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO 2 reduction ability. We reported complexes are of the type Re(N-N)(CO) 3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO 2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO 2 reduction by 1 in acetonitrile using densitymore » functional theory (DFT) supports the C–O bond cleavage step being the rate-determining step (RDS) (ΔG ‡ = 27.2 kcal mol –1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO) 3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (i cat/i p) 2, up to 7 times larger than that of I.« less

Drastic Effect of the Peptide Sequence on the Copper-Binding Properties of Tripeptides and the Electrochemical Behaviour of Their Copper(II) Complexes.

PubMed

Mena, Silvia; Mirats, Andrea; Caballero, Ana B; Guirado, Gonzalo; Barrios, Leoní A; Teat, Simon J; Rodriguez-Santiago, Luis; Sodupe, Mariona; Gamez, Patrick

2018-04-06

The binding and electrochemical properties of the complexes Cu II -HAH, Cu II -HWH, Cu II -Ac-HWH, Cu II -HHW, and Cu II -WHH have been studied by using NMR and UV/Vis spectroscopies, CV, and density functional calculations. The results obtained highlight the importance of the peptidic sequence on the coordination properties and, consequently, on the redox properties of their Cu II complexes. For Cu II -HAH and Cu II -HWH, no cathodic processes are observed up to -1.2 V; that is, the complexes exhibit very high stability towards copper reduction. This behaviour is associated with the formation of very stable square-planar (5,5,6)-membered chelate rings (ATCUN motif), which enclose two deprotonated amides. In contrast, for non-ATCUN Cu II -Ac-HWH, Cu II -HHW complexes, simulations seem to indicate that only one deprotonated amide is enclosed in the coordination sphere. In these cases, the main electrochemical feature is a reductive irreversible one electron-transfer process from Cu II to Cu I , accompanied with structural changes of the metal coordination sphere and reprotonation of the amide. Finally, for Cu II -WHH, two major species have been detected: one at low pH (<5), with no deprotonated amides, and another one at high pH (>10) with an ATCUN motif, both species coexisting at intermediate pH. The present study shows that the use of CV, using glassy carbon as a working electrode, is an ideal and rapid tool for the determination of the redox properties of Cu II metallopeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controllable synthesis of MnO2/polyaniline nanocomposite and its electrochemical capacitive property

PubMed Central

2013-01-01

Polyaniline (PANI) and MnO2/PANI composites are simply fabricated by one-step interfacial polymerization. The morphologies and components of MnO2/PANI composites are modulated by changing the pH of the solution. Formation procedure and capacitive property of the products are investigated by XRD, FTIR, TEM, and electrochemical techniques. We demonstrate that MnO2 as an intermedia material plays a key role in the formation of sample structures. The MnO2/PANI composites exhibit good cycling stability as well as a high capacitance close to 207 F g−1. Samples fabricated with the facile one-step method are also expected to be adopted in other field such as catalysis, lithium ion battery, and biosensor. PMID:23594724

Controllable synthesis of MnO2/polyaniline nanocomposite and its electrochemical capacitive property

NASA Astrophysics Data System (ADS)

Meng, Fanhui; Yan, Xiuling; Zhu, Ye; Si, Pengchao

2013-04-01

Polyaniline (PANI) and MnO2/PANI composites are simply fabricated by one-step interfacial polymerization. The morphologies and components of MnO2/PANI composites are modulated by changing the pH of the solution. Formation procedure and capacitive property of the products are investigated by XRD, FTIR, TEM, and electrochemical techniques. We demonstrate that MnO2 as an intermedia material plays a key role in the formation of sample structures. The MnO2/PANI composites exhibit good cycling stability as well as a high capacitance close to 207 F g-1. Samples fabricated with the facile one-step method are also expected to be adopted in other field such as catalysis, lithium ion battery, and biosensor.

Real space mapping of oxygen vacancy diffusion and electrochemical transformations by hysteretic current reversal curve measurements

DOEpatents

Kalinin, Sergei V.; Balke, Nina; Borisevich, Albina Y.; Jesse, Stephen; Maksymovych, Petro; Kim, Yunseok; Strelcov, Evgheni

2014-06-10

An excitation voltage biases an ionic conducting material sample over a nanoscale grid. The bias sweeps a modulated voltage with increasing maximal amplitudes. A current response is measured at grid locations. Current response reversal curves are mapped over maximal amplitudes of the bias cycles. Reversal curves are averaged over the grid for each bias cycle and mapped over maximal bias amplitudes for each bias cycle. Average reversal curve areas are mapped over maximal amplitudes of the bias cycles. Thresholds are determined for onset and ending of electrochemical activity. A predetermined number of bias sweeps may vary in frequency where each sweep has a constant number of cycles and reversal response curves may indicate ionic diffusion kinetics.

Receiver bandwidth effects on complex modulation and detection using directly modulated lasers.

PubMed

Yuan, Feng; Che, Di; Shieh, William

2016-05-01

Directly modulated lasers (DMLs) have long been employed for short- and medium-reach optical communications due to their low cost. Recently, a new modulation scheme called complex modulated DMLs has been demonstrated showing a significant optical signal to noise ratio sensitivity enhancement compared with the traditional intensity-only detection scheme. However, chirp-induced optical spectrum broadening is inevitable in complex modulated systems, which may imply a need for high-bandwidth receivers. In this Letter, we study the impact of receiver bandwidth effects on the performance of complex modulation and coherent detection systems based on DMLs. We experimentally demonstrate that such systems exhibit a reasonable tolerance for the reduced receiver bandwidth. For 10 Gbaud 4-level pulse amplitude modulation signals, the required electrical bandwidth is as low as 8.5 and 7.5 GHz for 7% and 20% forward error correction, respectively. Therefore, it is feasible to realize DML-based complex modulated systems using cost-effective receivers with narrow bandwidth.

Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

NASA Astrophysics Data System (ADS)

Al-Rashdi, Kamelah S.; Babgi, Bandar A.; Sahin, Cigdem; Eltayeb, Naser E.; Moxey, Graeme J.; Humphrey, Mark G.; Basaleh, Amal S.

2018-04-01

The complex with the formula [Ru(bpy)2(2,3-diaminonaphthalene)][PF6] (5) was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)2(diamine)][PF6]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV-vis absorption spectra of the complexes 2-5 were collected and compared to that of [Ru(bpy)3][PF6]2 (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1-5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1-5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.

Electrochemical-mechanical coupled modeling and parameterization of swelling and ionic transport in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Sauerteig, Daniel; Hanselmann, Nina; Arzberger, Arno; Reinshagen, Holger; Ivanov, Svetlozar; Bund, Andreas

2018-02-01

The intercalation and aging induced volume changes of lithium-ion battery electrodes lead to significant mechanical pressure or volume changes on cell and module level. As the correlation between electrochemical and mechanical performance of lithium ion batteries at nano and macro scale requires a comprehensive and multidisciplinary approach, physical modeling accounting for chemical and mechanical phenomena during operation is very useful for the battery design. Since the introduced fully-coupled physical model requires proper parameterization, this work also focuses on identifying appropriate mathematical representation of compressibility as well as the ionic transport in the porous electrodes and the separator. The ionic transport is characterized by electrochemical impedance spectroscopy (EIS) using symmetric pouch cells comprising LiNi1/3Mn1/3Co1/3O2 (NMC) cathode, graphite anode and polyethylene separator. The EIS measurements are carried out at various mechanical loads. The observed decrease of the ionic conductivity reveals a significant transport limitation at high pressures. The experimentally obtained data are applied as input to the electrochemical-mechanical model of a prismatic 10 Ah cell. Our computational approach accounts intercalation induced electrode expansion, stress generation caused by mechanical boundaries, compression of the electrodes and the separator, outer expansion of the cell and finally the influence of the ionic transport within the electrolyte.

Gold nanoparticles/4-aminothiophenol interfaces for direct electron transfer of horseradish peroxidase: Enzymatic orientation and modulation of sensitivity towards hydrogen peroxide detection.

PubMed

Huerta-Miranda, G A; Arrocha-Arcos, A A; Miranda-Hernández, M

2018-08-01

Hydrogen peroxide electrochemical detection by horseradish peroxidase has been widely studied. The use of gold nanoparticles to prepare electrode/enzyme bioconjugates has attracted attention due to their catalytic properties. In this work, it is reported the use of gold nanoparticles and 4-aminothiophenol as a scaffold to obtain a suitable matrix for enzyme bioconjugation with horseradish peroxidase. A critical factor in biosensors design and development is the enzymatic electrochemical activity understanding. Comparison of voltammetric studies of the heme prosthetic group showed a reversible electrochemical behavior when the enzymes were immobilized in a well-dispersed gold deposit; on the other hand, a discrete redox response was observed on a randomly deposited gold electrode. These results show that the distance between enzymes is essential. Hydrogen peroxide catalysis and the enzymatic behavior were analyzed considering two types of nanoparticles dispositions. The catalytic behavior observed in the well-dispersed nanoparticles configuration suggests a preserved enzyme folding, a decrease of steric impediments, and appears to be a better immobilization strategy. In contrast, the randomly electrodeposited gold electrode decreased the enzyme orientation and the electrochemical activity. The advantages of this methodology are the electrode fabrication affordable cost and the enzymatic direct electron transfer response improvement. Copyright © 2018 Elsevier B.V. All rights reserved.

Novel nanoarchitectures for electrochemical biosensing

NASA Astrophysics Data System (ADS)

Archibald, Michelle M.

Sensitive, real-time detection of biomarkers is of critical importance for rapid and accurate diagnosis of disease for point-of-care (POC) technologies. Current methods, while sensitive, do not adequately allow for POC applications due to several limitations, including complex instrumentation, high reagent consumption, and cost. We have investigated two novel nanoarchitectures, the nanocoax and the nanodendrite, as electrochemical biosensors towards the POC detection of infectious disease biomarkers to overcome these limitations. The nanocoax architecture is composed of vertically-oriented, nanoscale coaxial electrodes, with coax cores and shields serving as integrated working and counter electrodes, respectively. The dendritic structure consists of metallic nanocrystals extending from the working electrode, increasing sensor surface area. Nanocoaxial- and nanodendritic-based electrochemical sensors were fabricated and developed for the detection of bacterial toxins using an electrochemical enzyme-linked immunosorbent assay (ELISA) and differential pulse voltammetry (DPV). Proof-of-concept was demonstrated for the detection of cholera toxin (CT). Both nanoarchitectures exhibited levels of sensitivity that are comparable to the standard optical ELISA used widely in clinical applications. In addition to matching the detection profile of the standard ELISA, these electrochemical nanosensors provide a simple electrochemical readout and a miniaturized platform with multiplexing capabilities toward POC implementation. Further development as suggested in this thesis may lead to increases in sensitivity, enhancing the attractiveness of the architectures for future POC devices.

Comparison on exfoliated graphene nano-sheets and triturated graphite nano-particles for mode-locking the Erbium-doped fibre lasers

NASA Astrophysics Data System (ADS)

Yang, Chun-Yu; Lin, Yung-Hsiang; Wu, Chung-Lun; Cheng, Chih-Hsien; Tsai, Din-Ping; Lin, Gong-Ru

2018-06-01

Comparisons on exfoliated graphene nano-sheets and triturated graphite nano-particles for mode-locking the Erbium-doped fiber lasers (EDFLs) are performed. As opposed to the graphite nano-particles obtained by physically triturating the graphite foil, the tri-layer graphene nano-sheets is obtained by electrochemically exfoliating the graphite foil. To precisely control the size dispersion and the layer number of the exfoliated graphene nano-sheet, both the bias of electrochemical exfoliation and the speed of centrifugation are optimized. Under a threshold exfoliation bias of 3 volts and a centrifugation at 1000 rpm, graphene nano-sheets with an average diameter of 100  ±  40 nm can be obtained. The graphene nano-sheets with an area density of 15 #/µm2 are directly imprinted onto the end-face of a single-mode fiber made patchcord connector inside the EDFL cavity. Such electrochemically exfoliated graphene nano-sheets show comparable saturable absorption with standard single-graphene and perform the self-amplitude modulation better than physically triturated graphite nano-particles. The linear transmittance and modulation depth of the inserted graphene nano-sheets are 92.5% and 53%, respectively. Under the operation with a power gain of 21.5 dB, the EDFL can be passively mode-locked to deliver a pulsewidth of 454.5 fs with a spectral linewidth of 5.6 nm. The time-bandwidth product of 0.31 is close to the transform limit. The Kelly sideband frequency spacing of 1.34 THz is used to calculate the chirp coefficient as  ‑0.0015.

An H₂S Sensor Based on Electrochemistry for Chicken Coops.

PubMed

Zeng, Lihua; He, Mei; Yu, Huihui; Li, Daoliang

2016-08-31

The recent modernization of the livestock industry lags behind the scale of the livestock industry, particularly in indoor environmental monitoring. In particular, the H₂S gas concentration in chicken coops affects the growth and reproductive capacity of the chickens and threatens their health. Therefore, the research and development of a low-cost, environmentally friendly sensor that can achieve on-line monitoring of H₂S gas has a notably important practical significance. This paper reports the design of an H₂S gas sensor, with selection of an electrochemical probe with high accuracy and wide measurement range using the relatively mature technology of electrochemical sensors. Although the probe of the sensor is the main factor that affects the sensor accuracy, the probe must be combined with a specifically designed signal condition circuit that can overcome the lack of an electrode to satisfy the requirements for the interconnection and matching between the output signal and the test instrument. Because the output current of the electrochemical electrode is small and likely to be disturbed by noise, we designed signal-conditioning modules. Through the signal-conditioning circuit, the output signal of the current electrode can be converted into a voltage and amplified. In addition, we designed a power control module because a bias voltage is necessary for the electrode. Finally, after the calibration experiment, the accurate concentration of H₂S gas can be measured. Based on the experimental analysis, the sensor shows good linearity and selectivity, comparatively high sensitivity, perfect stability and an extremely long operating life of up to two years.

Electrochemical Aptamer-Based Sensors for Rapid Point-of-Use Monitoring of the Mycotoxin Ochratoxin A Directly in a Food Stream.

PubMed

Somerson, Jacob; Plaxco, Kevin W

2018-04-15

The ability to measure the concentration of specific small molecules continuously and in real-time in complex sample streams would impact many areas of agriculture, food safety, and food production. Monitoring for mycotoxin taint in real time during food processing, for example, could improve public health. Towards this end, we describe here an inexpensive electrochemical DNA-based sensor that supports real-time monitor of the mycotoxin ochratoxin A in a flowing stream of foodstuffs.

Metal (II) Complexes Derived from Naphthofuran-2-carbohydrazide and Diacetylmonoxime Schiff Base: Synthesis, Spectroscopic, Electrochemical, and Biological Investigation

PubMed Central

Sumathi, R. B.; Halli, M. B.

2014-01-01

A new Schiff base and a new series of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) complexes were synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime. Metal complexes of the Schiff base were prepared from their chloride salts of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) in ethanol. The ligand along with its metal complexes have been characterized on the basis of analytical data, IR, electronic, mass, 1HNMR, ESR spectral data, thermal studies, magnetic susceptibility, and molar conductance measurements. The nonelectrolytic behaviour of the complexes was assessed from the measured low conductance data. The elemental analysis of the complexes confirm the stoichiometry of the type CuL2Cl2 and MLCl2 where M = Ni(II), Co(II), Cd(II), and Hg(II) and L = Schiff base. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In the light of these results, Co(II), Ni(II), and Cu(II) complexes are assigned octahedral geometry, Cd(II), and Hg(II) complexes tetrahedral geometry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleaving capacity of all the complexes was analysed by agarose gel electrophoresis method. PMID:24592203

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 the core concepts from discipline-specific models and theories serve as visual tools to describe reversible redox half-reactions at equilibrium, predict the spontaneity of the electrochemical process and explain interfacial equilibrium between redox species and electrodes in solution. The integration of physics concepts into electrochemistry instruction facilitated describing the interactions between the chemical system (e.g., redox species) and the external circuit (e.g., voltmeter). The "Two worlds" theoretical framework was chosen to anchor a robust educational design where the world of objects and events is deliberately connected to the world of theories and models. The core concepts in Marcus theory and density of states (DOS) provided the scientific foundations to connect both worlds. The design of this teaching sequence involved three phases; the selection of the content to be taught, the determination of a coherent and explicit connection among concepts and the development of educational activities to engage students in the learning process. The reduction-oxidation and electrochemistry chapters of three of the most popular general chemistry textbooks were revised in order to identify potential gaps during instruction, taking into consideration learning and teaching difficulties. The electrochemistry curriculum was decomposed into manageable sections contained in modules. Thirteen modules were developed and each module addresses specific conceptions with regard to terminology, redox reactions in electrochemical cells, and the function of the external circuit in electrochemical process. The electrochemistry teaching sequence was evaluated using a phenomenographic approach. This approach allows describing the qualitative variation in instructors' consciousness about the teaching of electrochemistry. A phenomenographic analysis revealed that the most relevant aspect of variation came from instructors' expertise. Participant A expertise (electrochemist) promoted in-depth discussions of fundamental theories and models that explain the electrochemical process while participant B expertise (general chemistry instruction) emphasized a coherent and explicit presentation of such theories and models to students. Other categories of variation were identified as: recognizing students' conceptions, the use of teaching resources and instructors' expectations for the teaching sequence. For example, while Participant B depended heavily on representations and explanations found in textbooks, participant A recognized misleading representations and oversimplified statements in general chemistry textbooks. Participant A was also more inclined to question the significance of some conceptions such as the correlation between the use of the term circuit and students' conceptions related to the movement of electrons in solution in an electrochemical cell. The electrochemistry teaching sequence in this dissertation fulfils each of the instructors' expectations with regards to the content that incorporated discipline-specific theories and models, explicit connections and flow among concepts, and addressing students' conceptions via the educational activities developed.

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

Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ammonia release method for depositing metal oxides

DOEpatents

Silver, G.L.; Martin, F.S.

1994-12-13

A method is described for depositing metal oxides on substrates which is indifferent to the electrochemical properties of the substrates and which comprises forming ammine complexes containing metal ions and thereafter effecting removal of ammonia from the ammine complexes so as to permit slow precipitation and deposition of metal oxide on the substrates. 1 figure.

Ferrocene Derivatives Included in a Water-Soluble Cavitand: Are They Electroinactive?

PubMed Central

Podkoscielny, Dagmara; Hooley, Richard J.; Rebek, Julius; Kaifer, Angel E.

2009-01-01

The formation in aqueous solution of kinetically stable inclusion complexes between a deep-cavity cavitand and several redox active ferrocene derivatives was demonstrated using 1H NMR spectroscopy. The electrochemical kinetics of the inclusion complexes was strongly attenuated as compared to that observed with the free guests. PMID:18537255

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

Galan, Brandon R.; Wiedner, Eric S.; Helm, Monte L.

Nickel(II) complexes containing chelating N-heterocyclic carbene-phosphine ligands ([NiL2](BPh4)2, for which L = [MeIm(CH2)2PR2]) have been synthesized for the purpose of studying how this class of ligand effects the electrochemical properties compared to the nickel bis- diphosphine analogues. The nickel complexes were synthesized and characterized by x-ray crystallography and electrochemical methods. Based on the half wave potentials (E1/2), substitution of an NHC for one of the phosphines in a diphoshine ligand results in shifts in potential to 0.6 V to 1.2 V more negative than the corresponding nickel bis-diphosphine complexes. These quantitative results highlight the substantial effect that NHC ligands canmore » have upon the electronic properties of the metal complexes. BRG, JCL, and AMA acknowledge the support by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MLH acknoledges the support of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Novel thiourea derivative and its complexes: Synthesis, characterization, DFT computations, thermal and electrochemical behavior, antioxidant and antitumor activities

NASA Astrophysics Data System (ADS)

Yeşilkaynak, Tuncay; Muslu, Harun; Özpınar, Celal; Emen, Fatih Mehmet; Demirdöğen, Ruken Esra; Külcü, Nevzat

2017-08-01

A novel thiourea derivative, N-((2-chloropyridin-3-yl)carbamothioyl) thiophene-2-carboxamide,C11H8ClN3OS2 (HL) and its Co(II), Ni(II) and Cu(II) complexes (ML2 type) were prepared and characterized by elemental analysis, FT-IR,1H NMR and HR-MS methods. The crystal structure of HL was also investigated by single crystal X-ray diffraction study. The HL crystallizes in the orthorhombic crystal system with P 21 21 21 space group, Z = 4, a = 3.8875(3) Å, b = 14.6442(13) Å, c = 21.8950(19) Å. The [ML2] complex structures were optimized by using B97D/TZVP level. Molecular orbitals of HL ligand were calculated at the same level. Thermal and electrochemical behaviors of the complexes were investigated. Anticancer and antioxidant activities of the complexes were also investigated. Antioxidant activities were determined by using DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2‧-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) assays. Anticancer activities were studied via MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay in MCF-7 (Michigan Cancer Foundation-7) breast cancer cells.

Optical and electrochemical characteristics of Ir(III) complexes with metalated 4-(4-bromophenyl)-2-methyl-1,3-thiazole and isocyanide, ethylenediamine, and diethyldithiocarbamate ligands

NASA Astrophysics Data System (ADS)

Katlenok, E. A.; Kinzhalov, M. A.; Eremina, A. A.; Balashev, K. P.

2017-05-01

The influence of donor-acceptor properties of tert-butyl-, 2.6-dimethylphenyl-, and 4-bromophenyl-isocyanides (BuNC, XylNC, BpNC), ethylenediamine (En), and diethyldithiocarbamate ions (Dtc-) on the 1H and 13C NMR, IR, optical, and electrochemical characteristics of Ir(III) complexes with metalated 4-(4-bromophenyl)-2-methyl-1,3-thiazole is studied. Enhancement of the donor properties of BpNC, XylNC, BuNC, En, and Dtc- ligands leads to a bathochromic shift of metal-to-ligand charge transfer (MLCT) bands and to a decrease in the difference between the one-electron oxidation and reduction potentials of complexes. The bathochromic shift of the low-temperature phosphorescence of complexes in frozen (77 K) solutions with increasing donor properties of BpNC, XylNC, BuNC, En, and Dtc-ligands is caused by a decrease in the admixture of MLCT to the intraligand excited state of {Ir(bptz)2}. Quenching of the phosphorescence of complexes in liquid solutions is attributed to the thermally-induced population of excited d- d* states with subsequent nonradiative deactivation.

Phenyl substitution of cationic bis-cyclometalated iridium(iii) complexes for iTMC-LEECs.

PubMed

Suhr, Kristin J; Bastatas, Lyndon D; Shen, Yulong; Mitchell, Lauren A; Frazier, Gary A; Taylor, David W; Slinker, Jason D; Holliday, Bradley J

2016-11-28

A series of seven cationic bis-cyclometalated iridium(iii) complexes of the form [(C^N) 2 (N^N)Ir][PF 6 ] has been designed in order to examine the effect of bulky, hydrophobic phenyl substituents on the structure-property relationship of these ionic transition metal complexes (iTMCs) in light-emitting electrochemical cells (LEECs). Capping phenyl substituents on the cyclometalating and ancillary ligands allows for individual tuning of the HOMO and LUMO energy levels, respectively, yielding an emission range from yellow to red. The complexes in this series exhibit increased quantum yields, up to 70% higher than the unoptimized, archetypal [(2-phenylpyridine) 2 (2,2'-bipyridine)Ir][PF 6 ]. Among these, one complex, C3, was recently reported to produce devices with superior luminance and efficiency. Simultaneous measure of the series of complexes enabled the clear discernment of trends in device performance connected to fundamental structure-property relationships that elucidate the origin of enhanced luminance. In general, phenyl substitution of the 2-phenylpyridine ligands of the parent complex produced higher luminance and faster device response than phenyl substitution of the 2,2'-bipyridine ligand. Overall, complex design and device engineering produce competitive LEECs from simple, single-layer architectures. The synthesis, crystallographic, photophysical, and electrochemical properties of the iTMCs, along with the electroluminescence properties of the LEEC devices are reported herein.

Antitumor effects of electrochemical treatment

PubMed Central

González, Maraelys Morales; Zamora, Lisset Ortíz; Cabrales, Luis Enrique Bergues; Sierra González, Gustavo Victoriano; de Oliveira, Luciana Oliveira; Zanella, Rodrigo; Buzaid, Antonio Carlos; Parise, Orlando; Brito, Luciana Macedo; Teixeira, Cesar Augusto Antunes; Gomes, Marina das Neves; Moreno, Gleyce; Feo da Veiga, Venicio; Telló, Marcos; Holandino, Carla

2013-01-01

Electrochemical treatment is an alternative modality for tumor treatment based on the application of a low intensity direct electric current to the tumor tissue through two or more platinum electrodes placed within the tumor zone or in the surrounding areas. This treatment is noted for its great effectiveness, minimal invasiveness and local effect. Several studies have been conducted worldwide to evaluate the antitumoral effect of this therapy. In all these studies a variety of biochemical and physiological responses of tumors to the applied treatment have been obtained. By this reason, researchers have suggested various mechanisms to explain how direct electric current destroys tumor cells. Although, it is generally accepted this treatment induces electrolysis, electroosmosis and electroporation in tumoral tissues. However, action mechanism of this alternative modality on the tumor tissue is not well understood. Although the principle of Electrochemical treatment is simple, a standardized method is not yet available. The mechanism by which Electrochemical treatment affects tumor growth and survival may represent more complex process. The present work analyzes the latest and most important research done on the electrochemical treatment of tumors. We conclude with our point of view about the destruction mechanism features of this alternative therapy. Also, we suggest some mechanisms and strategies from the thermodynamic point of view for this therapy. In the area of Electrochemical treatment of cancer this tool has been exploited very little and much work remains to be done. Electrochemical treatment constitutes a good therapeutic option for patients that have failed the conventional oncology methods. PMID:23592904

Main chemical species and molecular structure of deep eutectic solvent studied by experiments with DFT calculation: a case of choline chloride and magnesium chloride hexahydrate.

PubMed

Zhang, Chao; Jia, Yongzhong; Jing, Yan; Wang, Huaiyou; Hong, Kai

2014-08-01

The infrared spectrum of deep eutectic solvent of choline chloride and magnesium chloride hexahydrate was measured by the FTIR spectroscopy and analyzed with the aid of DFT calculations. The main chemical species and molecular structure in deep eutectic solvent of [MgClm(H2O)6-m]2-m and [ChxCly]x+y complexes were mainly identified and the active ion of magnesium complex during the electrochemical process was obtained. The mechanism of the electrochemical process of deep eutectic solvent of choline chloride and magnesium chloride hexahydrate was well explained by combination theoretical calculations and experimental. Besides, based on our results we proposed a new system for the dehydration study of magnesium chloride hexahydrate.

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

DOE PAGES

Ellis, Ross J.; Bera, Mrinal K.; Reinhart, Benjamin; ...

2016-11-07

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, thismore » presents a new route for controlling anion transfer in electrochemically-driven separation applications.« less

Electrochemical Synthesis of Amorphous VO2 Colloids and Their Rapid Thermal Transforming to VO2 (M) Nanoparticles with Good Thermochromic Performance.

PubMed

Wu, Hao; Li, Ming; Zhong, Li; Luo, Yuan Yuan; Li, Guang Hai

2016-12-05

Amorphous VO 2 (a-VO 2 ) colloids were synthesized by electrochemical anodic oxidation of metallic vanadium. It was found that the a-VO 2 colloids have a cotton-like morphology composed of very small clusters, and that the crystallization temperature of the a-VO 2 colloids can be adjusted either by the electrolyte of the anodic oxidation or/and the dispersion agent of the colloids. VO 2 (M) nanoparticles (NPs) (and a NP film) with an average size of about 50 nm can be obtained by a rapid thermal annealing of the a-VO 2 colloids at 310 °C under air, which is beneficial for practical applications. The VO 2 (M) NP film shows an obvious metal-semiconductor transition with a resistance less than 10 Ω in the metallic state. An integral visible transmittance of 40.7 %, a solar transmittance modulation of 9.4 %, and a resistance modulation in the order of 5×10 4 were realized in the VO 2 (M) NP film. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validation of Electrochemically Modulated Separations Performed On-Line with MC-ICP-MS for Uranium and Plutonium Isotopic Analyses

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

Liezers, Martin; Olsen, Khris B.; Mitroshkov, Alexandre V.

2010-08-11

The most time consuming process in uranium or plutonium isotopic analyses is performing the requisite chromatographic separation of the actinides. Filament preparation for thermal ionization (TIMS) adds further delays, but is generally accepted due to the unmatched performance in trace isotopic analyses. Advances in Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) are beginning to rival the performance of TIMS. Methods, such as Electrochemically Modulated Separations (EMS) can efficiently pre-concentrate U or Pu quite selectively from small solution volumes in a matrix of 0.5 M nitric acid. When performed in-line with ICP-MS, the rapid analyte release from the electrode is fast,more » and large transient analyte signal enhancements of >100 fold can be achieved as compared to more conventional continuous nebulization of the original starting solution. This makes the approach ideal for very low level isotope ratio measurements. In this paper, some aspects of EMS performance are described. These include low level Pu isotope ratio behavior versus concentration by MC-ICP-MS and uranium rejection characteristics that are also important for reliable low level Pu isotope ratio determinations.« less

Complex Burn Region Module (CBRM) update

NASA Technical Reports Server (NTRS)

Adams, Carl L.; Jenkins, Billy

1991-01-01

Presented here is a Complex Burn Region Module (CBRM) update for the Solid Rocket Internal Ballistics Module (SRIBM) Program for the Advanced Solid Rocket Motor (ASRM) design/performance assessments. The goal was to develop an improved version of the solid rocket internal ballistics module program that contains a diversified complex region model for motor grain design, performance prediction, and evaluation.

Non-Invasive Breast Cancer Diagnosis through Electrochemical Biosensing at Different Molecular Levels

PubMed Central

Campuzano, Susana

2017-01-01

The rapid and accurate determination of specific circulating biomarkers at different molecular levels with non- or minimally invasive methods constitutes a major challenge to improve the breast cancer outcomes and life quality of patients. In this field, electrochemical biosensors have demonstrated to be promising alternatives against more complex conventional strategies to perform fast, accurate and on-site determination of circulating biomarkers at low concentrations in minimally treated body fluids. In this article, after discussing briefly the relevance and current challenges associated with the determination of breast cancer circulating biomarkers, an updated overview of the electrochemical affinity biosensing strategies emerged in the last 5 years for this purpose is provided highlighting the great potentiality of these methodologies. After critically discussing the most interesting features of the electrochemical strategies reported so far for the single or multiplexed determination of such biomarkers with demonstrated applicability in liquid biopsy analysis, existing challenges still to be addressed and future directions in this field will be pointed out. PMID:28858236

Electrochemical Performance of Glucose/Oxygen Biofuel Cells Based on Carbon Nanostructures.

PubMed

Koo, Min-Hye; Das, Gautam; Yoon, Hyon Hee

2016-03-01

The electrochemical performance of glucose/oxygen biofuel cells based on carbon nanostructures was investigated in the present study. Different types of carbon nanomaterials, including multi-walled carbon nanotubes (MWCNT), functionalized MWCNT (f-MWCNT), carbon nanofibers (CNF), and functionalized CNF (f-CNF) were examined for electrode fabrications. The anode for glucose/oxygen biofuel cells were prepared by sequential coating of carbon nanomaterials, charge transfer complex (CTC), glucose oxidase (GOx) and nafion membrane. The anode was then integrated with a bilirubin oxidase-immobilized cathode for the biofuel cell test. It was found that the electrochemical performance of the enzyme electrodes was remarkably enhanced by the amalgamation of carbon nanomaterials with the CTC. The biofuel cell with anode comprising of f-CNF and the cathode with MWCNT exhibited the best electrochemical performance with a maximum power density of 210 μW/cm2 at a cell voltage of 0.44 V for 20 mM glucose concentration, which is comparable with the best power density value reported earlier.

An electrochemical sensor based on nitrogen doped carbon material prepared from nitrogen-containing precursors

NASA Astrophysics Data System (ADS)

Cui, G. Y.; Wang, C. Y.; Xiang, G. Q.; Zhou, B.

2018-01-01

In this work, a nitrogen doped carbon material (NDC) was prepared by using a copper adenine complex as precursor and applied to electrochemical sensing of Vitamin B2 (VB2). The experimental results show that the nitrogen doped carbon material is obtained after calcination at 650 °C under argon atmosphere, afterwards, which were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), fourier transform infrared (FT-IR), and electrochemical method. According to the XRD data, the product was a carbon material, and infrared data demonstrates that there are two kinds of carbonyl nitrogen combination, respectively, C-N and C = N combination of ways. Importantly, we used NDC to construct electrochemical biosensor to detect VB2 by differential pulse voltammetry (DPV). The linear range was 6 × 10-6 - 3.5 × 10-4 M (R=0.9962), the minimum detection limit was 5.4 × 10-6 M, and the sensitivity is better. Consequently, it has better sensing performance.

Electrochemistry of redox-active self-assembled monolayers

PubMed Central

Eckermann, Amanda L.; Feld, Daniel J.; Shaw, Justine A.; Meade, Thomas J.

2010-01-01

Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redox-activated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C60). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs. PMID:20563297

Continuous, Real-Time Monitoring of Cocaine in Undiluted Blood Serum via a Microfluidic, Electrochemical Aptamer-Based Sensor

PubMed Central

Swensen, James S.; Xiao, Yi; Ferguson, Brian S.; Lubin, Arica A.; Lai, Rebecca Y.; Heeger, Alan J.; Plaxco, Kevin W.; Soh, H. Tom.

2009-01-01

The development of a biosensor system capable of continuous, real-time measurement of small-molecule analytes directly in complex, unprocessed aqueous samples has been a significant challenge, and successful implementation has been achieved for only a limited number of targets. Towards a general solution to this problem, we report here the Microfluidic Electrochemical Aptamer-based Sensor (MECAS) chip wherein we integrate target-specific DNA aptamers that fold, and thus generate an electrochemical signal, in response to the analyte with a microfluidic detection system. As a model, we demonstrate the continuous, real-time (~1 minute time resolution) detection of the small molecule drug cocaine at near physiological, low micromolar concentrations directly in undiluted, otherwise unmodified blood serum. We believe our approach of integrating folding-based electrochemical sensors with miniaturized detection systems may lay the ground work for the real-time, point-of-care detection of a wide variety of molecular targets. PMID:19271708

Removal of arsenic, phosphates and ammonia from well water using electrochemical/chemical methods and advanced oxidation: a pilot plant approach.

PubMed

Orescanin, Visnja; Kollar, Robert; Nad, Karlo; Halkijevic, Ivan; Kuspilic, Marin; Findri Gustek, Stefica

2014-01-01

The purpose of this work was to develop a pilot plant purification system and apply it to groundwater used for human consumption, containing high concentrations of arsenic and increased levels of phosphates, ammonia, mercury and color. The groundwater used was obtained from the production well in the Vinkovci County (Eastern Croatia). Due to a complex composition of the treated water, the purification system involved a combined electrochemical treatment, using iron and aluminum electrode plates with simultaneous ozonation, followed by a post-treatment with UV, ozone and hydrogen peroxide. The removal of the contaminant with the waste sludge collected during the electrochemical treatment was also tested. The combined electrochemical and advanced oxidation treatment resulted in the complete removal of arsenic, phosphates, color, turbidity, suspended solids and ammonia, while the removal of other contaminants of interest was up to 96.7%. Comparable removal efficiencies were obtained by using waste sludge as a coagulant.

Electrochemical analysis of gold-coated magnetic nanoparticles for detecting immunological interaction

NASA Astrophysics Data System (ADS)

Pham, Thao Thi-Hien; Sim, Sang Jun

2010-01-01

An electrochemical impedance immunosensor was developed for detecting the immunological interaction between human immunoglobulin (IgG) and protein A from Staphylococcus aureus based on the immobilization of human IgG on the surface of modified gold-coated magnetic nanoparticles. The nanoparticles with an Au shell and Fe oxide cores were functionalized by a self-assembled monolayer of 11-mercaptoundecanoic acid. The electrochemical analysis was conducted on the modified magnetic carbon paste electrodes with the nanoparticles. The magnetic nanoparticles were attached to the surface of the magnetic carbon paste electrodes via magnetic force. The cyclic voltammetry technique and electrochemical impedance spectroscopy measurements of the magnetic carbon paste electrodes coated with magnetic nanoparticles-human IgG complex showed changes in its alternating current (AC) response both after the modification of the surface of the electrode and the addition of protein A. The immunological interaction between human IgG on the surface of the modified magnetic carbon paste electrodes and protein A in the solution could be successfully monitored.

Electrochemistry and electron paramagnetic resonance spectroscopy of cytochrome c and its heme-disrupted analogs.

PubMed

Novak, David; Mojovic, Milos; Pavicevic, Aleksandra; Zatloukalova, Martina; Hernychova, Lenka; Bartosik, Martin; Vacek, Jan

2018-02-01

Cytochrome c (cyt c) is one of the most studied conjugated proteins due to its electron-transfer properties and ability to regulate the processes involved in homeostasis or apoptosis. Here we report an electrochemical strategy for investigating the electroactivity of cyt c and its analogs with a disrupted heme moiety, i.e. apocytochrome c (acyt c) and porphyrin cytochrome c (pcyt c). The electrochemical data are supplemented with low-temperature and spin-probe electron paramagnetic resonance (EPR) spectroscopy. The main contribution of this report is a complex evaluation of cyt c reduction and oxidation at the level of surface-localized amino acid residues and the heme moiety in a single electrochemical scan. The electrochemical pattern of cyt c is substantially different to both analogs acyt c and pcyt c, which could be applicable in further studies on the redox properties and structural stability of cytochromes and other hemeproteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

PubMed

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Tribocorrosion Performance of Cr/GLC Multilayered Films for Marine Protective Application.

PubMed

Li, Lei; Liu, Lin-Lin; Li, Xiaowei; Guo, Peng; Ke, Peiling; Wang, Aiying

2018-04-18

The corrosion and tribology are all closely related to the interface/surface of materials, which are extremely important for the mechanical components used in harsh marine environments. In this work, we fabricated Cr/graphite-like carbon (GLC) multilayered films with different modulation periods on the 316L stainless steels by direct current magnetron sputtering. Tribocorrosion tests in artificial seawater show that the tribocorrosion resistance of the Cr/GLC films is improved as the modulation period decreases from 1000 to 333 nm and then drastically drops with further decreasing to 250 nm. By taking a top-layer thickening strategy for the Cr/GLC film with 250 nm modulation period, the tribocorrosion performance is significantly enhanced. The corresponded mechanisms are discussed in terms of the film structure and electrochemical corrosion behavior.

New Cu (II), Co(II) and Ni(II) complexes of chalcone derivatives: Synthesis, X-ray crystal structure, electrochemical properties and DFT computational studies

NASA Astrophysics Data System (ADS)

Tabti, Salima; Djedouani, Amel; Aggoun, Djouhra; Warad, Ismail; Rahmouni, Samra; Romdhane, Samir; Fouzi, Hosni

2018-03-01

The reaction of nickel(II), copper(II) and cobalt(II) with 4-hydroxy-3-[(2E)-3-(1H-indol-3-yl)prop-2-enoyl]-6-methyl-2H-pyran-2-one (HL) leads to a series of new complexes: Ni(L)2(NH3), Cu(L)2(DMF)2 and Co(L)2(H2O). The crystal structure of the Cu(L)2(DMF)2 complex have been determined by X-ray diffraction methods. The Cu(II) lying on an inversion centre is coordinated to six oxygen atoms forming an octahedral elongated. Additionally, the electrochemical behavior of the metal complexes were investigated by cyclic voltammetry at a glassy carbon electrode (GC) in CH3CN solutions, showing the quasi-reversible redox process ascribed to the reduction of the MII/MI couples. The X-ray single crystal structure data of the complex was matched excellently with the optimized monomer structure of the desired compound; Hirschfeld surface analysis supported the packed crystal lattice 3D network intermolecular forces. HOMO/LUMO energy level and the global reactivity descriptors quantum parameters are also calculated. The electrophilic and nucleophilic potions in the complex surface are theoretically evaluated by molecular electrostatic potential and Mulliken atomic charges analysis.

Di/mono-nuclear iron(I)/(II) complexes as functional models for the 2Fe2S subunit and distal Fe moiety of the active site of [FeFe] hydrogenases: protonations, molecular structures and electrochemical properties.

PubMed

Gao, Shang; Fan, Jiangli; Sun, Shiguo; Song, Fengling; Peng, Xiaojun; Duan, Qian; Jiang, Dayong; Liang, Qingcheng

2012-10-21

Di/mono-nuclear iron(I)/(II) complexes containing conjugated and electron-withdrawing S-to-S linkers, [{(μ-S)(2)(C(4)N(2)H(2))}Fe(2)(CO)(6)] (1), [{(μ-S)(2)(C(4)N(2)H(2))}Fe(2)(CO)(5)(PMe(3))] (1P), and [{(μ-S)(2)(C(4)N(2)H(2))}Fe(CO)(2)(PMe(3))(2)] (2) were prepared as biomimetic models for the 2Fe2S subunit and distal Fe moiety of the active site of [FeFe] hydrogenases. The N atoms in the heterocyclic pyrazines of 1 and 2 were protonated in the presence of proton acid to generate one and two hydrides, [1(NH)](+) CF(3)SO(3)(-), [2(NH)](+) CF(3)SO(3)(-), and [2(NH)(2)](2+) (CF(3)SO(3)(-))(2), respectively. The protonation processes were evidenced by in situ IR and NMR spectroscopy. The molecular structures of the protonated species [1(NH)](+) CF(3)SO(3)(-) and [2(NH)(2)](2+) (CF(3)SO(3)(-))(2) together with their originating complexes and , and the mono-PMe(3) substituted diiron complex were identified by X-ray crystallography. The IR and single-crystal analysis data all suggested that the electron-withdrawing bridge, pyrazine, led to decreased electron density at the Fe centers of the model complexes, which was consistent with the electrochemical studies. The cyclic voltammograms indicated that complex exhibited a low primary reduction potential at -1.17 V vs. Fc-Fc(+) with a 270 mV positive shift compared with that of the benzene-1,2-dithiolate (bdt) bridged analogue [(μ-bdt)Fe(2)(CO)(6)]. Under the weak acid conditions, complexes 1 and 2 could electrochemically catalyze the proton reduction. More interestingly, the mononuclear ferrous complex 2 showed two catalytic peaks during the formation of hydrogen, confirming its potential as a catalyst for hydrogen production.

Electrochemically protected copper(I)-catalyzed azide-alkyne cycloaddition.

PubMed

Hong, Vu; Udit, Andrew K; Evans, Richard A; Finn, M G

2008-06-16

The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has found broad application in myriad fields. For the most demanding applications that require high yields at low substrate concentrations, highly active but air-sensitive copper complexes must be used. We describe here the use of an electrochemical potential to maintain catalysts in the active Cu(I) oxidation state in the presence of air. This simple procedure efficiently achieves excellent yields of CuAAC products from both small-molecule and protein substrates without the use of potentially damaging chemical reducing agents. A new water-soluble carboxylated version of the popular tris(benzyltriazolylmethyl)amine (TBTA) ligand is also described. Cyclic voltammetry revealed reversible or quasi-reversible electrochemical redox behavior of copper complexes of the TBTA derivative (2; E(1/2)=60 mV vs. Ag/AgCl), sulfonated bathophenanthroline (3; E(1/2)=-60 mV), and sulfonated tris(benzimidazoylmethyl)amine (4; E(1/2) approximately -70 mV), and showed catalytic turnover to be rapid relative to the voltammetry time scale. Under the influence of a -200 mV potential that was established by using a reticulated vitreous carbon working electrode, CuSO4 and 3 formed a superior catalyst. Electrochemically protected bioconjugations in air were performed by using bacteriophage Qbeta that was derivatized with azide moieties at surface lysine residues. Complete derivatization of more than 600 reactive sites per particle was demonstrated within 12 h of electrolysis with substoichiometric quantities of Cu3.

Influence of temperature on the aging behavior of 18650-type lithium ion cells: A comprehensive approach combining electrochemical characterization and post-mortem analysis

NASA Astrophysics Data System (ADS)

Friesen, Alex; Mönnighoff, Xaver; Börner, Markus; Haetge, Jan; Schappacher, Falko M.; Winter, Martin

2017-02-01

The understanding of the aging behavior of lithium ion batteries in automotive and energy storage applications is essential for the acceptance of the technology. Therefore, aging experiments were conducted on commercial 18650-type state-of-the-art cells to determine the influence of the temperature during electrochemical cycling on the aging behavior of the different cell components. The cells, based on Li(Ni0.5Co0.2Mn0.3)O2 (NCM532)/graphite, were aged at 20 °C and 45 °C to different states of health. The electrochemical performance of the investigated cells shows remarkable differences depending on the cycling temperature. At contrast to the expected behavior, the cells cycled at 45 °C show a better electrochemical performance over lifetime than the cells cycled at 20 °C. Comprehensive post-mortem analyses revealed the main aging mechanisms, showing a complex interaction between electrodes and electrolyte. The main aging mechanisms of the cells cycled at 45 °C differ strongly at contrast to cells cycled at 20 °C. A strong correlation between the formed SEI, the electrolyte composition and the electrochemical performance over lifetime was observed.

Enrichment of Pyrrolic Nitrogen by Hole Defects in Nitrogen and Sulfur Co-Doped Graphene Hydrogel for Flexible Supercapacitors.

PubMed

Tran, Ngoc Quang; Kang, Bong Kyun; Woo, Moo Hyun; Yoon, Dae Ho

2016-08-23

The effect of the doping configuration and concentration of nitrogen (N) and sulfur (S) on the electrochemical performance of 3 D N and S co-doped hole defect graphene hydrogel (NS-HGH) electrodes is investigated. Surprisingly, by introducing a hole defect on the graphene surface, the difference in the doping concentrations of N and S can be used to effectively modulate the electrochemical behavior of the NS-HGH. The hole defects provide a rapid ion diffusion path. Finally, we showed that the intriguing specific capacitance (536 F g(-1) ) of the NS-HGH could enhance the overall performance of the pseudocapacitance and electric double layer capacitance. The rational design of the NS-HGH-based flexible solid state supercapacitor results in not only outstanding electrochemical performance with a maximum energy density of 14.8 Wh kg(-1) and power density of 5.2 KW kg(-1) but also in extraordinary mechanical flexibility and excellent cycle stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

GO/PEDOT:PSS nanocomposites: effect of different dispersing agents on rheological, thermal, wettability and electrochemical properties

NASA Astrophysics Data System (ADS)

Giuri, Antonella; Masi, Sofia; Colella, Silvia; Listorti, Andrea; Rizzo, Aurora; Liscio, Andrea; Treossi, Emanuele; Palermo, Vincenzo; Gigli, Giuseppe; Mele, Claudio; Esposito Corcione, Carola

2017-04-01

In this work glucose (G), α-cyclodextrin (α-CD) and sodium salt of carboxymethyl cellulose (CMCNa) are used as dispersing agents for graphene oxide (GO), exploring the influence of both saccharide units and geometric/steric hindrance on the rheological, thermal, wettability and electrochemical properties of a GO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) nanocomposite. By acting on the saccharide-based additives, we can modulate the rheological, thermal, and wettability properties of the GO/PEDOT:PSS nanocomposite. Firstly, the influence of all the additives on the rheological behaviour of GO and PEDOT:PSS was investigated separately in order to understand the effect of the dispersing agent on both the components of the ternary nanocomposite, individually. Subsequently, steady shear and dynamic frequency tests were conducted on all the nanocomposite solutions, characterized by thermal, wettability and morphological analysis. Finally, the electrochemical properties of the GO/PEDOT composites with different dispersing agents for supercapacitors were investigated using cyclic voltammetry (CV). The CV results revealed that GO/PEDOT with glucose exhibited the highest specific capacitance among the systems investigated.

High-performance, polymer-based direct cellular interfaces for electrical stimulation and recording

NASA Astrophysics Data System (ADS)

Kim, Seong-Min; Kim, Nara; Kim, Youngseok; Baik, Min-Seo; Yoo, Minsu; Kim, Dongyoon; Lee, Won-June; Kang, Dong-Hee; Kim, Sohee; Lee, Kwanghee; Yoon, Myung-Han

2018-04-01

Due to the trade-off between their electrical/electrochemical performance and underwater stability, realizing polymer-based, high-performance direct cellular interfaces for electrical stimulation and recording has been very challenging. Herein, we developed transparent and conductive direct cellular interfaces based on a water-stable, high-performance poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) film via solvent-assisted crystallization. The crystallized PEDOT:PSS on a polyethylene terephthalate (PET) substrate exhibited excellent electrical/electrochemical/optical characteristics, long-term underwater stability without film dissolution/delamination, and good viability for primarily cultured cardiomyocytes and neurons over several weeks. Furthermore, the highly crystallized, nanofibrillar PEDOT:PSS networks enabled dramatically enlarged surface areas and electrochemical activities, which were successfully employed to modulate cardiomyocyte beating via direct electrical stimulation. Finally, the high-performance PEDOT:PSS layer was seamlessly incorporated into transparent microelectrode arrays for efficient, real-time recording of cardiomyocyte action potentials with a high signal fidelity. All these results demonstrate the strong potential of crystallized PEDOT:PSS as a crucial component for a variety of versatile bioelectronic interfaces.

Low pCO2 Air-Polarized CO2 Concentrator Development

NASA Technical Reports Server (NTRS)

Schubert, Franz H.

1997-01-01

Life Systems completed a Ground-based Space Station Experiment Development Study Program which verifies through testing the performance and applicability of the electrochemical Air-Polarized Carbon Dioxide Concentrator (APC) process technology for space missions requiring low (i.e., less than 3 mm Hg) CO2 partial pressure (pCO2) in the cabin atmosphere. Required test hardware was developed and testing was accomplished at an approximate one-person capacity CO2 removal level. Initially, two five-cell electrochemical modules using flight-like 0.5 sq ft cell hardware were tested individually, following by their testing at the integrated APC system level. Testing verified previously projected performance and established a database for sizing of APC systems. A four person capacity APC system was sized and compared with four candidate CO2 removal systems. At its weight of 252 lb, a volume of 7 cu ft and a power consumption of 566 W while operating at 2.2 mm Hg pCO2, the APC was surpassed only by an Electrochemical Depolarized CO2 Concentrator (EDC) (operating with H2), when compared on a total equivalent basis.

Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

NASA Astrophysics Data System (ADS)

Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

2017-07-01

We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

Transforming exoelectrogens for biotechnology using synthetic biology.

PubMed

TerAvest, Michaela A; Ajo-Franklin, Caroline M

2016-04-01

Extracellular electron transfer pathways allow certain bacteria to transfer energy between intracellular chemical energy stores and extracellular solids through redox reactions. Microorganisms containing these pathways, exoelectrogens, are a critical part of microbial electrochemical technologies that aim to impact applications in bioenergy, biosensing, and biocomputing. However, there are not yet any examples of economically viable microbial electrochemical technologies due to the limitations of naturally occurring exoelectrogens. Here we first briefly summarize recent discoveries in understanding extracellular electron transfer pathways, then review in-depth the creation of customized and novel exoelectrogens for biotechnological applications. We analyze engineering efforts to increase current production in native exoelectrogens, which reveals that modulating certain processes within extracellular electron transfer are more effective than others. We also review efforts to create new exoelectrogens and highlight common challenges in this work. Lastly, we summarize work utilizing engineered exoelectrogens for biotechnological applications and the key obstacles to their future development. Fueled by the development of genetic tools, these approaches will continue to expand and genetically modified organisms will continue to improve the outlook for microbial electrochemical technologies. © 2015 Wiley Periodicals, Inc.

Heterobimetallic acetylide bridged Cu(I)/Ru(II)-halide/pseudohalide hybrid complexes: Synthesis, structural characterization, luminescence and electrochemical studies

NASA Astrophysics Data System (ADS)

Lolage, Sanjay; Pawal, Sandip; Chavan, Sanjay

2018-01-01

A new series of heterobimetallic complexes [Cu(PPh3)(NC5H4HCdbnd NC6H4Ctbnd CC6H4Ctbnd CRu (dppe)2Cl)X] (1a-5a) have been prepared by the reaction of trans-(NC5H4HCdbnd NC6H4Ctbnd CC6H4Ctbnd C Ru(dppe)2Cl) with copper salts in presence of triphenylphosphine (where X = Cl, Br, I, N3, NCS). Our synthetic attempts and successes are discussed in combination with spectroscopic and electronic characterization of the compounds. Comparison between halides and pseudohalides were studied by thermal and electrochemical analysis where, thermally robust complexes demonstrate quasireversible redox behaviour analogous to CuI/II/RuII/III couple. Room temperature luminescence with varying electron donating and quenching abilities of halides and pseudohalides in blue-green region were observed. Concentration and solvent dependant emission displays positive solvatochromism at ambient temperature.

Label-free signal-on aptasensor for sensitive electrochemical detection of arsenite.

PubMed

Cui, Lin; Wu, Jie; Ju, Huangxian

2016-05-15

A signal-on aptasensor was fabricated for highly sensitive and selective electrochemical detection of arsenite with a label-free Ars-3 aptamer self-assembled on a screen-printed carbon electrode (SPCE) via Au-S bond. The Ars-3 aptamer could adsorb cationic polydiallyldimethylammonium (PDDA) via electrostatic interaction to repel other cationic species. In the presence of arsenite, the change of Ars-3 conformation due to the formation of Ars-3/arsenite complex led to less adsorption of PDDA, and the complex could adsorb more positively charged [Ru(NH3)6](3+) as an electrochemically active indicator on the aptasensor surface, which produced a sensitive "turn-on" response. The target-induced structure switching could be used for sensitive detection of arsenite with a linear range from 0.2 nM to 100 nM and a detection limit down to 0.15 nM. Benefiting from Ars-3 aptamer, the proposed system exhibited excellent specificity against other heavy metal ions. The SPCE-based aptasensor exhibited the advantages of low cost and simple fabrication, providing potential application of arsenite detection in environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

PubMed

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

Electrochemical preparation of nanostructured lanthanum using lanthanum chloride as a precursor in 1-butyl-3-methylimidazolium dicyanamide ionic liquid.

PubMed

Zhang, Q B; Yang, C; Hua, Y X; Li, Y; Dong, P

2015-02-14

Nanostructured lanthanum was electrochemically prepared on a platinum (Pt) substrate in the room temperature ionic liquid 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA) containing anhydrous LaCl3 at 333 K. The electrochemical reduction behavior of La(iii) was investigated using cyclic voltammetry and chronoamperometry techniques. Cyclic voltammogram revealed that the reduction of La(iii) in BMI-DCA involved an irreversible process controlled by diffusion. Chronoamperometric transient analysis confirmed the diffusion controlled electrodeposition process with the diffusion coefficient of La(iii) species in the range of 10(-10) cm(2) s(-1). The strong complexing capability of DCA(-) anions facilitated the displacement of chloride ligands and induced the solubility of LaCl3. The subsequent coordination of La(iii) and DCA(-) anions forming [La(DCA)4](-) complex anions was monitored by designing amperometric titration experiments. Potentiostatically deposited La-deposits with different nanostructures were characterized by SEM, XRD and XPS analyses. The electrodeposition potential was found to play an important role in controlling the nucleation and growth kinetics of the nanocrystal during the electrodeposition process. Depending on the deposition potential, metallic lanthanum with either nanoparticles or nanoporous structures was obtained.

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex.

PubMed

Raymundo-Pereira, Paulo A; Teixeira, Marcos F S; Fatibello-Filho, Orlando; Dockal, Edward R; Bonifácio, Viviane Gomes; Marcolino, Luiz H

2013-10-01

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L(-1) of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s(-1). A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9×10(-5) to 1.0×10(-3) mol L(-1), with a detection limit of 6.6×10(-5) mol L(-1) using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations. Copyright © 2013. Published by Elsevier B.V.

Reaction of Hydroquinone with Hematite I. Study of Adsorption by Electrochemical-Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy

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

Stack, Andrew G; Eggleston, Carrick M; Engelhard, Mark H

2004-06-15

The reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate ofreductive dissolution, especially by iron-reducing bacteria. Here, the electrochemical and physical properties of hydroquinone adsorbed on hematite surfaces at pH 2.5–3 were investigated with cyclic voltammetry (CV), electrochemical-scanning tunneling microscopy (EC-STM), and X-ray photoelectron spectroscopy (XPS). An oxidation peak for hydroquinone was observed in the CV experiments, as well as (photo)reduction of iron and decomposition of the solvent. The EC-STM results indicate that hydroquinone sometimes forms an ordered monolayer with ~1.1 H₂/nm², but can be fairly disordered (especiallymore » when viewed at larger scales). XPS results indicate that hydroquinone and benzoquinone are retained at the interface in increasing amounts as the reaction proceeds, but reduced iron is not observed. These results suggest that quinones do not adsorb by an inner-sphere complex where adsorbate–surface interactions determine the adsorbate surface structure, but rather in an outer-sphere complex where interactions among the adsorbate molecules dominate.« less

Reaction of hydroquinone with hematite I. Study of asdsorption by electrochemical-scanning tunneling microscopy and X-ray photoelectron spectroscopy.

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

Stack, Andrew G; Eggleston, Carrick M; Engelhard, Mark H

2003-12-01

The reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate of reductive dissolution, especially by iron-reducing bacteria. Here, the electrochemical and physical properties of hydroquinone adsorbed on hematite surfaces at pH 2.5-3 were investigated with cyclic voltammetry (CV), electrochemical-scanning tunneling microscopy (EC-STM), and X-ray photoelectron spectroscopy (XPS). An oxidation peak for hydroquinone was observed in the CV experiments, as well as (photo)reduction of iron and decomposition of the solvent. The EC-STM results indicate that hydroquinone sometimes forms an ordered monolayer with {approx}1.1 QH{sub 2}/nm{sup 2}, but can bemore » fairly disordered (especially when viewed at larger scales). XPS results indicate that hydroquinone and benzoquinone are retained at the interface in increasing amounts as the reaction proceeds, but reduced iron is not observed. These results suggest that quinones do not adsorb by an inner-sphere complex where adsorbate-surface interactions determine the adsorbate surface structure, but rather in an outer-sphere complex where interactions among the adsorbate molecules dominate.« less

3D printed stretchable capacitive sensors for highly sensitive tactile and electrochemical sensing

NASA Astrophysics Data System (ADS)

Li, Kai; Wei, Hong; Liu, Wenguang; Meng, Hong; Zhang, Peixin; Yan, Chaoyi

2018-05-01

Developments of innovative strategies for the fabrication of stretchable sensors are of crucial importance for their applications in wearable electronic systems. In this work, we report the successful fabrication of stretchable capacitive sensors using a novel 3D printing method for highly sensitive tactile and electrochemical sensing applications. Unlike conventional lithographic or templated methods, the programmable 3D printing technique can fabricate complex device structures in a cost-effective and facile manner. We designed and fabricated stretchable capacitive sensors with interdigital and double-vortex designs and demonstrated their successful applications as tactile and electrochemical sensors. Especially, our stretchable sensors exhibited a detection limit as low as 1 × 10-6 M for NaCl aqueous solution, which could have significant potential applications when integrated in electronics skins.

Electrochemical Nanoparticle-Enzyme Sensors for Screening Bacterial Contamination in Drinking Water

PubMed Central

Chen, Juhong; Jiang, Ziwen; Ackerman, Jonathan D.; Yazdani, Mahdieh; Hou, Singyuk

2015-01-01

Traditional plating and culturing methods used to quantify bacteria commonly require hours to days from sampling to results. We present here a simple, sensitive and rapid electrochemical method for bacteria detection in drinking water based on gold nanoparticle-enzyme complexes. The gold nanoparticles were functionalized with positively charged quaternary amine headgroups that could bind to enzymes through electrostatic interactions, resulting in inhibition of enzymatic activity. In the presence of bacteria, the nanoparticles released from the enzymes and preferentially bound to the bacteria, resulting in an increase in enzyme activity, releasing a redox-active phenol from the substrate. We employed this strategy for the electrochemical sensing of Escherichia coli and Staphylococcus aureus, resulting in a rapid detection (<1h) with high sensitivity (102 CFU·mL−1). PMID:26042607

Curious Case of Positive Current Collectors: Corrosion and Passivation at High Temperature.

PubMed

Sayed, Farheen N; Rodrigues, Marco-Tulio F; Kalaga, Kaushik; Gullapalli, Hemtej; Ajayan, P M

2017-12-20

In the evaluation of compatibility of different components of cell for high-energy and extreme-conditions applications, the highly focused are positive and negative electrodes and their interaction with electrolyte. However, for high-temperature application, the other components are also of significant influence and contribute toward the total health of battery. In present study, we have investigated the behavior of aluminum, the most common current collector for positive electrode materials for its electrochemical and temperature stability. For electrochemical stability, different electrolytes, organic and room temperature ionic liquids with varying Li salts (LiTFSI, LiFSI), are investigated. The combination of electrochemical and spectroscopic investigations reflects the varying mechanism of passivation at room and high temperature, as different compositions of decomposed complexes are found at the surface of metals.

3D printed stretchable capacitive sensors for highly sensitive tactile and electrochemical sensing.

PubMed

Li, Kai; Wei, Hong; Liu, Wenguang; Meng, Hong; Zhang, Peixin; Yan, Chaoyi

2018-05-04

Developments of innovative strategies for the fabrication of stretchable sensors are of crucial importance for their applications in wearable electronic systems. In this work, we report the successful fabrication of stretchable capacitive sensors using a novel 3D printing method for highly sensitive tactile and electrochemical sensing applications. Unlike conventional lithographic or templated methods, the programmable 3D printing technique can fabricate complex device structures in a cost-effective and facile manner. We designed and fabricated stretchable capacitive sensors with interdigital and double-vortex designs and demonstrated their successful applications as tactile and electrochemical sensors. Especially, our stretchable sensors exhibited a detection limit as low as 1 × 10 -6 M for NaCl aqueous solution, which could have significant potential applications when integrated in electronics skins.

Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.

PubMed

Maar, Ryan R; Rabiee Kenaree, Amir; Zhang, Ruizhong; Tao, Yichen; Katzman, Benjamin D; Staroverov, Viktor N; Ding, Zhifeng; Gilroy, Joe B

2017-10-16

The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N 2 O 2 3- formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M -1 cm -1 ) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.

Electrochemically controlled drug-mimicking protein release from iron-alginate thin-films associated with an electrode.

PubMed

Jin, Zhiyuan; Güven, Güray; Bocharova, Vera; Halámek, Jan; Tokarev, Ihor; Minko, Sergiy; Melman, Artem; Mandler, Daniel; Katz, Evgeny

2012-01-01

Novel biocompatible hybrid-material composed of iron-ion-cross-linked alginate with embedded protein molecules has been designed for the signal-triggered drug release. Electrochemically controlled oxidation of Fe(2+) ions in the presence of soluble natural alginate polymer and drug-mimicking protein (bovine serum albumin, BSA) results in the formation of an alginate-based thin-film cross-linked by Fe(3+) ions at the electrode interface with the entrapped protein. The electrochemically generated composite thin-film was characterized by electrochemistry and atomic force microscopy (AFM). Preliminary experiments demonstrated that the electrochemically controlled deposition of the protein-containing thin-film can be performed at microscale using scanning electrochemical microscopy (SECM) as the deposition tool producing polymer-patterned spots potentially containing various entrapped drugs. Application of reductive potentials on the modified electrode produced Fe(2+) cations which do not keep complexation with alginate, thus resulting in the electrochemically triggered thin-film dissolution and the protein release. Different experimental parameters, such as the film-deposition time, concentrations of compounds and applied potentials, were varied in order to demonstrate that the electrodepositon and electrodissolution of the alginate composite film can be tuned to the optimum performance. A statistical modeling technique was applied to find optimal conditions for the formation of the composite thin-film for the maximal encapsulation and release of the drug-mimicking protein at the lowest possible potential. © 2011 American Chemical Society

Diarylethene-containing cyclometalated platinum(II) complexes: tunable photochromism via metal coordination and rational ligand design.

PubMed

Chan, Jacky Chi-Hung; Lam, Wai Han; Wong, Hok-Lai; Zhu, Nianyong; Wong, Wing-Tak; Yam, Vivian Wing-Wah

2011-08-17

The synthesis, characterization, electrochemistry, photophysics and photochromic behavior of a new class of cyclometalated platinum(II) complexes [Pt(C(∧)N)(O(∧)O)] (1a-5a and 1b-5b), where C(∧)N is a cyclometalating 2-(2'-thienyl)pyridyl (thpy) or 2-(2'-thienothienyl)pyridyl (tthpy) ligand containing the photochromic dithienylethene (DTE) unit and O(∧)O is a β-diketonato ligand of acetylacetonato (acac) or hexafluoroacetylacetonato (hfac), have been reported. The X-ray crystal structures of five of the complexes have also been determined. The electrochemical studies reveal that the first quasi-reversible reduction couple, and hence the nature of lowest unoccupied molecular orbital (LUMO) of the complexes, is sensitive to the nature of the ancillary O(∧)O ligands. Upon photoexcitation, complexes 1a-3a and 1b-3b exhibit drastic color changes, ascribed to the reversible photochromic behavior, which is found to be sensitive to the substituents on the pyridyl ring and the extent of π-conjugation of the C(∧)N ligand as well as the nature of the ancillary ligand. The thermal bleaching kinetics of complex 1a has been studied in toluene at various temperatures, and the activation barrier for the thermal cycloreversion of the complex has been determined. Density functional theory (DFT) calculations have been performed to provide an insight into the electrochemical, photophysical and photochromic properties.

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

Kalnaus, Sergiy; Kumar, Abhishek; Lebrun-Grandie, Damien T.

Safety is a key element of any device designed to store energy, in particular electrochemical batteries, which convert energy of chemical reactions to electrical energy. Safety considerations are especially important when applied to large automotive batteries designed for propulsion of electric vehicles (EV). The high amount of energy stored in EV battery packs translates to higher probability of fire in case of severe deformation of battery compartment due to automotive crash or impact caused by road debris. While such demand for safety has resulted in heavier protection of battery enclosure, the mechanisms leading to internal short circuit due to deformationmore » of the battery are not well understood even on the level of a single electrochemical cell. Moreover, not all internal shorts result in thermal runaway, and thus a criterion for catastrophic failure needs to be developed. This report summarizes the effort to pinpoint the critical deformation necessary to trigger a short via experimental study on large format automotive Li-ion cells in a rigid spherical indentation configuration. Cases of single cells and cell stacks undergoing indentation were investigated. Mechanical properties of cell components were determined via experimental testing and served as input for constitutive models of Finite Element (FE) analysis. The ability of the model to predict the behavior of cell(s) under spherical indentation and to predict failure leading to internal short circuit was validated against experiments. The necessity of resolving pairs of negative and positive electrodes in the FE formulation is clearly demonstrated by comparing layer-resolved simulations with simulations involving batteries with homogenized material properties. Finally, a coupled solution of electrochemical-electrical-thermal (EET) problem on a Nissan Leaf battery module was demonstrated towards the goal of extending the simulations to module level.« less

Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.

PubMed

Han, Xue; Mendes, Sergio B

2014-02-04

An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.

Cyclodextrins Based Electrochemical Sensors for Biomedical and Pharmaceutical Analysis.

PubMed

Lenik, Joanna

2017-01-01

Electrochemical sensors are very convenient devices, as they may be used in a lot of fields starting from the food industry to environmental monitoring and medical diagnostics. They offer the values of simple design, reversible and reproducible measurements, as well as ensuring precise and accurate analytical information. Compared with other methods, electrochemical sensors are relatively simple as well as having low costs, which has led to intensive development, especially in the field of medicine and pharmaceuticals within the last decade. Recently, the number of publications covering the determination of aminoacids, dopamine, cholesterol, uric acid, biomarkers, vitamins and other pharmaceutical and biological compounds has significantly increased. Many possible types of such sensors and biosensors have been proposed: owing to the kind of the detection-potentiometric voltametric, amperometry, and the materials that can be used for, e.g. designing molecular architecture of the electrode/solution interface, carbon paste, carbon nanotubes, glass carbon, graphite, graphene, PVC, conductive polymers and/or nanoparticles. The active compounds which provide the complex formation with analyte (in the case of non-current techniques) or activate biomolecules electrochemically by particle recognition and selective preconcentration of analyte on the electrode surface (in the case of current techniques) are the most recently used cyclodextrins. These macrocyclic compounds have the ability to interact with a large diversity of guest particles to form complexes of the type of guest host, for example, with particles from drugs, biomolecules, through their hydrophilic outer surface and lipophilic inner cavities. Cyclodextrins have been the subject of frequent electrochemical studies that focused mostly on both their interactions in a solid state and in solution. The process of preparing of CDs modified electrodes would, consequently, open new avenues for new electrochemical sensors and, therefore, widen their use in biomedical and drug analysis. This review presents information on manufacturing techniques and performances of these sensors and biosensors. The opportunities for these sensors to carry out biomedical and pharmaceutical researches are demonstrated. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Amine functionalized graphene oxide/CNT nanocomposite for ultrasensitive electrochemical detection of trinitrotoluene.

PubMed

Sablok, Kavita; Bhalla, Vijayender; Sharma, Priyanka; Kaushal, Roohi; Chaudhary, Shilpa; Suri, C Raman

2013-03-15

Binding of electron-deficient trinitrotoluene (TNT) to the electron rich amine groups on a substrate form specific charge-transfer Jackson-Meisenheimer (JM) complex. In the present work, we report formation of specific JM complex on amine functionalized reduced graphene oxide/carbon nanotubes- (a-rGO/CNT) nanocomposite leading to sensitive detection of TNT. The CNT were dispersed using graphene oxide that provides excellent dispersion by attaching to CNT through its hydrophobic domains and solubilizes through the available OH and COOH groups on screen printed electrode (SPE). The GO was reduced electrochemically to form reduced graphene that remarkably increases electrochemical properties owing to the intercalation of high aspect CNT on graphene flakes as shown by TEM micrograph. The surface amine functionalization of dropcasted and rGO/CNT was carried out using a bi-functional cross linker ethylenediamine. The extent of amine functionalization on modified electrodes was confirmed using energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and confocal microscopy. The FTIR and Raman spectra further suggested the formation of JM complex between amine functionalized electrodes and TNT leading to a shift in peak intensity together with peak broadening. The a-rGO/CNT nanocomposite prepared electrode surface leads to ultra-trace detection of TNT upto 0.01 ppb with good reproducibility (n=3). The a-rGO/CNT sensing platform could be an alternate for sensitive detection of TNT explosive for various security and environmental applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Solvation-controlled lithium-ion complexes in a nonflammable solvent containing ethylene carbonate: structural and electrochemical aspects.

PubMed

Sogawa, Michiru; Kawanoue, Hikaru; Todorov, Yanko Marinov; Hirayama, Daisuke; Mimura, Hideyuki; Yoshimoto, Nobuko; Morita, Masayuki; Fujii, Kenta

2018-02-28

The structural and electrochemical properties of lithium-ion solvation complexes in a nonflammable organic solvent, tris(2,2,2-trifluoroethyl)phosphate (TFEP) containing ethylene carbonate (EC), were investigated using vibrational spectroscopic and electrochemical measurements. Based on quantitative Raman and infrared (IR) spectral analysis of the Li bis(trifluoromethanesulfonyl)amide (TFSA) salt in TFEP + EC electrolytes, we successfully evaluated the individual solvation numbers of EC (n EC ), TFEP (n TFEP ), and TFSA - (n TFSA ) in the first solvation sphere of the Li-ion. We found that the n EC value linearly increased with increasing EC mole fraction (x EC ), whereas the n TFEP and n TFSA values gradually decreased with increasing n EC . The ionic conductivity and viscosity (Walden plots) indicated that mainly Li + TFSA - ion pairs formed in neat TFEP (x EC = 0). This ion pair gradually dissociated into positively charged Li-ion complexes as x EC increased, which was consistent with the Raman/IR spectroscopy results. The redox reaction corresponding to an insertion/desertion of Li-ion into/from the graphite electrode occurred in the LiTFSA/TFEP + EC system at x EC ≥ 0.25. The same was not observed in the lower x EC cases. We discussed the relation between Li-ion solvation and electrode reaction behaviors at the molecular level and proposed that n EC plays a crucial role in the electrode reaction, particularly in terms of solid electrolyte interphase formation on the graphite electrode.

Nanotubular surface modification of metallic implants via electrochemical anodization technique.

PubMed

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

2014-01-01

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

Nanotubular surface modification of metallic implants via electrochemical anodization technique

PubMed Central

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

2014-01-01

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

DNA interactions with a Methylene Blue redox indicator depend on the DNA length and are sequence specific.

PubMed

Farjami, Elaheh; Clima, Lilia; Gothelf, Kurt V; Ferapontova, Elena E

2010-06-01

A DNA molecular beacon approach was used for the analysis of interactions between DNA and Methylene Blue (MB) as a redox indicator of a hybridization event. DNA hairpin structures of different length and guanine (G) content were immobilized onto gold electrodes in their folded states through the alkanethiol linker at the 5'-end. Binding of MB to the folded hairpin DNA was electrochemically studied and compared with binding to the duplex structure formed by hybridization of the hairpin DNA to a complementary DNA strand. Variation of the electrochemical signal from the DNA-MB complex was shown to depend primarily on the DNA length and sequence used: the G-C base pairs were the preferential sites of MB binding in the duplex. For short 20 nts long DNA sequences, the increased electrochemical response from MB bound to the duplex structure was consistent with the increased amount of bound and electrochemically readable MB molecules (i.e. MB molecules that are available for the electron transfer (ET) reaction with the electrode). With longer DNA sequences, the balance between the amounts of the electrochemically readable MB molecules bound to the hairpin DNA and to the hybrid was opposite: a part of the MB molecules bound to the long-sequence DNA duplex seem to be electrochemically mute due to long ET distance. The increasing electrochemical response from MB bound to the short-length DNA hybrid contrasts with the decreasing signal from MB bound to the long-length DNA hybrid and allows an "off"-"on" genosensor development.

Electrochemical and spectroelectrochemical studies on UO(2)(saloph)L (saloph = N,N'-disalicylidene-o-phenylenediaminate, L=dimethyl sulfoxide or N,N-dimethylformamide).

PubMed

Mizuoka, Koichiro; Kim, Seong-Yun; Hasegawa, Miki; Hoshi, Toshihiko; Uchiyama, Gunzo; Ikeda, Yasuhisa

2003-02-24

To examine properties of pentavalent uranium, U(V), we have carried out electrochemical and spectroelectrochemical studies on UO(2)(saloph)L [saloph = N,N'-disalicylidene-o-phenylenediaminate, L = dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF)]. The electrochemical reactions of UO(2)(saloph)L complexes in L were found to occur quasireversibly. The reduction processes of UO(2)(saloph)L complexes were followed spectroelectrochemically by using an optical transparent thin layer electrode cell. It was found that the absorption spectra measured at the applied potentials from 0 to -1.650 V versus ferrocene/ferrocenium ion redox couple (Fc/Fc(+)) for UO(2)(saloph)DMSO in DMSO have clear isosbestic points and that the evaluated electron stoichiometry equals 1.08. These results indicate that the reduction product of UO(2)(saloph)DMSO is [U(V)O(2)(saloph)DMSO](-), which is considerably stable in DMSO. Furthermore, it was clarified that the absorption spectrum of the [U(V)O(2)(saloph)DMSO](-) complex has a very small molar absorptivity in the visible region and characteristic absorption bands due to the 5f(1) orbital at around 750 and 900 nm. For UO(2)(saloph)DMF in DMF, the clear isosbestic points were not observed in the similar spectral changes. It is proposed that the UO(2)(saloph)DMF complex is reduced to [U(V)O(2)(saloph)DMF](-) accompanied by the dissociation of DMF as a successive reaction. The formal redox potentials of UO(2)(saloph)L in L (E(0), vs Fc/Fc(+)) for U(VI)/U(V) couple were determined to be -1.550 V for L = DMSO and -1.626 V for L = DMF.

Noise-Coupled Image Rejection Architecture of Complex Bandpass ΔΣAD Modulator

NASA Astrophysics Data System (ADS)

San, Hao; Kobayashi, Haruo

This paper proposes a new realization technique of image rejection function by noise-coupling architecture, which is used for a complex bandpass ΔΣAD modulator. The complex bandpass ΔΣAD modulator processes just input I and Q signals, not image signals, and the AD conversion can be realized with low power dissipation. It realizes an asymmetric noise-shaped spectra, which is desirable for such low-IF receiver applications. However, the performance of the complex bandpass ΔΣAD modulator suffers from the mismatch between internal analog I and Q paths. I/Q path mismatch causes an image signal, and the quantization noise of the mirror image band aliases into the desired signal band, which degrades the SQNDR (Signal to Quantization Noise and Distortion Ratio) of the modulator. In our proposed modulator architecture, an extra notch for image rejection is realized by noise-coupled topology. We just add some passive capacitors and switches to the modulator; the additional integrator circuit composed of an operational amplifier in the conventional image rejection realization is not necessary. Therefore, the performance of the complex modulator can be effectively raised without additional power dissipation. We have performed simulation with MATLAB to confirm the validity of the proposed architecture. The simulation results show that the proposed architecture can achieve the realization of image-rejection effectively, and improve the SQNDR of the complex bandpass ΔΣAD modulator.

Syntheses, structures, electrochemistry and catalytic oxidation degradation of organic dyes of two new coordination polymers derived from Cu(II) and Mn(II) and 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene

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

Song, Ming; Mu, Bao; Huang, Ru-Dan, E-mail: huangrd@bit.edu.cn

Two new coordination polymers (CPs), namely, [Cu{sub 2}(ttbz)(H{sub 2}btc){sub 2}(OH)]{sub n} (1) and [Mn(ttbz){sub 2}(H{sub 2}O){sub 2}]{sub n} (2) (Httbz =1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene, H{sub 3}btc =1,3,5-benzenetricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a (3,5,5,5)-connected 2D layer with a Schläfli symbol of (3·4{sup 2})(3·4{sup 4}0.5{sup 2}0.6{sup 3})(3{sup 2}0.4{sup 4}0.5{sup 2}0.6{sup 2})(3{sup 2}0.4{sup 4}0.5{sup 3}0.6), in which the ttbz{sup -} ligand can be described as μ{sub 5}-bridge, linking Cu(II) ions into a 2D layer and H{sub 2}btc{sup -} ions play a supporting role in complex 1. The ttbz{sup -} ligand in complex 2 represents the bridging coordination mode, connectingmore » two Mn(II) ions to form the infinite 1D zigzag chains, respectively, which are further connected by two different types of hydrogen bonds to form a 3D supramolecular. Furthermore, catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated at room temperature in aqueous solutions, indicating these complexes may be applicable to color removal in a textile wastewater stream and practical applications in areas of electrocatalytic reduction toward nitrite, respectively. - Graphical abstract: Two new coordination polymers based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated. - Highlights: • The organic ligand containing the tetrazolyl group and triazolyl group with some advantages has been used. • Two new coordination polymers with different structural characteristics has been discussed in detail. • Catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated.« less

Relaxation Time Distribution (RTD) of Spectral Induced Polarization (SIP) data from environmental studies

NASA Astrophysics Data System (ADS)

Ntarlagiannis, D.; Ustra, A.; Slater, L. D.; Zhang, C.; Mendonça, C. A.

2015-12-01

In this work we present an alternative formulation of the Debye Decomposition (DD) of complex conductivity spectra, with a new set of parameters that are directly related to the continuous Debye relaxation model. The procedure determines the relaxation time distribution (RTD) and two frequency-independent parameters that modulate the induced polarization spectra. The distribution of relaxation times quantifies the contribution of each distinct relaxation process, which can in turn be associated with specific polarization processes and characterized in terms of electrochemical and interfacial parameters as derived from mechanistic models. Synthetic tests show that the procedure can successfully fit spectral induced polarization (SIP) data and accurately recover the RTD. The procedure was applied to different data sets, focusing on environmental applications. We focus on data of sand-clay mixtures artificially contaminated with toluene, and crude oil-contaminated sands experiencing biodegradation. The results identify characteristic relaxation times that can be associated with distinct polarization processes resulting from either the contaminant itself or transformations associated with biodegradation. The inversion results provide information regarding the relative strength and dominant relaxation time of these polarization processes.

Luminescent Dinuclear Ruthenium Terpyridine Complexes with a Bis-Phenylbenzimidazole Spacer.

PubMed

Mondal, Debiprasad; Biswas, Sourav; Paul, Animesh; Baitalik, Sujoy

2017-07-17

A conjugated bis-terpyridine bridging ligand, 2-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)-6-(2-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)-1H-benzo[d]imidazol-6-yl)-1H-benzo[d] imidazole (tpy-BPhBzimH 2 -tpy), was designed in this work by covalent coupling of 3,3'-diaminobenzidine and two 4'-(p-formylphenyl)-2,2':6',2″-terpyridine units to synthesize a new series of bimetallic Ru(II)-terpyridine light-harvesting complexes. Photophysical and electrochemical properties were modulated by the variation of the terminal ligands in the complexes. The new compounds were thoroughly characterized by 1 H NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis. Absorption spectra of the complexes consist of very strong ligand-centered π-π* and n-π* transitions in the UV, metal-to-ligand, and intraligand charge transfer bands in the visible regions. Steady-state and time-resolved emission spectral measurements indicate that the complexes exhibit moderately intense luminescence at room temperature within the spectral domain of 653-687 nm having luminescence lifetimes in the range between 6.3 and 55.2 ns, depending upon terminal tridentate ligand and solvent. Variable-temperature luminescence measurements suggest substantial increase of the energy gap between luminescent 3 metal-to-ligand charge transfer state and nonluminescent 3 metal centered in the complexes compared to the parent [Ru(tpy) 2 ] 2+ . Each of the three bimetallic complexes exhibits only one reversible couple in the positive potential window with almost no detectable splitting corresponding to simultaneous oxidation of the two remote Ru centers. All the complexes possess a number of imidazole NH protons, which became sufficiently acidic upon metal ion coordination. By utilizing these NH protons, we thoroughly studied anion recognition properties of the complexes in pure organic as well as predominantly aqueous media through multiple optical channels and spectroscopic methods. Finally computation investigations employing density functional theory (DFT) and time-dependent DFT were done to examine the electronic structures of the complexes and accurate assignment of experimentally observed optical spectral bands.

Abnormal Magnetic Field Effects on Electrogenerated Chemiluminescence

NASA Astrophysics Data System (ADS)

Pan, Haiping; Shen, Yan; Wang, Hongfeng; He, Lei; Hu, Bin

2015-03-01

We report abnormal magnetic field effects on electrogenerated chemiluminescence (MFEECL) based on triplet emission from the Ru(bpy)3Cl2-TPrA electrochemical system: the appearance of MFEECL after magnetic field ceases. In early studies the normal MFEECL have been observed from electrochemical systems during the application of magnetic field. Here, the abnormal MFEECL suggest that the activated charge-transfer [Ru(bpy)33+ … TPrA•] complexes may become magnetized in magnetic field and experience a long magnetic relaxation after removing magnetic field. Our analysis indicates that the magnetic relaxation can gradually increase the density of charge-transfer complexes within reaction region due to decayed magnetic interactions, leading to a positive component in the abnormal MFEECL. On the other hand, the magnetic relaxation facilitates an inverse conversion from triplets to singlets within charge-transfer complexes. The inverse triplet --> singlet conversion reduces the density of triplet light-emitting states through charge-transfer complexes and gives rise to a negative component in the abnormal MFEECL. The combination of positive and negative components can essentially lead to a non-monotonic profile in the abnormal MFEECL after ceasing magnetic field. Nevertheless, our experimental studies may reveal un-usual magnetic behaviors with long magnetic relaxation from the activated charge-transfer [Ru(bpy)33+ … TPrA•] complexes in solution at room temperature.

Time dependent-density functional theory (TD-DFT) and experimental studies of UV-Visible spectra and cyclic voltammetry for Cu(II) complex with Et2DTC

NASA Astrophysics Data System (ADS)

Valle, Eliana Maira A.; Maltarollo, Vinicius Gonçalves; Almeida, Michell O.; Honorio, Kathia Maria; dos Santos, Mauro Coelho; Cerchiaro, Giselle

2018-04-01

In this work, we studied the complexation mode between copper(II) ion and the specific ligand investigated as carriers of metals though biological membranes, diethyldithiocarbamate (Et2DTC). It is important to understand how this occurs because it is an important intracellular chelator with potential therapeutic applications. Theoretical and experimental UV visible studies were performed to investigate the complexation mode between copper and the ligand. Electrochemical studies were also performed to complement the spectroscopic analyses. According to the theoretical calculations, using TD-DFT (Time dependent density functional theory), with B3LYP functional and DGDVZP basis set, implemented in Gaussian 03 package, it was observed that the formation of the complex [Cu(Et2DTC)2] is favorable with higher electron density over the sulfur atoms of the ligand. UV/Vis spectra have a charge transfer band at 450 nm, with the DMSO-d6 band shift from 800 to 650 nm. The electrochemical experiments showed the formation of a new redox process, referring to the complex, where the reduction peak potential of copper is displaced to less positive region. Therefore, the results obtained from this study give important insights on possible mechanisms involved in several biological processes related to the studied system.

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

2004-01-01

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Zwitterionic peptide anchored to conducting polymer PEDOT for the development of antifouling and ultrasensitive electrochemical DNA sensor.

PubMed

Wang, Guixiang; Han, Rui; Su, Xiaoli; Li, Yinan; Xu, Guiyun; Luo, Xiliang

2017-06-15

Zwitterionic peptides were anchored to a conducting polymer of citrate doped poly(3,4-ethylenedioxythiophene) (PEDOT) via the nickel cation coordination, and the obtained peptide modified PEDOT, with excellent antifouling ability and good conductivity, was further used for the immobilization of a DNA probe to construct an electrochemical biosensor for the breast cancer marker BRCA1. The DNA biosensor was highly sensitive (with detection limit of 0.03fM) and selective, and it was able to detect BRCA1 in 5% (v/v) human plasma with satisfying accuracy and low fouling. The marriage of antifouling and biocompatible peptides with conducting polymers opened a new avenue to construct electrochemical biosensors capable of assaying targets in complex biological media with high sensitivity and without biofouling. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and characterization of an effective organic/inorganic hybrid green corrosion inhibitive complex based on zinc acetate/Urtica Dioica

NASA Astrophysics Data System (ADS)

Salehi, E.; Naderi, Reza; Ramezanzadeh, B.

2017-02-01

This study aims at synthesis and characterization of an effective corrosion inhibitive complex based on zinc acetate/Urtica Dioica (ZnA-U.D) for corrosion protection of mild steel in chloride solution. The chemical structure and morphology of the complex were characterized by Fourier transform infrared spectroscopy (FT-IR), UV-vis, thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The corrosion protection performance of the mild steel samples dipped in 3.5 wt.% NaCl solutions with and without ZnA-U.D extract was investigated by visual observations, open circuit potential (OCP) measurements, electrochemical impedance spectroscopy (EIS) and polarization test. Results revealed that the ZnA successfully chelated with organic inhibitive compounds (i.e Quercetin, Quinic acid, Caffeic acid, Hystamine and Serotonin) present in the U.D extract. The electrochemical measurements revealed the effective inhibition action of ZnA-U.D complex in the sodium chloride solution on the mild steel. The synergistic effect between Zn2+ and organic compounds present in the U.D extract resulted in protective film deposition on the steel surface, which was proved by SEM and XPS analyses.

Characterization of inclusion complexes of organic ions with hydrophilic hosts by ion transfer voltammetry with solvent polymeric membranes.

PubMed

Olmos, José Manuel; Laborda, Eduardo; Ortuño, Joaquín Ángel; Molina, Ángela

2017-03-01

The quantitative characterization of inclusion complexes formed in aqueous phase between organic ions and hydrophilic hosts by ion-transfer voltammetry with solvent polymeric membrane ion sensors is studied, both in a theoretical and experimental way. Simple analytical solutions are presented for the determination of the binding constant of the complex from the variation with the host concentration of the electrochemical signal. These solutions are valid for any voltammetric technique and for solvent polymeric membrane ion sensors comprising one polarisable interface (1PI) and also, for the first time, two polarisable interfaces (2PIs). Suitable experimental conditions and data analysis procedures are discussed and applied to the study of the interactions of a common ionic liquid cation (1-octyl-3-metyl-imidazolium) and an ionisable drug (clomipramine) with two hydrophilic cyclodextrins: α-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. The experimental study is performed via square wave voltammetry with 2PIs and 1PI solvent polymeric membranes and in both cases the electrochemical experiments enable the detection of inclusion complexes and the determination of the corresponding binding constant. Copyright © 2016 Elsevier B.V. All rights reserved.

Phosphorescent Iridium(III) Complexes Bearing Fluorinated Aromatic Sulfonyl Group with Nearly Unity Phosphorescent Quantum Yields and Outstanding Electroluminescent Properties.

PubMed

Zhao, Jiang; Yu, Yue; Yang, Xiaolong; Yan, Xiaogang; Zhang, Huiming; Xu, Xianbin; Zhou, Guijiang; Wu, Zhaoxin; Ren, Yixia; Wong, Wai-Yeung

2015-11-11

A series of heteroleptic functional Ir(III) complexes bearing different fluorinated aromatic sulfonyl groups has been synthesized. Their photophysical features, electrochemical behaviors, and electroluminescent (EL) properties have been characterized in detail. These complexes emit intense yellow phosphorescence with exceptionally high quantum yields (ΦP > 0.9) at room temperature, and the emission maxima of these complexes can be finely tuned depending upon the number of the fluorine substituents on the pendant phenyl ring of the sulfonyl group. Furthermore, the electrochemical properties and electron injection/transporting (EI/ET) abilities of these Ir(III) phosphors can also be effectively tuned by the fluorinated aromatic sulfonyl group to furnish some desired characters for enhancing the EL performance. Hence, the maximum luminance efficiency (ηL) of 81.2 cd A(-1), corresponding to power efficiency (ηP) of 64.5 lm W(-1) and external quantum efficiency (ηext) of 19.3%, has been achieved, indicating the great potential of these novel phosphors in the field of organic light-emitting diodes (OLEDs). Furthermore, a clear picture has been drawn for the relationship between their optoelectronic properties and chemical structures. These results should provide important information for developing highly efficient phosphors.

An electrochemical label-free and sensitive thrombin aptasensor based on graphene oxide modified pencil graphite electrode.

PubMed

Ahour, F; Ahsani, M K

2016-12-15

In this work, we tactfully constructed a novel label-free electrochemical aptasensor for rapid and facile detection of thrombin using graphene oxide (GO) and thrombin binding aptamer (TBA). The strategy relies on the preferential adsorption of single-stranded DNA (ssDNA) to GO over aptamer-target complexes. The TBA-thrombin complex formation was monitored by differential pulse voltammetry (DPV) using the guanine oxidation signal. In the absence of thrombin, the aptamers adsorbed onto the surface of GO leading to a strong background guanine oxidation signal. Conversely, in the presence of thrombin, the conformational transformation of TBA after incubating with the thrombin solution and formation of the aptamer-thrombin complexes which had weak binding ability to GO, leads to the desorption of TBA-thrombin complex from electrode surface and significant oxidation signal decrease. The selectivity of the biosensor was studied using other biological substances. The biosensor's signal was proportional to the thrombin concentration from 0.1 to 10nM with a detection limit of 0.07nM. Particularly, the proposed method could be widely applied to the aptamer-based determination of other target analytes. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

PubMed Central

2012-01-01

LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method. PMID:22221711

Effect of complexing agents on the electrochemical performance of LiFePO4/C prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Yang, Rong; Kang, Erwei; Jiang, Bailing; Ahn, Jou-Hyeon

2012-01-01

LiFePO4/C is synthesized via sol-gel method using Fe3+ as iron sources and different complexing agents, followed by sintering at high temperature for crystallization. The amount of carbon in these composites is less than 6.8 wt.%, and the X-ray diffraction experiment confirms that all samples are pure single phase indexed with the orthorhombic Pnma space group. The particle size of the LiFePO4/C synthesized by acetic acid as a complexing agent is very fine with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, is better than those of LiFePO4/C synthesized by other complexing agents. The cell of this sample can deliver a discharge capacity of 161.1 mAh g-1 at the first cycle. After 30 cycles, the capacity decreases to 157.5 mAh g-1, and the capacity fading rate is 2.2%. The mechanism is studied to explain the effect of a complexing agent on the synthesis of LiFePO4/C by sol-gel method. The results show that the complexing agent with a low stability constant may be proper for the synthetic process of LiFePO4/C via sol-gel method.

Thermo-electrochemical analysis of lithium ion batteries for space applications using Thermal Desktop

NASA Astrophysics Data System (ADS)

Walker, W.; Ardebili, H.

2014-12-01

Lithium-ion batteries (LIBs) are replacing the Nickel-Hydrogen batteries used on the International Space Station (ISS). Knowing that LIB efficiency and survivability are greatly influenced by temperature, this study focuses on the thermo-electrochemical analysis of LIBs in space orbit. Current finite element modeling software allows for advanced simulation of the thermo-electrochemical processes; however the heat transfer simulation capabilities of said software suites do not allow for the extreme complexities of orbital-space environments like those experienced by the ISS. In this study, we have coupled the existing thermo-electrochemical models representing heat generation in LIBs during discharge cycles with specialized orbital-thermal software, Thermal Desktop (TD). Our model's parameters were obtained from a previous thermo-electrochemical model of a 185 Amp-Hour (Ah) LIB with 1-3 C (C) discharge cycles for both forced and natural convection environments at 300 K. Our TD model successfully simulates the temperature vs. depth-of-discharge (DOD) profiles and temperature ranges for all discharge and convection variations with minimal deviation through the programming of FORTRAN logic representing each variable as a function of relationship to DOD. Multiple parametrics were considered in a second and third set of cases whose results display vital data in advancing our understanding of accurate thermal modeling of LIBs.

Reliable clinical serum analysis with reusable electrochemical sensor: Toward point-of-care measurement of the antipsychotic medication clozapine.

PubMed

Kang, Mijeong; Kim, Eunkyoung; Winkler, Thomas E; Banis, George; Liu, Yi; Kitchen, Christopher A; Kelly, Deanna L; Ghodssi, Reza; Payne, Gregory F

2017-09-15

Clozapine is one of the most promising medications for managing schizophrenia but it is under-utilized because of the challenges of maintaining serum levels in a safe therapeutic range (1-3μM). Timely measurement of serum clozapine levels has been identified as a barrier to the broader use of clozapine, which is however challenging due to the complexity of serum samples. We demonstrate a robust and reusable electrochemical sensor with graphene-chitosan composite for rapidly measuring serum levels of clozapine. Our electrochemical measurements in clinical serum from clozapine-treated and clozapine-untreated schizophrenia groups are well correlated to centralized laboratory analysis for the readily detected uric acid and for the clozapine which is present at 100-fold lower concentration. The benefits of our electrochemical measurement approach for serum clozapine monitoring are: (i) rapid measurement (≈20min) without serum pretreatment; (ii) appropriate selectivity and sensitivity (limit of detection 0.7μM); (iii) reusability of an electrode over several weeks; and (iv) rapid reliability testing to detect common error-causing problems. This simple and rapid electrochemical approach for serum clozapine measurements should provide clinicians with the timely point-of-care information required to adjust dosages and personalize the management of schizophrenia. Copyright © 2017 Elsevier B.V. All rights reserved.

Immobilized-free miniaturized electrochemical sensing system for Pb2+ detection based on dual Pb2+-DNAzyme assistant feedback amplification strategy.

PubMed

Cai, Wei; Xie, Shunbi; Zhang, Jin; Tang, Dianyong; Tang, Ying

2018-06-08

We presented a novel dual-DNAzyme feedback amplification (DDFA) strategy for Pb 2+ detection based on a micropipette tip-based miniaturized homogeneous electrochemical device. The DDFA system involves two rolling circle amplification (RCA) processes in which two circular DNA templates (C1 and C2) have been designed with a Pb 2+ -DNAzyme sequence (8-17 DNAzyme, anti-GR-5 DNAzyme) and an antisense sequence of G-quadruplex. And a linear DNA (L-DNA), which consists of a primer sequence and a Pb 2+ -DNAzyme substrate sequence, could hybridize with C1 and C2 to form two DNA complexes. In presence of Pb 2+ , the Pb 2+ -DNAzyme exhibited excellent cleavage specificity toward the substrate sequence in L-DNA, leaving primer sequence to trigger two paths of RCA process and finally resulting in massive long nanosolo DNA strands with reduplicated G-quadruplex sequences. And then, methylene blue (MB) could selectively intercalate into G-quadruplex to reduce the free MB concentration in the solution. Thereafter, a carbon fiber microelectrode-based miniaturized electrochemical device was constructed to record the decrease of electrochemical signal due to the much lower diffusion rate of MB/G-quadruplex complex than that of free MB. Therefore, the concentration of Pb 2+ could be correctively and sensitively determined in a homogeneous solution by combining DDFA with miniaturized electrochemical device. This protocol not only exhibited high selectivity and sensitivity toward Pb 2+ with a detection limit of 0.048 pM, but also reduced sample volume to 10 µL. In addition, this sensing system has been successfully applied to Pb 2+ detection in Yangtze River with desirable quantitative manners, which matched well with the atomic absorption spectrometry (AAS). Copyright © 2018 Elsevier B.V. All rights reserved.

MEG evidence that the central auditory system simultaneously encodes multiple temporal cues.

PubMed

Simpson, Michael I G; Barnes, Gareth R; Johnson, Sam R; Hillebrand, Arjan; Singh, Krish D; Green, Gary G R

2009-09-01

Speech contains complex amplitude modulations that have envelopes with multiple temporal cues. The processing of these complex envelopes is not well explained by the classical models of amplitude modulation processing. This may be because the evidence for the models typically comes from the use of simple sinusoidal amplitude modulations. In this study we used magnetoencephalography (MEG) to generate source space current estimates of the steady-state responses to simple one-component amplitude modulations and to a two-component amplitude modulation. A two-component modulation introduces the simplest form of modulation complexity into the waveform; the summation of the two-modulation rates introduces a beat-like modulation at the difference frequency between the two modulation rates. We compared the cortical representations of responses to the one-component and two-component modulations. In particular, we show that the temporal complexity in the two-component amplitude modulation stimuli was preserved at the cortical level. The method of stimulus normalization that we used also allows us to interpret these results as evidence that the important feature in sound modulations is the relative depth of one modulation rate with respect to another, rather than the absolute carrier-to-sideband modulation depth. More generally, this may be interpreted as evidence that modulation detection accurately preserves a representation of the modulation envelope. This is an important observation with respect to models of modulation processing, as it suggests that models may need a dynamic processing step to effectively model non-stationary stimuli. We suggest that the classic modulation filterbank model needs to be modified to take these findings into account.

Numerical study on the thermal management system of a liquid metal battery module

NASA Astrophysics Data System (ADS)

Guo, Zhenlin; Xu, Cheng; Li, Wei; Zhu, Fangfang; Li, Haomiao; Wang, Kangli; Cheng, Shijie; Jiang, Kai

2018-07-01

Liquid metal battery (LMB), with three-liquid-layer structure and high operating temperature (300-700 °C), is a newly emerging technology for large scale energy storage applications. A thermal management system is critical to achieve satisfied LMB performance and extend the life of batteries. In this work, an improved coupling model composing of a 3D heat-transfer model and a 1D electrochemical model is developed for the thermal analysis of a Li||Sb-Sn LMBs module (5.5 kWh). Key results including transient values, the contribution ratio of heat sources, temperature homogeneity and distribution, as well as the energy efficiency of the battery module, are presented. Based on the coupling model, the changeable-power-heating mode, sand filling material and vacuum insulation are further proposed to achieve the high energy efficiency and optimal performance of the LMBs module. Moreover, the LMBs module can achieve "self-heating" when operated at 0.2 C charge/discharge, under the vacuum insulation (0.01 W m-1 K-1 thermal conductivity, 100 mm thickness), requiring no external heating to keep the batteries at operating temperature.

Organic electrochemical transistors

NASA Astrophysics Data System (ADS)

Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto; Owens, Róisín M.; Berggren, Magnus; Malliaras, George G.

2018-02-01

Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Scanning electrochemical microscopy of menadione-glutathione conjugate export from yeast cells

PubMed Central

Mauzeroll, Janine; Bard, Allen J.

2004-01-01

The uptake of menadione (2-methyl-1,4-naphthoquinone), which is toxic to yeast cells, and its expulsion as a glutathione complex were studied by scanning electrochemical microscopy. The progression of the in vitro reaction between menadione and glutathione was monitored electrochemically by cyclic voltammetry and correlated with the spectroscopic (UV–visible) behavior. By observing the scanning electrochemical microscope tip current of yeast cells suspended in a menadione-containing solution, the export of the conjugate from the cells with time could be measured. Similar experiments were performed on immobilized yeast cell aggregates stressed by a menadione solution. From the export of the menadione-glutathione conjugate detected at a 1-μm-diameter electrode situated 10 μm from the cells, a flux of about 30,000 thiodione molecules per second per cell was extracted. Numerical simulations based on an explicit finite difference method further revealed that the observation of a constant efflux of thiodione from the cells suggested the rate was limited by the uptake of menadione and that the efflux through the glutathione-conjugate pump was at least an order of magnitude faster. PMID:15148374

Diagnostics Strategies with Electrochemical Affinity Biosensors Using Carbon Nanomaterials as Electrode Modifiers

PubMed Central

Campuzano, Susana; Yáñez-Sedeño, Paloma; Pingarrón, José M.

2016-01-01

Early diagnosis is often the key to successful patient treatment and survival. The identification of various disease signaling biomarkers which reliably reflect normal and disease states in humans in biological fluids explain the burgeoning research field in developing new methodologies able to determine the target biomarkers in complex biological samples with the required sensitivity and selectivity and in a simple and rapid way. The unique advantages offered by electrochemical sensors together with the availability of high affinity and specific bioreceptors and their great capabilities in terms of sensitivity and stability imparted by nanostructuring the electrode surface with different carbon nanomaterials have led to the development of new electrochemical biosensing strategies that have flourished as interesting alternatives to conventional methodologies for clinical diagnostics. This paper briefly reviews the advantages of using carbon nanostructures and their hybrid nanocomposites as electrode modifiers to construct efficient electrochemical sensing platforms for diagnosis. The review provides an updated overview of some selected examples involving attractive amplification and biosensing approaches which have been applied to the determination of relevant genetic and protein diagnostics biomarkers. PMID:28035946

Sensitive polarographic electrochemical determination of clarithromycin in blood serum

PubMed Central

Jain, Ashish; Jain, Ankit; Jain, Anki

2013-01-01

Clarithromycin is an antibacterial widely used for the treatment of a myriad of infections. Various methods including HPLC have been reported for its drug plasma concentration but they are more complex. In this study, we developed an electrochemical method for estimation of clarithromycin in blood using differential pulse polarography (DPP) after oral administration of pure clarithromycin suspension. The differential pulse polarography of clarithromycin showed peak with peak potential Ep is −1460 mV SCE at pH 6.5 ± 0.1. The developed electrochemical method was standardized and validated for the determination of clarithromycin in blood serum of albino rats. PK analysis included Cmax, Tmax, AUC0-24, elimination rate constant (Kel) and t1/2. Cmax were found to be 1.34 ± 0.16 mg/ml and 1.99 ± 0.22 mg/ml for plain clarithromycin and suspension formulation, respectively. Effects of ammonium tartarate concentration and pH were also studied as specificity parameters. Developed electrochemical method was found to be simple, accurate method for to estimate blood-clarithromycin profile and can also be used similarly for various dosage forms. PMID:24023459

Ce(III, IV)-MOF electrocatalyst as signal-amplifying tag for sensitive electrochemical aptasensing.

PubMed

Yu, Hua; Han, Jing; An, Shangjie; Xie, Gang; Chen, Sanping

2018-06-30

Metal-organic frameworks (MOFs) as a new class of porous materials have attracted increasing attention in the field of biomimetic catalysis. This study firstly reports a mixed valence state Ce-MOF possessing intrinsic catalytic activity towards thionine (Thi), and its application in constructing an amplified electrochemical aptasensor for thrombin detection. As noticed, the novel catalytic process combines the advantages of 3D infinite extension of the Ce(III, IV)-MOF skeleton containing large amounts of catalytic sites and spontaneous recycling of the Ce(III)/Ce(IV) for electrochemical reduction of Thi, thereby presenting amplified electrochemical signals. To further improve the aptasensor performance, the high selectivity of proximity binding-induced DNA strand displacement and high efficiency of exonuclease III-assisted recycling amplification were incorporated into the assay. The aptasensor was employed to detect thrombin in complex serum samples, which shows high sensitivity, specificity, stability and reproducibility. This work offers an opportunity to develop MOF-based electrocatalyst as signal-amplifying tag for versatile bioassays and catalytic applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Fully Depleted Ti-Nb-Ta-Zr-O Nanotubes: Interfacial Charge Dynamics and Solar Hydrogen Production.

PubMed

Chiu, Yi-Hsuan; Lai, Ting-Hsuan; Chen, Chun-Yi; Hsieh, Ping-Yen; Ozasa, Kazunari; Niinomi, Mitsuo; Okada, Kiyoshi; Chang, Tso-Fu Mark; Matsushita, Nobuhiro; Sone, Masato; Hsu, Yung-Jung

2018-05-01

Poor kinetics of hole transportation at the electrode/electrolyte interface is regarded as a primary cause for the mediocre performance of n-type TiO 2 photoelectrodes. By adopting nanotubes as the electrode backbone, light absorption and carrier collection can be spatially decoupled, allowing n-type TiO 2 , with its short hole diffusion length, to maximize the use of the available photoexcited charge carriers during operation in photoelectrochemical (PEC) water splitting. Here, we presented a delicate electrochemical anodization process for the preparation of quaternary Ti-Nb-Ta-Zr-O mixed-oxide (denoted as TNTZO) nanotube arrays and demonstrated their utility in PEC water splitting. The charge-transfer dynamics for the electrodes was investigated using time-resolved photoluminescence, electrochemical impedance spectroscopy, and the decay of open-circuit voltage analysis. Data reveal that the superior photoactivity of TNTZO over pristine TiO 2 originated from the introduction of Nd, Ta, and Zr elements, which enhanced the amount of accessible charge carriers, modified the electronic structure, and improved the hole injection kinetics for expediting water splitting. By modulating the water content of the electrolyte employed in the anodization process, the wall thickness of the grown TNTZO nanotubes can be reduced to a size smaller than that of the depletion layer thickness, realizing a fully depleted state for charge carriers to further advance the PEC performance. Hydrogen evolution tests demonstrate the practical efficacy of TNTZO for realizing solar hydrogen production. Furthermore, with the composition complexity and fully depleted band structure, the present TNTZO nanotube arrays may offer a feasible and universal platform for the loading of other semiconductors to construct a sophisticated heterostructure photoelectrode paradigm, in which the photoexcited charge carriers can be entirely utilized for efficient solar-to-fuel conversion.

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.

Nitric oxide activation by distal redox modulation in tetranuclear iron nitrosyl complexes.

PubMed

de Ruiter, Graham; Thompson, Niklas B; Lionetti, Davide; Agapie, Theodor

2015-11-11

A series of tetranuclear iron complexes displaying a site-differentiated metal center was synthesized. Three of the metal centers are coordinated to our previously reported ligand, based on a 1,3,5-triarylbenzene motif with nitrogen and oxygen donors. The fourth (apical) iron center is coordinatively unsaturated and appended to the trinuclear core through three bridging pyrazolates and an interstitial μ4-oxide moiety. Electrochemical studies of complex [LFe3(PhPz)3OFe][OTf]2 revealed three reversible redox events assigned to the Fe(II)4/Fe(II)3Fe(III) (-1.733 V), Fe(II)3Fe(III)/Fe(II)2Fe(III)2 (-0.727 V), and Fe(II)2Fe(III)2/Fe(II)Fe(III)3 (0.018 V) redox couples. Combined Mössbauer and crystallographic studies indicate that the change in oxidation state is exclusively localized at the triiron core, without changing the oxidation state of the apical metal center. This phenomenon is assigned to differences in the coordination environment of the two metal sites and provides a strategy for storing electron and hole equivalents without affecting the oxidation state of the coordinatively unsaturated metal. The presence of a ligand-binding site allowed the effect of redox modulation on nitric oxide activation by an Fe(II) metal center to be studied. Treatment of the clusters with nitric oxide resulted in binding of NO to the apical iron center, generating a {FeNO}(7) moiety. As with the NO-free precursors, the three reversible redox events are localized at the iron centers distal from the NO ligand. Altering the redox state of the triiron core resulted in significant change in the NO stretching frequency, by as much as 100 cm(-1). The increased activation of NO is attributed to structural changes within the clusters, in particular, those related to the interaction of the metal centers with the interstitial atom. The differences in NO activation were further shown to lead to differential reactivity, with NO disproportionation and N2O formation performed by the more electron-rich cluster.

Application of electrochemical processes to membrane bioreactors for improving nutrient removal and fouling control.

PubMed

Borea, Laura; Naddeo, Vincenzo; Belgiorno, Vincenzo

2017-01-01

Membrane bioreactor (MBR) technology is becoming increasingly popular as wastewater treatment due to the unique advantages it offers. However, membrane fouling is being given a great deal of attention so as to improve the performance of this type of technology. Recent studies have proven that the application of electrochemical processes to MBR represents a promising technological approach for membrane fouling control. In this work, two intermittent voltage gradients of 1 and 3 V/cm were applied between two cylindrical perforated electrodes, immersed around a membrane module, at laboratory scale with the aim of investigating the treatment performance and membrane fouling formation. For comparison purposes, the reactor also operated as a conventional MBR. Mechanisms of nutrient removal were studied and membrane fouling formation evaluated in terms of transmembrane pressure variation over time and sludge relative hydrophobicity. Furthermore, the impact of electrochemical processes on transparent exopolymeric particles (TEP), proposed as a new membrane fouling precursor, was investigated in addition to conventional fouling precursors such as bound extracellular polymeric substances (bEPS) and soluble microbial products (SMP). All the results indicate that the integration of electrochemical processes into a MBR has the advantage of improving the treatment performance especially in terms of nutrient removal, with an enhancement of orthophosphate (PO 4 -P) and ammonia nitrogen (NH 4 -N) removal efficiencies up to 96.06 and 69.34 %, respectively. A reduction of membrane fouling was also observed with an increase of floc hydrophobicity to 71.72 %, a decrease of membrane fouling precursor concentrations, and, thus, of membrane fouling rates up to 54.33 %. The relationship found between TEP concentration and membrane fouling rate after the application of electrochemical processes confirms the applicability of this parameter as a new membrane fouling indicator.

Nonylphenol and Octylphenol Differently Affect Cell Redox Balance by Modulating the Nitric Oxide Signaling

PubMed Central

Magnifico, Maria Chiara; Xhani, Marla; Popov, Milica

2018-01-01

Nonylphenol (NP) and octylphenol (OP) are pervasive environmental contaminants belonging to the broader class of compounds known as alkylphenols, with potential human toxic effects. Classified as “xenoestrogens,” NP and OP are able to interfere with the cell endocrine physiology via a direct interaction with the estrogen receptors. Here, using HepG2 cells in culture, the changes of the cell redox balance and mitochondrial activity induced by OP and NP have been investigated at μM concentrations, largely below those provoking acute toxicity, as those typical of environmental contaminants. Following 24 h cell exposure to both OP and NP, ROS production appeared significantly increased (p ≤ 0.01), together with the production of higher NO oxides (p = 0.003) and peroxynitrated protein-derivatives (NP versus CTR, p = 0.003). The mitochondrial proton electrochemical potential gradient instead was decreased (p ≤ 0.05), as the oxygen consumption by complex IV, particularly following incubation with NP (NP versus CTR, p = 0.017). Consistently, the RT-PCR and Western blot analyses proved that the OP and NP can modulate to a different extent the expression of the inducible NOS (NP versus CTR, p ≤ 0.01) and the endothelial NOS (OP versus CTR, p ≤ 0.05), with a significant variation of the coupling efficiency of the latter (NP versus CTR, p ≤ 0.05), a finding that may provide a novel clue to understand the specific xenoestrogenic properties of OP and NP. PMID:29805728

A detailed study on the working mechanism of a heteropoly acid modified TiO2 photoanode for efficient dye-sensitized solar cells.

PubMed

Jiang, Yanxia; Yang, Yulin; Qiang, Liangsheng; Fan, Ruiqing; Li, Liang; Ye, Tengling; Na, Yong; Shi, Yan; Luan, Tianzhu

2015-03-14

A novel heteropolyacid (HPA) K6SiW11O39Ni(H2O)·xH2O (SiW11Ni) modified TiO2 has been successfully synthesized and introduced into the photoanode of dye-sensitized solar cells (DSSCs). The performance of the cell with the HPA-modified photoanode (SiW11Ni/TiO2), mixed with P25 powder in the ratio of 2 : 8, is better than the cell with a pristine P25 photoanode. An increase of 31% in the photocurrent and 22% improvement in the conversion efficiency are obtained. The effect of the heteropolyacid was well studied by UV-vis spectroscopy, spectro-electrochemical spectroscopy, dark current, intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy, open-circuit voltage decay and electrochemical impedance spectroscopy. The results show that the interfacial layer modified by SiW11Ni can enhance the injection and transport of electrons, and then retard the recombination of electrons, which results in a longer electron lifetime. What's more, the introduction of SiW11Ni can simultaneously broaden the absorption in the visible region, eventually leading to an efficient increase in energy conversion efficiency.

Suitability of representative electrochemical energy storage technologies for ramp-rate control of photovoltaic power

NASA Astrophysics Data System (ADS)

Jiang, Yu; Fletcher, John; Burr, Patrick; Hall, Charles; Zheng, Bowen; Wang, Da-Wei; Ouyang, Zi; Lennon, Alison

2018-04-01

Photovoltaic (PV) systems can exhibit rapid variances in their power output due to irradiance changes which can destabilise an electricity grid. This paper presents a quantitative comparison of the suitability of different electrochemical energy storage system (ESS) technologies to provide ramp-rate control of power in PV systems. Our investigations show that, for PV systems ranging from residential rooftop systems to megawatt power systems, lithium-ion batteries with high energy densities (up to 600 Wh L-1) require the smallest power-normalised volumes to achieve the ramp rate limit of 10% min-1 with 100% compliance. As the system size increases, the ESS power-normalised volume requirements are significantly reduced due to aggregated power smoothing, with high power lithium-ion batteries becoming increasingly more favourable with increased PV system size. The possibility of module-level ramp-rate control is also introduced, and results show that achievement of a ramp rate of 10% min-1 with 100% compliance with typical junction box sizes will require ESS energy and power densities of 400 Wh L-1 and 2300 W L-1, respectively. While module-level ramp-rate control can reduce the impact of solar intermittence, the requirement is challenging, especially given the need for low cost and long cycle life.

Role of Oxygen in Ionic Liquid Gating on Two-Dimensional Cr2Ge2Te6: A Non-oxide Material.

PubMed

Chen, Yangyang; Xing, Wenyu; Wang, Xirui; Shen, Bowen; Yuan, Wei; Su, Tang; Ma, Yang; Yao, Yunyan; Zhong, Jiangnan; Yun, Yu; Xie, X C; Jia, Shuang; Han, Wei

2018-01-10

Ionic liquid gating can markedly modulate a material's carrier density so as to induce metallization, superconductivity, and quantum phase transitions. One of the main issues is whether the mechanism of ionic liquid gating is an electrostatic field effect or an electrochemical effect, especially for oxide materials. Recent observation of the suppression of the ionic liquid gate-induced metallization in the presence of oxygen for oxide materials suggests the electrochemical effect. However, in more general scenarios, the role of oxygen in the ionic liquid gating effect is still unclear. Here, we perform ionic liquid gating experiments on a non-oxide material: two-dimensional ferromagnetic Cr 2 Ge 2 Te 6 . Our results demonstrate that despite the large increase of the gate leakage current in the presence of oxygen, the oxygen does not affect the ionic liquid gating effect on  the channel resistance of Cr 2 Ge 2 Te 6 devices (<5% difference), which suggests the electrostatic field effect as the mechanism on non-oxide materials. Moreover, our results show that ionic liquid gating is more effective on the modulation of the channel resistances compared to the back gating across the 300 nm thick SiO 2 .

Advanced Cu chemical displacement technique for SiO2-based electrochemical metallization ReRAM application.

PubMed

Chin, Fun-Tat; Lin, Yu-Hsien; You, Hsin-Chiang; Yang, Wen-Luh; Lin, Li-Min; Hsiao, Yu-Ping; Ko, Chum-Min; Chao, Tien-Sheng

2014-01-01

This study investigates an advanced copper (Cu) chemical displacement technique (CDT) with varying the chemical displacement time for fabricating Cu/SiO2-stacked resistive random-access memory (ReRAM). Compared with other Cu deposition methods, this CDT easily controls the interface of the Cu-insulator, the switching layer thickness, and the immunity of the Cu etching process, assisting the 1-transistor-1-ReRAM (1T-1R) structure and system-on-chip integration. The modulated shape of the Cu-SiO2 interface and the thickness of the SiO2 layer obtained by CDT-based Cu deposition on SiO2 were confirmed by scanning electron microscopy and atomic force microscopy. The CDT-fabricated Cu/SiO2-stacked ReRAM exhibited lower operation voltages and more stable data retention characteristics than the control Cu/SiO2-stacked sample. As the Cu CDT processing time increased, the forming and set voltages of the CDT-fabricated Cu/SiO2-stacked ReRAM decreased. Conversely, decreasing the processing time reduced the on-state current and reset voltage while increasing the endurance switching cycle time. Therefore, the switching characteristics were easily modulated by Cu CDT, yielding a high performance electrochemical metallization (ECM)-type ReRAM.

Modeling the photoacoustic signal during the porous silicon formation

NASA Astrophysics Data System (ADS)

Ramirez-Gutierrez, C. F.; Castaño-Yepes, J. D.; Rodriguez-García, M. E.

2017-01-01

Within this work, the kinetics of the growing stage of porous silicon (PS) during the etching process was studied using the photoacoustic technique. A p-type Si with low resistivity was used as a substrate. An extension of the Rosencwaig and Gersho model is proposed in order to analyze the temporary changes that take place in the amplitude of the photoacoustic signal during the PS growth. The solution of the heat equation takes into account the modulated laser beam, the changes in the reflectance of the PS-backing heterostructure, the electrochemical reaction, and the Joule effect as thermal sources. The model includes the time-dependence of the sample thickness during the electrochemical etching of PS. The changes in the reflectance are identified as the laser reflections in the internal layers of the system. The reflectance is modeled by an additional sinusoidal-monochromatic light source and its modulated frequency is related to the velocity of the PS growth. The chemical reaction and the DC components of the heat sources are taken as an average value from the experimental data. The theoretical results are in agreement with the experimental data and hence provided a method to determine variables of the PS growth, such as the etching velocity and the thickness of the porous layer during the growing process.

Electrochemical and PM-IRRAS Studies of the Effect of Cholesterol on the Structure of a DMPC Bilayer Supported at an Au (111) Electrode Surface, Part 1: Properties of the Acyl Chains

PubMed Central

Bin, Xiaomin; Horswell, Sarah L.; Lipkowski, Jacek

2005-01-01

Charge density measurements and polarization modulation infrared reflection absorption spectroscopy were employed to investigate the spreading of small unilamellar vesicles of a dimyristoylphosphatidylcholine (DMPC)/cholesterol (7:3 molar ratio) mixture onto an Au (111) electrode surface. The electrochemical experiments demonstrated that vesicles fuse and spread onto the Au (111) electrode surface, forming a bilayer, at rational potentials −0.4 V < (E − Epzc) < 0.4 V or field strength <6×107 V m−1. Polarization modulation infrared reflection absorption spectroscopy experiments provided information concerning the conformation and orientation of the acyl chains of DMPC molecules. Deuterated DMPC was used to subtract the contribution of C-H stretching bands of cholesterol and of the polar head region of DMPC from spectra in the C-H stretching region. The absorption spectra of the C-H stretch bands in the acyl chains were determined in this way. The properties of the DMPC/cholesterol bilayer have been compared with the properties of a pure DMPC bilayer. The presence of 30% cholesterol gives a thicker and more fluid bilayer characterized by a lower capacity and lower tilt angle of the acyl chains. PMID:15849259

Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

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

Lin, Hong-Yan; Lu, Huizhe; Le, Mao

2015-03-15

Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){submore » 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology. • Complex 2 is a 1D “cage+cage”-like chain. • Complex 3 is a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology. • The fluorescent, electrochemical and magnetic properties of 1–3 were reported.« less

Li-air batteries: Decouple to stabilize

NASA Astrophysics Data System (ADS)

Xu, Ji-Jing; Zhang, Xin-Bo

2017-09-01

The utilization of porous carbon cathodes in lithium-air batteries is hindered by their severe decomposition during battery cycling. Now, dual redox mediators are shown to decouple the complex electrochemical reactions at the cathode, avoiding cathode passivation and decomposition.

Organic electrochemical transistor based immunosensor for prostate specific antigen (PSA) detection using gold nanoparticles for signal amplification.

PubMed

Kim, Duck-Jin; Lee, Nae-Eung; Park, Joon-Shik; Park, In-Jun; Kim, Jung-Gu; Cho, Hyoung J

2010-07-15

We demonstrated a highly sensitive organic electrochemical transistor (OECT) based immunosensor with a low detection limit for prostate specific antigen/alpha1-antichymotrypsin (PSA-ACT) complex. The poly(styrenesulfonate) doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) based OECT with secondary antibody conjugated gold nanoparticles (AuNPs) provided a detection limit of the PSA-ACT complex as low as 1pg/ml, as well as improved sensitivity and a dynamic range, due to the role of AuNPs in the signal amplification. The sensor performances were particularly improved in the lower concentration range where the detection is clinically important for the preoperative diagnosis and screening of prostate cancer. This result shows that the OECT-based immunosensor can be used as a transducer platform acceptable to the point-of-care (POC) diagnostic systems and demonstrates adaptability of organic electronics to clinical applications. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Antifouling and ultrasensitive biosensing interface based on self-assembled peptide and aptamer on macroporous gold for electrochemical detection of immunoglobulin E in serum.

PubMed

Wang, Yu; Cui, Min; Jiao, Mingxia; Luo, Xiliang

2018-06-25

Accurate detection of protein biomarkers in complex media remains a challenge due to severe nonspecific adsorption and biofouling, and sensing interfaces that combine the high sensitivity and antifouling ability are highly desirable. Herein, an antifouling sensing interface capable of sensitively assaying immunoglobulin E (IgE) in biological samples was constructed. The sensing interface was fabricated through the self-assembly of a zwitterionic peptide and the IgE aptamer onto a macroporous Au substrate, which was electrochemically fabricated with the aid of multilayer polystyrene nanospheres self-assembled on glassy carbon electrode. Due to the huge surface area arising from porous morphology and high specificity of aptamer, the developed electrochemical biosensor exhibits ultrahigh sensitivity and selectivity towards IgE, with the linear range of 0.1-10 pg mL -1 , and a very low limit of detection down to 42 fg mL -1 . Interestingly, owing to the presence of the zwitterionic peptide, the biosensing interface can satisfyingly reduce the nonspecific adsorption and fouling effect. Consequently, the biosensor was successfully applied to detect IgE in complex biological samples, indicating great promise of this peptide-based sensing interface for antifouling assays. Graphical abstract ᅟ.

Hierarchical and Well-Ordered Porous Copper for Liquid Transport Properties Control.

PubMed

Pham, Quang N; Shao, Bowen; Kim, Yongsung; Won, Yoonjin

2018-05-09

Liquid delivery through interconnected pore network is essential for various interfacial transport applications ranging from energy storage to evaporative cooling. The liquid transport performance in porous media can be significantly improved through the use of hierarchical morphology that leverages transport phenomena at different length scales. Traditional surface engineering techniques using chemical or thermal reactions often show nonuniform surface nanostructuring within three-dimensional pore network due to uncontrollable diffusion and reactivity in geometrically complex porous structures. Here, we demonstrate hierarchical architectures on the basis of crystalline copper inverse opals using an electrochemistry approach, which offers volumetric controllability of structural and surface properties within the complex porous metal. The electrochemical process sequentially combines subtractive and additive steps-electrochemical polishing and electrochemical oxidation-to improve surface wetting properties without sacrificing structural permeability. We report the transport performance of the hierarchical inverse opals by measuring the capillary-driven liquid rise. The capillary performance parameter of hierarchically engineered inverse opal ( K/ R eff = ∼5 × 10 -3 μm) is shown to be higher than that of a typical crystalline inverse opal ( K/ R eff = ∼1 × 10 -3 μm) owing to the enhancement in fluid permeable and hydrophilic pathways. The new surface engineering method presented in this work provides a rational approach in designing hierarchical porous copper for transport performance enhancements.

Indirect electroreduction as pretreatment to enhance biodegradability of metronidazole.

PubMed

Saidi, I; Soutrel, I; Floner, D; Fourcade, F; Bellakhal, N; Amrane, A; Geneste, F

2014-08-15

The removal of metronidazole, a biorecalcitrant antibiotic, by coupling an electrochemical reduction with a biological treatment was examined. Electroreduction was performed in a home-made flow cell at -1.2V/SCE on graphite felt. After only one pass through the cell, analysis of the electrolyzed solution showed a total degradation of metronidazole. The biodegradability estimated from the BOD5/COD ratio increased from 0.07 to 0.2, namely below the value usually considered as the limit of biodegradability (0.4). In order to improve these results, indirect electrolysis of metronidazole was performed with a titanium complex known to reduce selectively nitro compounds into amine. The catalytic activity of the titanium complex towards electroreduction of metronidazole was shown by cyclic voltammetry analyses. Indirect electrolysis led to an improvement of the biodegradability from 0.07 to 0.42. To confirm the interest of indirect electroreduction to improve the electrochemical pretreatment, biological treatment was then carried out on activated sludge after direct and indirect electrolyses; different parameters were followed during the culture such as pH, TOC and metronidazole concentration. Both electrochemical processes led to a more efficient biodegradation of metronidazole compared with the single biological treatment, leading to an overall mineralization yield for the coupling process of 85%. Copyright © 2014 Elsevier B.V. All rights reserved.

SEMICONDUCTOR TECHNOLOGY A new cleaning process for the metallic contaminants on a post-CMP wafer's surface

NASA Astrophysics Data System (ADS)

Baohong, Gao; Yuling, Liu; Chenwei, Wang; Yadong, Zhu; Shengli, Wang; Qiang, Zhou; Baimei, Tan

2010-10-01

This paper presents a new cleaning process using boron-doped diamond (BDD) film anode electrochemical oxidation for metallic contaminants on polished silicon wafer surfaces. The BDD film anode electrochemical oxidation can efficiently prepare pyrophosphate peroxide, pyrophosphate peroxide can oxidize organic contaminants, and pyrophosphate peroxide is deoxidized into pyrophosphate. Pyrophosphate, a good complexing agent, can form a metal complex, which is a structure consisting of a copper ion, bonded to a surrounding array of two pyrophosphate anions. Three polished wafers were immersed in the 0.01 mol/L CuSO4 solution for 2 h in order to make comparative experiments. The first one was cleaned by pyrophosphate peroxide, the second by RCA (Radio Corporation of America) cleaning, and the third by deionized (DI) water. The XPS measurement result shows that the metallic contaminants on wafers cleaned by the RCA method and by pyrophosphate peroxide is less than the XPS detection limits of 1 ppm. And the wafer's surface cleaned by pyrophosphate peroxide is more efficient in removing organic carbon residues than RCA cleaning. Therefore, BDD film anode electrochemical oxidation can be used for microelectronics cleaning, and it can effectively remove organic contaminants and metallic contaminants in one step. It also achieves energy saving and environmental protection.

In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach

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

Wang, Zhaoying; Zhang, Yanyan; Liu, Bingwen

The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability we report themore » first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.« less

Technological advancement in electrochemical biosensor based detection of Organophosphate pesticide chlorpyrifos in the environment: A review of status and prospects.

PubMed

Uniyal, Shivani; Sharma, Rajesh Kumar

2018-09-30

Chlorpyrifos (CP), an organophosphate insecticide is broadly used in the agricultural and industrial sectors to control a broad-spectrum of insects of economically important crops. CP detection has been gaining prominence due to its widespread contamination in different environmental matrices, high acute toxicity, and potential to cause long-term environmental and ecological damage even at trace levels. Traditional chromatographic methods for CP detection are complex and require sample preparation and highly skilled personnel for their operation. Over the past decades, electrochemical biosensors have emerged as a promising technology for CP detection as these circumvent deficiencies associated with classical chromatographic techniques. The advantageous features such as appreciable detection limit, miniaturization, sensitivity, low-cost and onsite detection potential are the propulsive force towards sustainable growth of electrochemical biosensing platforms. Recent development in enzyme immobilization methods, novel surface modifications, nanotechnology and fabrication techniques signify a foremost possibility for the design of electrochemical biosensing platforms with improved sensitivity and selectivity. The prime objective of this review is to accentuate the recent advances in the design of biosensing platforms based on diverse biomolecules and biomimetic molecules with unique properties, which would potentially fascinate their applicability for detection of CP residues in real samples. The review also covers the sensing principle of the prime biomolecule and biomimetic molecule based electrochemical biosensors along with their analytical performance, advantages and shortcomings. Present challenges and future outlooks in the field of electrochemical biosensors based CP detection are also discussed. This deep analysis of electrochemical biosensors will provide research directions for further approaching towards commercial development of the broad range of organophosphorus compounds. Copyright © 2018 Elsevier B.V. All rights reserved.

Phosphate determination in seawater: toward an autonomous electrochemical method.

PubMed

Jońca, Justyna; León Fernández, Violeta; Thouron, Danièle; Paulmier, Aurélien; Graco, Michelle; Garçon, Véronique

2011-12-15

Initial steps to create an autonomous in situ electrochemical sensor for orthophosphate determination in seawater are presented. First, the optimal conditions to form the molybdophosphate complex in artificial seawater medium were determined by addition of sulphuric acid and sodium molybdate to the solution containing orthophosphate. Secondly, the anodic oxidation of molybdenum to form molybdate ions and protons was used to create the molybdophosphate complex without addition of any liquid reagents. The molybdophosphate complex is detectable by amperometry with an average precision of 2.2% for the concentration range found in the open ocean and the detection limit is 0.12 μM. Three solutions are proposed to address the silicate interferences issue and one of these methods is used for the natural samples collected in the coastal waters offshore Peru during the Pelagico 1011-12-BIC OLAYA cruise in November-December 2010. Results showed a good precision with an average of 2.5% and a reasonable deviation of the amperometric analysis as compared with colorimetric measurements (4.9%). Copyright © 2011 Elsevier B.V. All rights reserved.

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

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

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE PAGES

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.; ...

2017-05-31

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

A new 3D POMOF based on CuI/CuII-bis(triazole) complexes and BW12 Keggin polyoxoanions: Synthesis, characterization and electrochemical properties

NASA Astrophysics Data System (ADS)

Zhang, Yanjun; Fu, Xin; Zhang, Chunjing; Pang, Hainjun; Ma, Huiyuan; Zhao, Xi; Wang, Cheng

2018-02-01

A novel organic-inorganic hybrid compound, {[CuI(btpe)2][CuII2(H2O)2(btpe)2][BW12O40]}·2H2O, (btpe = 1,5-bis(1,2,4-triazol-1-yl)pentane) (1) has been synthesized by hydrothermal reaction, and characterized by elemental analyses, IR spectroscopy, TG and single X-ray diffraction. Compound 1 is composed of α-Keggin type [BW12O40]5- (BW12) polyoxoanions and copper-btpe complexes. The copper-btpe complexes are stagger-packed to form an open framework containing the two kinds of channels with parallelogram-like apertures, in which the BW12 guests are encapsulated into the bigger channels. The electrochemical studies show that 1 has a good electrocatalytic activity towards reduction of hydrogen peroxide (H2O2), thanking to its special porous POMOF structure. The molecular design of 1 not only generates a new POMOF, but also opens a new avenue to the electrocatalytic materials.

Conformational order of n-dodecanethiol and n-dodecaneselenol monolayers on polycrystalline copper investigated by PM-IRRAS and SFG spectroscopy

NASA Astrophysics Data System (ADS)

Fonder, G.; Cecchet, F.; Peremans, A.; Thiry, P. A.; Delhalle, J.; Mekhalif, Z.

2009-08-01

Self-assembled monolayers (SAMs) of n-dodecanethiol (C 12H 25SH) and n-dodecaneselenol (C 12H 25SeH) on polycrystalline copper have been elaborated with the purpose of achieving densely packed and crystalline-like assemblies. By combining the surface sensitivity of polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), the effect of the self-assembly time (15 min, 30 min, 1 h, 2 h and 24 h) on the formation of n-dodecanethiol and n-dodecaneselenol monolayers on untreated and electrochemically reduced polycrystalline copper has been investigated. On electrochemically reduced copper, PM-IRRAS spectroscopy shows that both molecules are able to form well organized layers. SFG spectroscopy indicates that the C 12H 25SeH SAMs are slightly better ordered than those achieved with C 12H 25SH. On untreated copper, the two molecules lead to different film organizations. Both PM-IRRAS and SFG indicate that C 12H 25SH SAMs are of the same film quality as those obtained on electrochemically reduced copper. On the contrary, C 12H 25SeH monolayers are invariably poorly organized at the molecular level.

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

Branch, Shirmir D.; Lines, Amanda M.; Lynch, John

The electrochemical and spectroelectrochemical applications of an optically transparent thin film electrode chip are investigated. The working electrode is composed of indium tin oxide (ITO); the counter and quasi-reference electrodes are composed of platinum. The stability of the platinum quasi-reference electrode is modified by coating it with a planar, solid state Ag/AgCl layer. The Ag/AgCl reference is characterized with scanning electron microscopy and energy-dispersive X-ray spectroscopy. Open circuit potential measurements indicate that the potential of the planar Ag/AgCl electrode varies a maximum of 20 mV over four days. Cyclic voltammetry measurements show that the electrode chip is comparable to amore » standard electrochemical cell. Randles-Sevcik analysis of 10 mM K3[Fe(CN)6] in 0.1 M KCl using the electrode chip shows a diffusion coefficient of 1.59 × 10-6 cm2/s, in comparison to the standard electrochemical cell value of 2.38 × 10-6 cm2/s. By using the electrode chip in an optically transparent thin layer electrode (OTTLE), the spectroelectrochemical modulation of [Ru(bpy)3]2+ florescence was demonstrated, achieving a detection limit of 36 nM.« less

Metal | polypyrrole battery with the air regenerated positive electrode

NASA Astrophysics Data System (ADS)

Grgur, Branimir N.

2014-12-01

Recharge characteristics of the battery based on the electrochemically synthesized polypyrrole cathode and aluminum, zinc, or magnesium anode in 2 M NH4Cl are investigated. It is shown that polypyrrole electrode can be regenerated by the reoxidation with the dissolved oxygen from the air. Using the polypyrrole synthesized on high surface graphite-felt electrode under modest discharge conditions, stable discharge voltage of 1.1 V is obtained. Such behavior is explained by the complex interaction of polypyrrole and hydrogen peroxide produced by the oxygen reduction reaction. The electrochemical characteristics are compared with the zinc-manganese dioxide and zinc-air systems.

Rare Earth Electrochemical Property Measurements and Phase Diagram Development in a Complex Molten Salt Mixture for Molten Salt Recycle

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

Zhang, Jinsuo; Guo, Shaoqiang

Pyroprocessing is a promising alternative for the reprocessing of used nuclear fuel (UNF) that uses electrochemical methods. Compared to the hydrometallurgical reprocessing method, pyroprocessing has many advantages such as reduced volume of radioactive waste, simple waste processing, ability to treat refractory material, and compatibility with fast reactor fuel recycle. The key steps of the process are the electro-refining of the spent metallic fuel in the LiCl-KCl eutectic salt, which can be integrated with an electrolytic reduction step for the reprocessing of spent oxide fuels.

Electrochemical Impedance Imaging via the Distribution of Diffusion Times

NASA Astrophysics Data System (ADS)

Song, Juhyun; Bazant, Martin Z.

2018-03-01

We develop a mathematical framework to analyze electrochemical impedance spectra in terms of a distribution of diffusion times (DDT) for a parallel array of random finite-length Warburg (diffusion) or Gerischer (reaction-diffusion) circuit elements. A robust DDT inversion method is presented based on complex nonlinear least squares regression with Tikhonov regularization and illustrated for three cases of nanostructured electrodes for energy conversion: (i) a carbon nanotube supercapacitor, (ii) a silicon nanowire Li-ion battery, and (iii) a porous-carbon vanadium flow battery. The results demonstrate the feasibility of nondestructive "impedance imaging" to infer microstructural statistics of random, heterogeneous materials.

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

NASA Astrophysics Data System (ADS)

Kang, Young C.

The following work is the study to evaluate the impact of corrosion inhibitors on the copper metal in drinking water and to investigate the corrosion mechanism in the presence and absence of inhibitors. Electrochemical experiments were conducted to understand the effect of specific corrosion inhibitors in synthetic drinking water which was prepared with controlled specific water quality parameters. Water chemistry was studied by Inductively Coupled Plasma--Atomic Emission Spectroscopy (ICP--AES) to investigate the copper leaching rate with time. Surface morphology, crystallinity of corrosion products, copper oxidation status, and surface composition were characterized by various solid surface analysis methods, such as Scanning Electron Microscopy/Energy--Dispersive Spectrometry (SEM/EDS), Grazing-Incidence-angle X-ray Diffraction (GIXRD), X-ray Photoelectron Spectroscopy (XPS), and Time-of-Flight Secondary Ions Mass Spectrometry (ToF-SIMS). The purpose of the first set of experiments was to test various electrochemical techniques for copper corrosion for short term before studying a long term loop system. Surface analysis techniques were carried out to identify and study the corrosion products that form on the fresh copper metal surface when copper coupons were exposed to test solutions for 2 days of experiments time. The second phase of experiments was conducted with a copper pipe loop system in a synthetic tap water over an extended period of time, i.e., 4 months. Copper release and electrochemically measured corrosion activity profiles were monitored carefully with and without corrosion inhibitor, polyphosphate. A correlation between the copper released into the solution and the electrochemically measured corrosion activities was also attempted. To investigate corrosion products on the copper pipe samples, various surface analysis techniques were applied in this study. Especially, static mass spectra acquisition and element distribution mapping were carried out by ToF-SIMS. Dynamic SIMS provided shallow depth profile of corroded copper sample. The third set of the experiments was related to electrochemical noise (EN) measurement through copper coupons to pipes. Calculating corrosion rate of a metal and predicting exactly how long it lasts are problematic since the metal corrosion may be caused by combined corrosion types. Many other metals undergo not only uniform corrosion, but localized corrosion. Uniform corrosion may be conducive for copper pipe to prevent it from further severe corrosion and form passivated film, but localized corrosion causes pinhole leaks and limits the copper pipe applications. The objective of this set of experiment is to discuss the application of electrochemical noise approaches to drinking water copper corrosion problems. Specially, a fundamental description of EN is presented including a discussion of how to interpret the results and technique limitations. Although it was indicated with electrochemical analysis that the corrosion activity was affected by orthophosphate addition in the short-term test, no copper-phosphate complex or compound was found by copper surface characterization. Apparently, orthophosphate can inhibit corrosion by adsorption on the copper surface, but cannot form solid complexes with copper in such a short time, 2 days. When polyphosphate was added into recirculating copper pipe system, copper level increased and polarization resistance decreased. Greenish blue residue on the copper pipe was suspected as copper phosphate complex and corrosion inhibition mechanism was proposed.

Mechanistic studies of hydrogen evolution in aqueous solution catalyzed by a tertpyridine-amine cobalt complex

DOE PAGES

Lewandowska-Andralojc, Anna; Baine, Teera; Zhao, Xuan; ...

2015-04-22

The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. In addition, while the basic mechanism of proton reduction promoted by cobalt species is well understood, the reactivity of certain reaction intermediates, such as Co I and Co III–H, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH₂)] n+ (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH₂)] n+ wheremore » L is the pentadentate DPA-Bpy ligand or [ Co(OH₂)] n+ as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by DFT calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a Co II species results in weakening the Co–O bond. The further reduction to a Co I species leads to the loss of the aqua ligand and the formation of [ CoI–VS)]⁺ (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [Co I(κ⁴-L)(OH₂)]⁺ species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the Co I species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [ CoIII–H]⁺. We propose that this RDS may originate from the slow removal of a solvent ligand in the intermediate [Co I(κ⁴-L)(OH₂)]⁺ in addition to the significant structural reorganization of the metal complex and surrounding solvent resulting in a high free energy of activation.« less

Azobenzene Pd(II) complexes with N^N- and N^O-type ligands

NASA Astrophysics Data System (ADS)

Nikolaeva, M. V.; Puzyk, An. M.; Puzyk, M. V.

2017-05-01

Methods of synthesis of cyclometalated azobenzene palladium(II) complexes of [Pd(N^N)Azb]ClO4 and [Pd(N^O)Azb]ClO4 types (where Azb- is the deprotonated form of azobenzene; N^N is 2NH3, ethylenediamine, or 2,2'-bipyridine; and (N^O)- is the deprotonated form of amino acid (glycine, α-alanine, β-alanine, tyrosine, or tryptophan)) are developed. The electronic absorption and the electrochemical properties of these complexes are studied.

Terpyridine complexes of first row transition metals and electrochemical reduction of CO₂ to CO.

PubMed

Elgrishi, Noémie; Chambers, Matthew B; Artero, Vincent; Fontecave, Marc

2014-07-21

Homoleptic terpyridine complexes of first row transition metals are evaluated as catalysts for the electrocatalytic reduction of CO2. Ni and Co-based catalytic systems are shown to reduce CO2 to CO under the conditions tested. The Ni complex was found to exhibit selectivity for CO2 over proton reduction while the Co-based system generates mixtures of CO and H2 with CO : H2 ratios being tuneable through variation of the applied potential.

Using Modules in Teaching Complex Analysis

ERIC Educational Resources Information Center

Kinney, William M.

2017-01-01

Educational modules can play an important part in revitalizing the teaching and learning of complex analysis. At the Westmont College workshop on the subject in June 2014, time was spent generating ideas and creating structures for module proposals. Sharing some of those ideas and giving a few example modules is the main purpose of this paper. The…

Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications.

PubMed

Stauber, Julia M; Zhang, Shiyu; Gvozdik, Nataliya; Jiang, Yanfeng; Avena, Laura; Stevenson, Keith J; Cummins, Christopher C

2018-01-17

An electrochemical cell consisting of cobalt ([Co II/III (P 3 O 9 ) 2 ] 4-/3- ) and vanadium ([V III/II (P 3 O 9 ) 2 ] 3-/4- ) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up to 100 total cycles. The [Co(P 3 O 9 ) 2 ] 4- (1) and [V(P 3 O 9 ) 2 ] 3- (2) complexes have favorable properties for flow-battery applications, including reversible redox chemistry, high stability toward electrochemical cycling, and high solubility in MeCN (1.09 ± 0.02 M, [PPN] 4 [1]·2MeCN; 0.77 ± 0.06 M, [PPN] 3 [2]·DME). The [PPN] 4 [1]·2MeCN and [PPN] 3 [2]·DME salts were isolated as crystalline solids in 82 and 68% yields, respectively, and characterized by 31 P NMR, UV/vis, ESI-MS(-), and IR spectroscopy. The [PPN] 4 [1]·2MeCN salt was also structurally characterized, crystallizing in the monoclinic P2 1 /c space group. Treatment of 1 with [(p-BrC 6 H 4 ) 3 N] + allowed for isolation of the one-electron-oxidized spin-crossover (SCO) complex, [Co(P 3 O 9 ) 2 ] 3- (3), which is the active catholyte species generated during cell charging. The success of the 1-2 cell provides a promising entry point to a potential future class of transition-metal metaphosphate-based all-inorganic non-aqueous redox-flow battery electrolytes.

Fluorinated graphenes as advanced biosensors - effect of fluorine coverage on electron transfer properties and adsorption of biomolecules

NASA Astrophysics Data System (ADS)

Urbanová, Veronika; Karlický, František; Matěj, Adam; Šembera, Filip; Janoušek, Zbyněk; Perman, Jason A.; Ranc, Václav; Čépe, Klára; Michl, Josef; Otyepka, Michal; Zbořil, Radek

2016-06-01

Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms.Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms. Electronic supplementary information (ESI) available: SEM, HRTEM, and AFM images the sheet in pristine graphene sample, survey XPS spectrum, high resolution C 1s XPS spectrum, and Raman spectrum of pristine graphene precursor used for controlled fluorination, survey and high resolution F 1s XPS spectra of the CF0.084, CF0.158, and CF0.218 samples, EDS chemical mapping of fluorine in CF0.158, contact angle measurement of CF0.084, CF0.158, CF0.218, and HOPG, and additional electrochemical data. See DOI: 10.1039/c6nr00353b

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Characterization of LiMn 2O 4 cathodes by electrochemical strain microscopy

DOE PAGES

Alikin, D. O.; Ievlev, A. V.; Luchkin, S. Yu.; ...

2016-03-15

Electrochemical strain microscopy (ESM) is a scanning probe microscopy(SPM) method in which the local electrodiffusion is probed via application of AC voltage to the SPM tip and registration of resulting electrochemical strain. In this study, we implemented ESM to measure local strain in bulk LiMn 2O 4 cathodes of a commercial Li-battery in different states of charge to investigate distribution of Li-ion mobility and concentration. Ramped AC ESM imaging and voltage spectroscopy were used to find the most reliable regime of measurements allowing separating and diminishing different contributions to ESM. This is not a trivial task due to complex geometrymore » of the sample and various obstacles resulting in less predictable contributions of different origins into ESM response: electrostatic tip–surface interactions, charge injection, electrostriction, and flexoelectricity. Finally, understanding and control of these contributions is an important step towards quantitative interpretation of ESM data.« less

Nanomaterial-based electrochemical sensors for arsenic - A review.

PubMed

Kempahanumakkagari, Sureshkumar; Deep, Akash; Kim, Ki-Hyun; Kumar Kailasa, Suresh; Yoon, Hye-On

2017-09-15

The existence of arsenic in the environment poses severe global health threats. Considering its toxicity, the sensing of arsenic is extremely important. Due to the complexity of environmental and biological samples, many of the available detection methods for arsenic have serious limitations on selectivity and sensitivity. To improve sensitivity and selectivity and to circumvent interferences, different electrode systems have been developed based on surface modification with nanomaterials including carbonaceous nanomaterials, metallic nanoparticles (MNPs), metal nanotubes (MNTs), and even enzymes. Despite the progress made in electrochemical sensing of arsenic, some issues still need to be addressed to realize cost effective, portable, and flow-injection type sensor systems. The present review provides an in-depth evaluation of the nanoparticle-modified electrode (NME) based methods for the electrochemical sensing of arsenic. NME based sensing systems are projected to become an important option for monitoring hazardous pollutants in both environmental and biological media. Copyright © 2017 Elsevier B.V. All rights reserved.

A signal amplification electrochemical aptasensor for the detection of breast cancer cell via free-running DNA walker.

PubMed

Cai, Shuxian; Chen, Mei; Liu, Mengmeng; He, Wenhui; Liu, Zhijing; Wu, Dongzhi; Xia, Yaokun; Yang, Huanghao; Chen, Jinghua

2016-11-15

Herein, a signal magnification electrochemical aptasensor for the detection of breast cancer cell via free-running DNA walker is constructed. Theoretically, just one DNA walker, released by target cell-responsive reaction, can automatically cleave all D-RNA (a chimeric DNA/RNA oligonucleotide with a cleavage point rArU) anchored on electrode into shorter produces, giving rise to considerably detectable signal finally. Under the optimal conditions, the electrochemical signal decreased linearly with the concentration of MCF-7 cell. The linear range is from 0 to 500 cells mL(-1) with a detection limit of 47 cellsmL(-1). In a word, this approach may have advantages over traditional reported DNA machines for bioassay, particularly in terms of ease of operation, cost efficiency, free of labeling and of complex track design, which may hold great potential for wide application. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemical alkaline Fe(VI) water purification and remediation.

PubMed

Licht, Stuart; Yu, Xingwen

2005-10-15

Fe(VI) is an unusual and strongly oxidizing form of iron, which provides a potentially less hazardous water-purifying agent than chlorine. A novel on-line electrochemical Fe(VI) water purification methodology is introduced. Fe(VI) addition had been a barrier to its effective use in water remediation, because solid Fe(VI) salts require complex (costly) syntheses steps and solutions of Fe(VI) decompose. Online electrochemical Fe(VI) water purification avoids these limitations, in which Fe(VI) is directly prepared in solution from an iron anode as the FeO42- ion, and is added to the contaminant stream. Added FeO42- decomposes, by oxidizing a wide range of water contaminants including sulfides (demonstrated in this study) and other sulfur-containing compounds, cyanides (demonstrated in this study), arsenic (demonstrated in this study), ammonia and other nitrogen-containing compounds (previously demonstrated), a wide range of organics (phenol demonstrated in this study), algae, and viruses (each previously demonstrated).

Electrochemical Liquid Phase Epitaxy (ec-LPE): A New Methodology for the Synthesis of Crystalline Group IV Semiconductor Epifilms.

PubMed

Demuth, Joshua; Fahrenkrug, Eli; Ma, Luyao; Shodiya, Titilayo; Deitz, Julia I; Grassman, Tyler J; Maldonado, Stephen

2017-05-24

Deposition of epitaxial germanium (Ge) thin films on silicon (Si) wafers has been achieved over large areas with aqueous feedstock solutions using electrochemical liquid phase epitaxy (ec-LPE) at low temperatures (T ≤ 90 °C). The ec-LPE method uniquely blends the simplicity and control of traditional electrodeposition with the material quality of melt growth. A new electrochemical cell design based on the compression of a liquid metal electrode into a thin cavity that enables ec-LPE is described. The epitaxial nature, low strain character, and crystallographic defect content of the resultant solid Ge films were analyzed by electron backscatter diffraction, scanning transmission electron microscopy, high resolution X-ray diffraction, and electron channeling contrast imaging. The results here show the first step toward a manufacturing infrastructure for traditional crystalline inorganic semiconductor epifilms that does not require high temperature, gaseous precursors, or complex apparatus.

Comparison of Four Human Papillomavirus Genotyping Methods: Next-generation Sequencing, INNO-LiPA, Electrochemical DNA Chip, and Nested-PCR.

PubMed

Nilyanimit, Pornjarim; Chansaenroj, Jira; Poomipak, Witthaya; Praianantathavorn, Kesmanee; Payungporn, Sunchai; Poovorawan, Yong

2018-03-01

Human papillomavirus (HPV) infection causes cervical cancer, thus necessitating early detection by screening. Rapid and accurate HPV genotyping is crucial both for the assessment of patients with HPV infection and for surveillance studies. Fifty-eight cervicovaginal samples were tested for HPV genotypes using four methods in parallel: nested-PCR followed by conventional sequencing, INNO-LiPA, electrochemical DNA chip, and next-generation sequencing (NGS). Seven HPV genotypes (16, 18, 31, 33, 45, 56, and 58) were identified by all four methods. Nineteen HPV genotypes were detected by NGS, but not by nested-PCR, INNO-LiPA, or electrochemical DNA chip. Although NGS is relatively expensive and complex, it may serve as a sensitive HPV genotyping method. Because of its highly sensitive detection of multiple HPV genotypes, NGS may serve as an alternative for diagnostic HPV genotyping in certain situations. © The Korean Society for Laboratory Medicine

Secondary-Phase Stochastics in Lithium-Ion Battery Electrodes

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

Mistry, Aashutosh N.; Smith, Kandler; Mukherjee, Partha P.

Lithium-ion battery electrodes exhibit complex interplay among multiple electrochemically coupled transport processes, which rely on the underlying functionality and relative arrangement of different constituent phases. The electrochemically inactive solid phases (e.g., conductive additive and binder, referred to as the secondary phase), while beneficial for improved electronic conductivity and mechanical integrity, may partially block the electrochemically active sites and introduce additional transport resistances in the pore (electrolyte) phase. In this work, the role of mesoscale interactions and inherent stochasticity in porous electrodes is elucidated in the context of short-range (interface) and long-range (transport) characteristics. The electrode microstructure significantly affects kinetically andmore » transport-limiting scenarios and thereby the cell performance. The secondary-phase morphology is also found to strongly influence the microstructure-transport-kinetics interactions. Apropos, strategies have been proposed for performance improvement via electrode microstructural modifications.« less

Secondary-Phase Stochastics in Lithium-Ion Battery Electrodes

DOE PAGES

Mistry, Aashutosh N.; Smith, Kandler; Mukherjee, Partha P.

2018-01-12

Lithium-ion battery electrodes exhibit complex interplay among multiple electrochemically coupled transport processes, which rely on the underlying functionality and relative arrangement of different constituent phases. The electrochemically inactive solid phases (e.g., conductive additive and binder, referred to as the secondary phase), while beneficial for improved electronic conductivity and mechanical integrity, may partially block the electrochemically active sites and introduce additional transport resistances in the pore (electrolyte) phase. In this work, the role of mesoscale interactions and inherent stochasticity in porous electrodes is elucidated in the context of short-range (interface) and long-range (transport) characteristics. The electrode microstructure significantly affects kinetically andmore » transport-limiting scenarios and thereby the cell performance. The secondary-phase morphology is also found to strongly influence the microstructure-transport-kinetics interactions. Apropos, strategies have been proposed for performance improvement via electrode microstructural modifications.« less

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

DOE R&D Accomplishments Database

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

SPR and electrochemical analyses of interactions between CYP3A4 or 3A5 and cytochrome b5

NASA Astrophysics Data System (ADS)

Gnedenko, O. V.; Yablokov, E. O.; Usanov, S. A.; Mukha, D. V.; Sergeev, G. V.; Bulko, T. V.; Kuzikov, A. V.; Moskaleva, N. E.; Shumyantseva, V. V.; Ivanov, A. S.; Archakov, A. I.

2014-02-01

The combination of SPR biosensor with electrochemical analysis was used for the study of protein-protein interaction between cytochromes CYP3A4 or 3А5 and cytochromes b5: the microsomal, mitochondrial forms of this protein, and 2 ≪chimeric≫ proteins. Kinetic constants of CYP3A4 and CYP3А5 complex formation with cytochromes b5 were determined by the SPR biosensor. Essential distinction between CYP3A4 and CYP3A5 was observed upon their interactions with mitochondrial cytochrome b5. The electrochemical analysis of CYP3A4, CYP3A5, and cytochromes b5 immobilized on screen printed graphite electrodes modified with membranous matrix revealed that these proteins have very close reduction potentials -0.435 to -0.350 V (vs. Ag/AgCl).

Bandwidth efficient coding for satellite communications

NASA Technical Reports Server (NTRS)

Lin, Shu; Costello, Daniel J., Jr.; Miller, Warner H.; Morakis, James C.; Poland, William B., Jr.

1992-01-01

An error control coding scheme was devised to achieve large coding gain and high reliability by using coded modulation with reduced decoding complexity. To achieve a 3 to 5 dB coding gain and moderate reliability, the decoding complexity is quite modest. In fact, to achieve a 3 dB coding gain, the decoding complexity is quite simple, no matter whether trellis coded modulation or block coded modulation is used. However, to achieve coding gains exceeding 5 dB, the decoding complexity increases drastically, and the implementation of the decoder becomes very expensive and unpractical. The use is proposed of coded modulation in conjunction with concatenated (or cascaded) coding. A good short bandwidth efficient modulation code is used as the inner code and relatively powerful Reed-Solomon code is used as the outer code. With properly chosen inner and outer codes, a concatenated coded modulation scheme not only can achieve large coding gains and high reliability with good bandwidth efficiency but also can be practically implemented. This combination of coded modulation and concatenated coding really offers a way of achieving the best of three worlds, reliability and coding gain, bandwidth efficiency, and decoding complexity.

Development of a Sensitive Electrochemical Enzymatic Reaction-Based Cholesterol Biosensor Using Nano-Sized Carbon Interdigitated Electrodes Decorated with Gold Nanoparticles

PubMed Central

Sharma, Deepti; Lee, Jongmin; Seo, Junyoung; Shin, Heungjoo

2017-01-01

We developed a versatile and highly sensitive biosensor platform. The platform is based on electrochemical-enzymatic redox cycling induced by selective enzyme immobilization on nano-sized carbon interdigitated electrodes (IDEs) decorated with gold nanoparticles (AuNPs). Without resorting to sophisticated nanofabrication technologies, we used batch wafer-level carbon microelectromechanical systems (C-MEMS) processes to fabricate 3D carbon IDEs reproducibly, simply, and cost effectively. In addition, AuNPs were selectively electrodeposited on specific carbon nanoelectrodes; the high surface-to-volume ratio and fast electron transfer ability of AuNPs enhanced the electrochemical signal across these carbon IDEs. Gold nanoparticle characteristics such as size and morphology were reproducibly controlled by modulating the step-potential and time period in the electrodeposition processes. To detect cholesterol selectively using AuNP/carbon IDEs, cholesterol oxidase (ChOx) was selectively immobilized via the electrochemical reduction of the diazonium cation. The sensitivity of the AuNP/carbon IDE-based biosensor was ensured by efficient amplification of the redox mediators, ferricyanide and ferrocyanide, between selectively immobilized enzyme sites and both of the combs of AuNP/carbon IDEs. The presented AuNP/carbon IDE-based cholesterol biosensor exhibited a wide sensing range (0.005–10 mM) and high sensitivity (~993.91 µA mM−1 cm−2; limit of detection (LOD) ~1.28 µM). In addition, the proposed cholesterol biosensor was found to be highly selective for the cholesterol detection. PMID:28914766

Cyclometalated platinum(ii) complexes of 2,2'-bipyridine N-oxide containing a 1,1'-bis(diphenylphosphino)ferrocene ligand: structural, computational and electrochemical studies.

PubMed

Shahsavari, Hamid R; Fereidoonnezhad, Masood; Niazi, Maryam; Mosavi, S Talaat; Habib Kazemi, Sayed; Kia, Reza; Shirkhan, Shima; Abdollahi Aghdam, Siamak; Raithby, Paul R

2017-02-14

The preparation and characterization of new heteronuclear-platinum(ii) complexes containing a 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ 2 N,C-bipyO-H)(SMe 2 )], A, in which bipyO-H is a cyclometalated rollover 2,2'-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of the corresponding binuclear complex [Pt 2 Me 2 (κ 2 N,C-bipyO-H) 2 (μ-dppf)], 1, or the mononuclear complex [PtMe(κ 1 C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelating ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by the single-crystal X-ray diffraction method and it was shown that the chelating dppf ligand in this complex was arranged in a "synclinal-staggered" conformation. Also, the occurrence of intermolecular C-H Cp O bipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.

Coordination-organometallic hybrid materials based on the trinuclear M(II)-Ru(II) (M=Ni and Zn) complexes: Synthesis, structural characterization, luminescence and electrochemical properties

NASA Astrophysics Data System (ADS)

Pawal, S. B.; Lolage, S. R.; Chavan, S. S.

2018-02-01

A new series of trinuclear complexes of the type Ni[R-C6H4Ndbnd CH(O)C6H3Ctbnd CRu(dppe)2Cl]2 (1a-c) and Zn[Rsbnd C6H4Ndbnd CH(O)C6H3Ctbnd CRu(dppe)2Cl]2 (2a-c) have been prepared from the reaction of trans-[RuCl(dppe)2Ctbnd Csbnd C6H3(OH)(CHO)] (1) with aniline, 4-nitroaniline and 4-methoxyaniline (R1-3) in presence of nickel acetate and zinc acetate in CH2Cl2/MeOH (1:1) mixture. The structural properties of the complexes have been characterized by elemental analyses and spectroscopic techniques viz. FTIR, UV-Visible, 1H NMR and 31P NMR spectral studies. The crystal structure and morphology of the hybrid complexes was investigated with the help of X-ray powder diffraction (XRPD), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). The thermal properties of 1a-c and 2a-c were studied by thermogravimetric (TG) analysis. The electrochemical behaviour of the complexes reveals that all complexes displayed a quasireversible redox behaviour corresponding to Ru(II)/Ru(III) and Ni(II)/Ni(III) couples for 1a-c and only Ru(II)/Ru(III) couple for 2a-c. All complexes are emissive in solution at room temperature revealing the influence of substituents and solvent polarity on emission properties of the complexes.

Structural and Electrochemical Consequences of [Cp*] Ligand Protonation.

PubMed

Peng, Yun; Ramos-Garcés, Mario V; Lionetti, Davide; Blakemore, James D

2017-09-05

There are few examples of the isolation of analogous metal complexes bearing [η 5 -Cp*] and [η 4 -Cp*H] (Cp* = pentamethylcyclopentadienyl) complexes within the same metal/ligand framework, despite the relevance of such structures to catalytic applications. Recently, protonation of Cp*Rh(bpy) (bpy = 2,2'-bipyridyl) has been shown to yield a complex bearing the uncommon [η 4 -Cp*H] ligand, rather than generating a [Rh III -H] complex. We now report the purification and isolation of this protonated species, as well as characterization of analogous complexes of 1,10-phenanthroline (phen). Specifically, reaction of Cp*Rh(bpy) or Cp*Rh(phen) with 1 equiv of Et 3 NH + Br - affords rhodium compounds bearing endo-η 4 -pentamethylcyclopentadiene (η 4 -Cp*H) as a ligand. NMR spectroscopy and single-crystal X-ray diffraction studies confirm protonation of the Cp* ligand, rather than formation of metal hydride complexes. Analysis of new structural data and electronic spectra suggests that phen is significantly reduced in Cp*Rh(phen), similar to the case of Cp*Rh(bpy). Backbonding interactions with olefinic motifs are activated by formation of [η 4 -Cp*H]; protonation of [Cp*] stabilizes the low-valent metal center and results in loss of reduced character on the diimine ligands. In accord with these changes in electronic structure, electrochemical studies reveal a distinct manifold of redox processes that are accessible in the [Cp*H] complexes in comparison with their [Cp*] analogues; these processes suggest new applications in catalysis for the complexes bearing endo-η 4 -Cp*H.

High current density cathode for electrorefining in molten electrolyte

DOEpatents

Li, Shelly X.

2010-06-29

A high current density cathode for electrorefining in a molten electrolyte for the continuous production and collection of loose dendritic or powdery deposits. The high current density cathode eliminates the requirement for mechanical scraping and electrochemical stripping of the deposits from the cathode in an anode/cathode module. The high current density cathode comprises a perforated electrical insulated material coating such that the current density is up to 3 A/cm.sup.2.

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center.

PubMed

Chen, Lingjing; Guo, Zhenguo; Wei, Xi-Guang; Gallenkamp, Charlotte; Bonin, Julien; Anxolabéhère-Mallart, Elodie; Lau, Kai-Chung; Lau, Tai-Chu; Robert, Marc

2015-09-02

Molecular catalysis of carbon dioxide reduction using earth-abundant metal complexes as catalysts is a key challenge related to the production of useful products--the "solar fuels"--in which solar energy would be stored. A direct approach using sunlight energy as well as an indirect approach where sunlight is first converted into electricity could be used. A Co(II) complex and a Fe(III) complex, both bearing the same pentadentate N5 ligand (2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene), were synthesized, and their catalytic activity toward CO2 reduction was investigated. Carbon monoxide was formed with the cobalt complex, while formic acid was obtained with the iron-based catalyst, thus showing that the catalysis product can be switched by changing the metal center. Selective CO2 reduction occurs under electrochemical conditions as well as photochemical conditions when using a photosensitizer under visible light excitation (λ > 460 nm, solvent acetonitrile) with the Co catalyst. In the case of the Fe catalyst, selective HCOOH production occurs at low overpotential. Sustained catalytic activity over long periods of time and high turnover numbers were observed in both cases. A catalytic mechanism is suggested on the basis of experimental results and preliminary quantum chemistry calculations.

Advancements in oxygen generation and humidity control by water vapor electrolysis

NASA Technical Reports Server (NTRS)

Heppner, D. B.; Sudar, M.; Lee, M. C.

1988-01-01

Regenerative processes for the revitalization of manned spacecraft atmospheres or other manned habitats are essential for realization of long-term space missions. These processes include oxygen generation through water electrolysis. One promising technique of water electrolysis is the direct conversion of the water vapor contained in the cabin air to oxygen. This technique is the subject of the present program on water vapor electrolysis development. The objectives were to incorporate technology improvements developed under other similar electrochemical programs and add new ones; design and fabricate a mutli-cell electrochemical module and a testing facility; and demonstrate through testing the improvements. Each aspect of the water vapor electrolysis cell was reviewed. The materials of construction and sizing of each element were investigated analytically and sometime experimentally. In addition, operational considerations such as temperature control in response to inlet conditions were investigated. Three specific quantitative goals were established.

Electrotunable nanoplasmonic liquid mirror

NASA Astrophysics Data System (ADS)

Montelongo, Yunuen; Sikdar, Debabrata; Ma, Ye; McIntosh, Alastair J. S.; Velleman, Leonora; Kucernak, Anthony R.; Edel, Joshua B.; Kornyshev, Alexei A.

2017-11-01

Recently, there has been a drive to design and develop fully tunable metamaterials for applications ranging from new classes of sensors to superlenses among others. Although advances have been made, tuning and modulating the optical properties in real time remains a challenge. We report on the first realization of a reversible electrotunable liquid mirror based on voltage-controlled self-assembly/disassembly of 16 nm plasmonic nanoparticles at the interface between two immiscible electrolyte solutions. We show that optical properties such as reflectivity and spectral position of the absorption band can be varied in situ within +/-0.5 V. This observed effect is in excellent agreement with theoretical calculations corresponding to the change in average interparticle spacing. This electrochemical fully tunable nanoplasmonic platform can be switched from a highly reflective `mirror' to a transmissive `window' and back again. This study opens a route towards realization of such platforms in future micro/nanoscale electrochemical cells, enabling the creation of tunable plasmonic metamaterials.

Extended duration orbiter study: CO2 removal and water recovery

NASA Technical Reports Server (NTRS)

Marshall, R. D.; Ellis, G. S.; Schubert, F. H.; Wynveen, R. A.

1979-01-01

Two electrochemical depolarized carbon dioxide concentrator subsystems were evaluated against baseline lithium hydroxide for (1) the baseline orbiter when expanded to accommodate a crew of seven (mission option one), (2) an extended duration orbiter with a power extension package to reduce fuel cell expendables (mission option two), and (3) an extended duration orbiter with a full capability power module to eliminate fuel cell expendables (mission option three). The electrochemical depolarized carbon dioxide concentrator was also compared to the solid amine regenerable carbon dioxide removal concept. Water recovery is not required for Mission Option One since sufficient water is generated by the fuel cells. The vapor compression distillation subsystem was evaluated for mission option two and three only. Weight savings attainable using the vapor compression distillation subsystem for water recovery versus on-board water storage were determined. Combined carbon dioxide removal and water recovery was evaluated to determine the effect on regenerable carbon dioxide removal subsystem selection.

Multilayer porous structures of HVPE and MOCVD grown GaN for photonic applications

NASA Astrophysics Data System (ADS)

Braniste, T.; Ciers, Joachim; Monaico, Ed.; Martin, D.; Carlin, J.-F.; Ursaki, V. V.; Sergentu, V. V.; Tiginyanu, I. M.; Grandjean, N.

2017-02-01

In this paper we report on a comparative study of electrochemical processes for the preparation of multilayer porous structures in hydride vapor phase epitaxy (HVPE) and metal organic chemical vapor phase deposition (MOCVD) grown GaN. It was found that in HVPE-grown GaN, multilayer porous structures are obtained due to self-organization processes leading to a fine modulation of doping during the crystal growth. However, these processes are not totally under control. Multilayer porous structures with a controlled design have been produced by optimizing the technological process of electrochemical etching in MOCVD-grown samples, consisting of five pairs of thin layers with alternating-doping profiles. The samples have been characterized by SEM imaging, photoluminescence spectroscopy, and micro-reflectivity measurements, accompanied by transfer matrix analysis and simulations by a method developed for the calculation of optical reflection spectra. We demonstrate the applicability of the produced structures for the design of Bragg reflectors.

Quantum-Dot-Based Electrochemical Immunoassay for High-Throughput Screening of the Prostate-Specific Antigen

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

Wang, Jun; Liu, Guodong; Wu, Hong

2008-01-01

In this paper, we demonstrate an electrochemical high-throughput sensing platform for simple, sensitive detection of PSA based on QD labels. This sensing platform uses a microplate for immunoreactions and disposable screen-printed electrodes (SPE) for electrochemical stripping analysis of metal ions released from QD labels. With the 96-well microplate, capturing antibodies are conveniently immobilized to the well surface, and the process of immunoreaction is easily controlled. The formed sandwich complexes on the well surface are also easily isolated from reaction solutions. In particular, a microplate-based electrochemical assay can make it feasible to conduct a parallel analysis of several samples or multiplemore » protein markers. This assay offers a number of advantages including (1) simplicity, cost-effectiveness, (2) high sensitivity, (3) capability to sense multiple samples or targets in parallel, and (4) a potentially portable device with an SPE array implanted in the microplate. This PSA assay is sensitive because it uses two amplification processes: (1) QDs as a label for enhancing electrical signal since secondary antibodies are linked to QDs that contain a large number of metal atoms and (2) there is inherent signal amplification for electrochemical stripping analysis—preconcentration of metal ion onto the electrode surface for amplifying electrical signals. Therefore, the high sensitivity of this method, stemming from dual signal amplification via QD labels and pre-concentration, allows low concentration levels to be detected while using small sample volumes. Thus, this QD-based electrochemical detection approach offers a simple, rapid, cost-effective, and high throughput assay of PSA.« less

Problems analysis and new fabrication strategies of mediated electrochemical biosensors for wastewater toxicity assessment.

PubMed

Yang, Yajie; Fang, Deyu; Liu, Yanran; Liu, Runze; Wang, Xiaoshen; Yu, Yuan; Zhi, Jinfang

2018-06-15

Conventional mediated electrochemical biosensors for toxicity assessment were almost based on 'one-pot' principle, i.e., mediators and the under-test chemicals were mixed together in the same vessel. In this process, the electron mediator is assumed to be merely an electron acceptor and cannot react with under-test toxicants. Actually，some under-test pollutants (such as metal ions) could react with the electron mediators, thus affecting the detection accuracy and sensitivity of the sensors. It was also found that at least two other interference factors have been ignored in present'one-pot' mediated electrochemical biosensor systems, i.e., (1) the electrochemical sensitivity of mediators to pH; and (2) the potential reactions between under-test chemicals and buffers and the consequent pH changes. In this study, the three ignored interference factors have been investigated systematically and demonstrated by significance tests. Moreover, a solving strategy, an isolation method, is proposed for fabrication of novel mediated electrochemical biosensor to avoid the interference factors existing at present mediated electrochemical biosensor. According to the testing results obtained from the isolation method, IC 50 values of Cu 2+ , Cd 2+ , Zn 2+ , Fe 3+ , Ni 2+ and Cr 3+ were 21.3 mg/L, 3.7 mg/L, 26.7 mg/L, 4.4 mg/L and 10.7 mg/L, respectively. The detection results of four real water samples also suggested this method could be applied for the practical and complex samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Pencil graphite electrodes for improved electrochemical detection of oleuropein by the combination of Natural Deep Eutectic Solvents and graphene oxide.

PubMed

Gomez, Federico J V; Spisso, Adrian; Fernanda Silva, María

2017-11-01

A novel methodology is presented for the enhanced electrochemical detection of oleuropein in complex plant matrices by Graphene Oxide Pencil Grahite Electrode (GOPGE) in combination with a buffer modified with a Natural Deep Eutectic Solvent, containing 10% (v/v) of Lactic acid, Glucose and H 2 O (LGH). The electrochemical behavior of oleuropein in the modified-working buffer was examined using differential pulse voltammetry. The combination of both modifications, NADES modified buffer and nanomaterial modified electrode, LGH-GOPGE, resulted on a signal enhancement of 5.3 times higher than the bare electrode with unmodified buffer. A calibration curve of oleuropein was performed between 0.10 to 37 μM and a good linearity was obtained with a correlation coefficient of 0.989. Detection and quantification limits of the method were obtained as 30 and 102 nM, respectively. In addition, precision studies indicated that the voltammetric method was sufficiently repeatable, %RSD 0.01 and 3.16 (n = 5) for potential and intensity, respectively. Finally, the proposed electrochemical sensor was successfully applied to the determination of oleuropein in an olive leaf extract prepared by ultrasound-assisted extraction. The results obtained with the proposed electrochemical sensor were compared with Capillary Zone Electrophoresis analysis with satisfactory results. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of loading carbon nanotubes onto chitosan films on electrochemical dopamine sensing in the presence of biological interference.

PubMed

Shukla, Sudheesh K; Lavon, Avia; Shmulevich, Offir; Ben-Yoav, Hadar

2018-05-01

In vivo monitoring of the neurotransmitter dopamine can potentially improve the diagnosis of neurological disorders and elucidate their underlying biochemical mechanisms. While electrochemical sensors can detect unlabeled dopamine molecules, their sensing performance is dramatically reduced by electrochemical currents generated by other, interfering molecules (e.g., uric acid) in the biological environment. To overcome this caveat, the surface of the sensor is often modified with electrocatalytic materials, which are encapsulated inside a polymeric film; however, the effect of the encapsulating film on the sensing performance of the electrode has not been systematically studied. This study characterizes the effect of loading carbon nanotubes (CNTs) onto a chitosan film on the electrochemical sensing performance of dopamine in the presence of uric acid. Higher CNT loading increases the diffusion and electron transfer rate coefficients of the sensor and, in the presence of uric acid, provides better sensitivity (3.00µALµmol -1 for 1.75% CNT loading, vs 0.01µALµmol -1 for 1% loading) but a poorer limit-of-detection (2.00µmolL -1 vs 1.00, respectively), as reported here for the first time. These findings can help optimize the sensitivity and the limit-of-detection of electrochemical sensors in complex biofluids to enable an in vivo monitoring of dopamine and other redox-active molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrochemical Genosensing of Circulating Biomarkers

PubMed Central

Campuzano, Susana; Yáñez-Sedeño, Paloma; Pingarrón, José Manuel

2017-01-01

Management and prognosis of diseases requires the measurement in non- or minimally invasively collected samples of specific circulating biomarkers, consisting of any measurable or observable factors in patients that indicate normal or disease-related biological processes or responses to therapy. Therefore, on-site, fast and accurate determination of these low abundance circulating biomarkers in scarcely treated body fluids is of great interest for health monitoring and biological applications. In this field, electrochemical DNA sensors (or genosensors) have demonstrated to be interesting alternatives to more complex conventional strategies. Currently, electrochemical genosensors are considered very promising analytical tools for this purpose due to their fast response, low cost, high sensitivity, compatibility with microfabrication technology and simple operation mode which makes them compatible with point-of-care (POC) testing. In this review, the relevance and current challenges of the determination of circulating biomarkers related to relevant diseases (cancer, bacterial and viral infections and neurodegenerative diseases) are briefly discussed. An overview of the electrochemical nucleic acid–based strategies developed in the last five years for this purpose is given to show to both familiar and non-expert readers the great potential of these methodologies for circulating biomarker determination. After highlighting the main features of the reported electrochemical genosensing strategies through the critical discussion of selected examples, a conclusions section points out the still existing challenges and future directions in this field. PMID:28420103

Exploration of two-dimensional bio-functionalized phosphorene nanosheets (black phosphorous) for label free haptoglobin electro-immunosensing applications

NASA Astrophysics Data System (ADS)

Tuteja, Satish K.; Neethirajan, Suresh

2018-04-01

We report on the development of an antibody-functionalized interface based on electrochemically active liquid-exfoliated two-dimensional phosphorene (Ph) nanosheets—also known as black phosphorous nanosheets—for the label-free electrochemical immunosensing of a haptoglobin (Hp) biomarker, a clinical marker of severe inflammation. The electrodeposition has been achieved over the screen-printed electrode (SPE) using liquid-assisted ultrasonically exfoliated black phosphorus nanosheets. Subsequently, Ph-SPEs bioconjugated with Hp antibodies (Ab), using electrostatic interactions via a poly-L-lysine linker for biointerface development. Electrochemical analysis demonstrates that the Ab-modified Ph-SPEs (Ab@Ph-SPE) exhibit enhanced electroconducting behavior as compared to the pristine electrodes. This Ab-functionalized phosphorene-based electrochemical immunosensor platform has demonstrated remarkable sensitivity and specificity, having a dynamic linear response range from 0.01-10 mg ml-1 for Hp in standard and serum samples with a low detection limit (˜0.011 mg ml-1) using the label-free electrochemical technique. The sensor electrodes were also studied with other closely relative interferents to investigate cross reactivity and specificity. This strategy opens up avenues to POC (point-of-care) and on-farm livestock disease monitoring technologies for multiplexed diagnosis in complex biological samples such as serum. The technique is simple in fabrication and provides an analytical response in less than 60 s.

Electrochemical Deposition of Conformal and Functional Layers on High Aspect Ratio Silicon Micro/Nanowires.

PubMed

Ozel, Tuncay; Zhang, Benjamin A; Gao, Ruixuan; Day, Robert W; Lieber, Charles M; Nocera, Daniel G

2017-07-12

Development of new synthetic methods for the modification of nanostructures has accelerated materials design advances to furnish complex architectures. Structures based on one-dimensional (1D) silicon (Si) structures synthesized using top-down and bottom-up methods are especially prominent for diverse applications in chemistry, physics, and medicine. Yet further elaboration of these structures with distinct metal-based and polymeric materials, which could open up new opportunities, has been difficult. We present a general electrochemical method for the deposition of conformal layers of various materials onto high aspect ratio Si micro- and nanowire arrays. The electrochemical deposition of a library of coaxial layers comprising metals, metal oxides, and organic/inorganic semiconductors demonstrate the materials generality of the synthesis technique. Depositions may be performed on wire arrays with varying diameter (70 nm to 4 μm), pitch (5 μ to 15 μ), aspect ratio (4:1 to 75:1), shape (cylindrical, conical, hourglass), resistivity (0.001-0.01 to 1-10 ohm/cm 2 ), and substrate orientation. Anisotropic physical etching of wires with one or more coaxial shells yields 1D structures with exposed tips that can be further site-specifically modified by an electrochemical deposition approach. The electrochemical deposition methodology described herein features a wafer-scale synthesis platform for the preparation of multifunctional nanoscale devices based on a 1D Si substrate.

Real time in situ ellipsometric and gravimetric monitoring for electrochemistry experiments.

PubMed

Broch, Laurent; Johann, Luc; Stein, Nicolas; Zimmer, Alexandre; Beck, Raphaël

2007-06-01

This work describes a new system using real time spectroscopic ellipsometer with simultaneous electrochemical and electrochemical quartz crystal microbalance (EQCM) measurements. This method is particularly adapted to characterize electrolyte/electrode interfaces during electrochemical and chemical processes in liquid medium. The ellipsometer, based on a rotating compensator Horiba Jobin-Yvon ellipsometer, has been adapted to acquire Psi-Delta spectra every 25 ms on a spectral range fixed from 400 to 800 nm. Measurements with short sampling times are only achievable with a fixed analyzer position (A=45 degrees ). Therefore the ellipsometer calibration is extremely important for high precision measurements and we propose a spectroscopic calibration (i.e., determination of the azimuth of elements according to the wavelength) on the whole spectral range. A homemade EQCM was developed to detect mass variations attached to the electrode. This additional instrument provides further information useful for ellipsometric data modeling of complex electrochemical systems. The EQCM measures frequency variations of piezoelectric quartz crystal oscillator working at 5 MHz. These frequency variations are linked to mass variations of electrode surface with a precision of 20 ng cm(-2) every 160 ms. Data acquisition has been developed in order to simultaneously record spectroscopic ellipsometry, EQCM, and electrochemical measurements by a single computer. Finally the electrodeposition of bismuth telluride film was monitored by this new in situ experimental setup and the density of electroplated layers was extracted from the optical thickness and EQCM mass.

Poly(vinyl Alcohol) Borate Gel Polymer Electrolytes Prepared by Electrodeposition and Their Application in Electrochemical Supercapacitors.

PubMed

Jiang, Mengjin; Zhu, Jiadeng; Chen, Chen; Lu, Yao; Ge, Yeqian; Zhang, Xiangwu

2016-02-10

Gel polymer electrolytes (GPEs) have been studied for preparing flexible and compact electrochemical energy storage devices. However, the preparation and use of GPEs are complex, and most GPEs prepared through traditional methods do not have good wettability with the electrodes, which retard them from achieving their performance potential. In this study, these problems are addressed by conceiving and implementing a simple, but effective, method of electrodepositing poly(vinyl alcohol) potassium borate (PVAPB) GPEs directly onto the surfaces of active carbon electrodes for electrochemical supercapacitors. PVAPB GPEs serve as both the electrolyte and the separator in the assembled supercapacitors, and their scale and shape are determined solely by the geometry of the electrodes. PVAPB GPEs have good bonding to the active electrode materials, leading to excellent and stable electrochemical performance of the supercapacitors. The electrochemical performance of PVAPB GPEs and supercapacitors can be manipulated simply by adjusting the concentration of KCl salt used during the electrodeposition process. With a 0.9 M KCl concentration, the as-prepared supercapacitors deliver a specific capacitance of 65.9 F g(-1) at a current density of 0.1 A g(-1) and retain more than 95% capacitance after 2000 charge/discharge cycles at a current density of 1 A g(-1). These supercapacitors also exhibit intelligent high voltage self-protection function due to the electrolysis-induced cross-linking effect of PVAPB GPEs.

A sensitive electrochemical biosensor for detection of protein kinase A activity and inhibitors based on Phos-tag and enzymatic signal amplification.

PubMed

Yin, Huanshun; Wang, Mo; Li, Bingchen; Yang, Zhiqing; Zhou, Yunlei; Ai, Shiyun

2015-01-15

A simple, highly sensitive and selective electrochemical assay is developed for the detection of protein kinase A (PKA) activity based on the specific recognition utility of Phos-tag for kinase-induced phosphopeptides and enzymatic signal amplification. When the substrate peptide was phosphorylated by PKA reaction, they could specifically bind with Phos-tag-biotin in the presence of Zn(2+) through the formation of a specific noncovalent complex with the phosphomonoester dianion in phosphorylated peptides. Through the further specific interaction between biotin and avidin, avidin functionalized horseradish peroxidase (HRP) can be captured on the electrode surface. Under the catalytic effect of HRP, a sensitive electrochemical signal for benzoquinone was obtained, which was related to PKA activity. Under the optimal experiment conditions, the proposed electrochemical method presented dynamic range from 0.5 to 25 unit/mL with low detection limit of 0.15 unit/mL. This new detection strategy was also successfully applied to analyze the inhibition effect of inhibitors (ellagic acid and H-89) on PKA activity and monitored the PKA activity in cell lysates. Therefore, this Phos-tag-based electrochemical assay offers an alternative platform for PKA activity assay and inhibitor screening, and thus it might be a valuable tool for development of targeted therapy and clinical diagnosis. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemical control of a DNA Holliday Junction nanoswitch by Mg2+ ions.

PubMed

Ferapontova, E E; Mountford, C P; Crain, J; Buck, A H; Dickinson, P; Beattie, J S; Ghazal, P; Terry, J G; Walton, A J; Mount, A R

2008-11-15

The molecular conformation of a synthetic branched, 4-way DNA Holliday junction (HJ) was electrochemically switched between the open and closed (stacked) conformers. Switching was achieved by electrochemically induced quantitative release of Mg(2+) ions from the oxidised poly(N-methylpyrrole) film (PPy), which contained polyacrylate as an immobile counter anion and Mg(2+) ions as charge compensating mobile cations. This increase in the Mg(2+) concentration screened the electrostatic repulsion between the widely separated arms in the open HJ configuration, inducing switching to the closed conformation. Upon electrochemical reduction of PPy, entrapment of Mg(2+) ions back into the PPy film induced the reverse HJ switching from the closed to open state. The conformational transition was monitored using fluorescence resonance energy transfer (FRET) between donor and acceptor dyes each located at the terminus of one of the arms. The demonstrated electrochemical control of the conformation of the used probe-target HJ complex, previously reported as a highly sequence specific nanodevice for detecting of unlabelled target [Buck, A.H., Campbell, C.J., Dickinson, P., Mountford, C.P., Stoquert, H.C., Terry, J.G., Evans, S.A.G., Keane, L., Su, T.J., Mount, A.R., Walton, A.J., Beattie, J.S., Crain, J., Ghazal, P., 2007. Anal. Chem., 79, 4724-4728], allows the development of electronically addressable DNA nanodevices and label-free gene detection assays.

Synthesis, characterization, DNA-binding and cleavage studies of polypyridyl copper(II) complexes

NASA Astrophysics Data System (ADS)

Gubendran, Ammavasi; Rajesh, Jegathalaprathaban; Anitha, Kandasamy; Athappan, Periyakaruppan

2014-10-01

Six new mixed-ligand copper(II) complexes were synthesized namely [Cu(phen)2OAc]ClO4ṡH2O(1), [Cu(bpy)2OAc]ClO4ṡH2O(2), [Cu(o-ampacac)(phen)]ClO4(3), [Cu(o-ampbzac)(phen)]ClO4(4), [Cu(o-ampacac)(bpy)]ClO4(5), and [Cu(o-ampbzac)(bpy)]ClO4(6) (phen = 1,10-phenanthroline, bpy = 2, 2‧-bipyridine, o-ampacac = (Z)-4-(2-hydroxylamino)pent-3-ene-2-one,o-ampbzac = (Z)-4-(2-hydroxylamino)-4-phenylbut-3-ene-2-one)and characterized by UV-Vis, IR, EPR and cyclic voltammetry. Ligands were characterized by NMR spectra. Single crystal X-ray studies of the complex 1 shows Cu(II) ions are located in a highly distorted octahedral environment. Absorption spectral studies reveal that the complexes 1-6 exhibit hypochromicity during the interaction with DNA and binding constant values derived from spectral and electrochemical studies indicate that complexes 1, 2 and 3 bind strongly with DNA possibly by an intercalative mode. Electrochemical studies reveal that the complexes 1-4 prefer to bind with DNA in Cu(I) rather than Cu(II) form. The shift in the formal potentials E1/2 and CD spectral studies suggest groove or electrostatic binding mode for the complexes 4-6. Complex 1 can cleave supercoiled (SC) pUC18 DNA efficiently into nicked form II under photolytic conditions and into an open circular form (form II) and linear form (form III) in the presence of H2O2 at pH 8.0 and 37 °C, while the complex 2 does not cleave DNA under similar conditions.

Synthesis, spectroscopic characterization, electrochemical behavior and computational analysis of mixed diamine ligand gold(III) complexes: antiproliferative and in vitro cytotoxic evaluations against human cancer cell lines.

PubMed

Al-Jaroudi, Said S; Monim-ul-Mehboob, M; Altaf, Muhammad; Al-Saadi, Abdulaziz A; Wazeer, Mohammed I M; Altuwaijri, Saleh; Isab, Anvarhusein A

2014-12-01

The gold(III) complexes of the type [(DACH)Au(en)]Cl3, 1,2-Diaminocyclohexane ethylenediamine gold(III) chloride [where 1,2-DACH = cis-, trans-1,2- and S,S-1,2diaminocyclohexane and en = ethylenediamine] have been synthesized and characterized using various analytical and spectroscopic techniques including elemental analysis, UV-Vis and FTIR spectra; and solution as well as solid-state NMR measurements. The solid-state (13)C NMR shows that 1,2-diaminocyclohexane (1,2-DACH) and ethylenediamine (en) are strongly bound to the gold(III) center via N donor atoms. The stability of the mixed diamine ligand gold(III) was determined by (1)H and (13)C NMR spectra. Their electrochemical behavior was studied by cyclic voltammetry. The structural details and relative stabilities of the four possible isomers of the complexes were also reported at the B3LYP/LANL2DZ level of theory. The coordination sphere of these complexes around gold(III) center adopts distorted square planar geometry. The computational study also demonstrates that trans- conformations is slightly more stable than the cis-conformations. The antiproliferative effects and cytotoxic properties of the mixed diamine ligand gold(III) complexes were evaluated in vitro on human gastric SGC7901 and prostate PC3 cancer cells using MTT assay. The antiproliferative study of the gold(III) complexes on PC3 and SGC7901 cells indicate that complex 1 is the most effective antiproliferative agent among mixed ligand based gold(III) complexes 1-3. The IC50 data reveal that the in vitro cytotoxicity of complexes 1 and 3 against SGC7901 cancer cells are fairly better than that of cisplatin.

Complexes of silver(I) ions and silver phosphate nanoparticles with hyaluronic acid and/or chitosan as promising antimicrobial agents for vascular grafts.

PubMed

Chudobova, Dagmar; Nejdl, Lukas; Gumulec, Jaromir; Krystofova, Olga; Rodrigo, Miguel Angel Merlos; Kynicky, Jindrich; Ruttkay-Nedecky, Branislav; Kopel, Pavel; Babula, Petr; Adam, Vojtech; Kizek, Rene

2013-06-28

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes.

Complexes of Silver(I) Ions and Silver Phosphate Nanoparticles with Hyaluronic Acid and/or Chitosan as Promising Antimicrobial Agents for Vascular Grafts

PubMed Central

Chudobova, Dagmar; Nejdl, Lukas; Gumulec, Jaromir; Krystofova, Olga; Rodrigo, Miguel Angel Merlos; Kynicky, Jindrich; Ruttkay-Nedecky, Branislav; Kopel, Pavel; Babula, Petr; Adam, Vojtech; Kizek, Rene

2013-01-01

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes. PMID:23812079

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1984

1984-01-01

Presents an experiment which links mass spectrometry to gas chromatography. Also presents a simulation of iron extraction using a ZX81 computer and discussions of Fehling versus Benedict's solutions, transition metal ammine complexes, electrochemical and other chemical series, and a simple model of dynamic equilibria. (JN)

Resonance-Raman spectro-electrochemistry of intermediates in molecular artificial photosynthesis of bimetallic complexes.

PubMed

Zedler, Linda; Guthmuller, Julien; Rabelo de Moraes, Inês; Kupfer, Stephan; Krieck, Sven; Schmitt, Michael; Popp, Jürgen; Rau, Sven; Dietzek, Benjamin

2014-05-25

The sequential order of photoinduced charge transfer processes and accompanying structure changes were analyzed by UV-vis and resonance-Raman spectroscopy of intermediates of a Ru(ii) based photocatalytic hydrogen evolving system obtained by electrochemical reduction.

Selective electrochemical reduction of CO2 to CO with a cobalt chlorin complex adsorbed on multi-walled carbon nanotubes in water.

PubMed

Aoi, Shoko; Mase, Kentaro; Ohkubo, Kei; Fukuzumi, Shunichi

2015-06-25

Electrocatalytic reduction of CO2 occurred efficiently using a glassy carbon electrode modified with a cobalt(II) chlorin complex adsorbed on multi-walled carbon nanotubes at an applied potential of -1.1 V vs. NHE to yield CO with a Faradaic efficiency of 89% with hydrogen production accounting for the remaining 11% at pH 4.6.

Synthesis, structure, spectroscopic and electrochemical properties of (2-amino-4-methylpyrimidine)-(pyridine-2,6-dicarboxylato)copper(II) monohydrate

NASA Astrophysics Data System (ADS)

Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet; Büyükgüngör, Orhan

2007-05-01

The (2-amino-4-methylpyrimidine)-(pyridine-2,6-dicarboxylato)copper(II) monohydrate complex was synthesized and characterized by spectroscopic (IR, UV/Vis, EPR), thermal (TG/DTA) and electrochemical methods. X-ray structural analysis of the title complex revealed that the copper ion can be considered to have two coordination spheres. In the first coordination sphere the copper ion forms distorted square-planar geometry with trans-N 2O 2 donor set, and also the metal ion is weakly bonded to the amino-nitrogen in the layer over and to the carboxylic oxygen in the layer underneath in the second coordination sphere. The second coordination environment on the copper ion is attributed to pseudo octahedron. The powder EPR spectra of Cu(II) complex at room and liquid nitrogen temperature were recorded. The calculated g and A parameters have indicated that the paramagnetic centre is axially symmetric. The molecular orbital bond coefficients of the Cu(II) ion in d 9 state is also calculated by using EPR and optical absorption parameters. The cyclic voltammogram of the title complex investigated in DMSO (dimethylsulfoxide) solution exhibits only metal centered electroactivity in the potential range -1.25 to 1.5 V versus Ag/AgCl reference electrode.

Synthesis, spectroscopic, electrochemical and computational studies of rhenium(i) tricarbonyl complexes based on bidentate-coordinated 2,6-di(thiazol-2-yl)pyridine derivatives.

PubMed

Klemens, Tomasz; Czerwińska, Katarzyna; Szlapa-Kula, Agata; Kula, Slawomir; Switlicka, Anna; Kotowicz, Sonia; Siwy, Mariola; Bednarczyk, Katarzyna; Krompiec, Stanisław; Smolarek, Karolina; Maćkowski, Sebastian; Danikiewicz, Witold; Schab-Balcerzak, Ewa; Machura, Barbara

2017-07-25

Nine rhenium(i) complexes possessing three carbonyl groups together with a bidentate coordinated 2,6-di(thiazol-2-yl)pyridine derivative were synthesized to examine the impact of structure modification of the triimine ligand on the photophysical, thermal and electrochemical properties of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)]. The Re(i) complexes were fully characterized using IR, 1 H and 13 C, HRMS-ESI and single crystal X-ray analysis. Their thermal properties were evaluated using DSC and TGA measurements. Photoluminescence spectra of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)] were investigated in solution and in the solid state, at 298 and 77 K. Both emission wavelengths and quantum yields of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)] were found to be structure-related, demonstrating a crucial role of the substituent attached to the 2,6-di(thiazol-2-yl)pyridine skeleton. In order to fully understand the photophysical properties of [ReCl(CO) 3 (4-R n -dtpy-κ 2 N)], density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed. Furthermore, the complexes which showed appropriate solubility in chloroform were tested as an emissive active layer in OLED devices.

EPR, UV-vis, magnetic, spectral studies and electrochemical behaviour of mononuclear transition metal complexes derived from novel hexa-aza-macrotricyclic ligand

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Gupta, Nidhi; Gupta, Rachna; Bawa, Sukhwant Singh

2005-11-01

Aza-macrocyclic complexes have gained importance because of their pharmacological properties [N.K. Singh, Srivastava, Trans. Met. Chem. 25 (2000) 133]. Hexa-aza-macrocyles containing glutarimide efficiently coordinate as hexa-dentate ligand, to give complexes of Cu(II) possessing tetragonal structure and Mn(II), Co(II) and Ni(II) metal ions that are essentially octahedral. Spectroscopic, and chemical characterizations of these systems are presented in this article. For Ni(II) complexes results on electron transfer processes measured by cyclic voltammetry and colourimetry have been studied.

Synthesis, characterization and electrochemical studies of some Ni(II)Cu(II) heterobimetallic complexes derived from succinoyldihydrazones.

PubMed

Borthakur, R; Kumar, A; Lal, R A

2015-10-05

Synthesis, structural characterization and redox properties of three heterobimetallic complexes with formule {[NiCu(L(n))(CH3OH)3]·CH3OH} using [Cu(H2L(n))(H2O)] as metalloligand have been demonstrated in the present paper. Electronic spectroscopy suggests that the copper center has a pseudo square pyramidal stereochemistry in all the complexes while the nickel center has a distorted octahedral stereochemistry. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, characterization and properties of some divalent metal(II) complexes: Their electrochemical, catalytic, thermal and antimicrobial activity studies

NASA Astrophysics Data System (ADS)

Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

2007-07-01

In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H 3A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H 3A) with phtaldialdehyde (H 2L), 4-methyl-2,6-di-formlyphenol (H 3L 1) and 4- t-butyl-2,6-di-formylphenol (H 3L 2) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H 2L, H 3L 1 and H 3L 2 have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di- tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di- tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

Vapor-Phase Atomic Layer Deposition of Co9S8 and Its Application for Supercapacitors.

PubMed

Li, Hao; Gao, Yuanhong; Shao, Youdong; Su, Yantao; Wang, Xinwei

2015-10-14

Atomic layer deposition (ALD) of cobalt sulfide (Co9S8) is reported. The deposition process uses bis(N,N'-diisopropylacetamidinato)cobalt(II) and H2S as the reactants and is able to produce high-quality Co9S8 films with an ideal layer-by-layer ALD growth behavior. The Co9S8 films can also be conformally deposited into deep narrow trenches with aspect ratio of 10:1, which demonstrates the high promise of this ALD process for conformally coating Co9S8 on high-aspect-ratio 3D nanostructures. As Co9S8 is a highly promising electrochemical active material for energy devices, we further explore its electrochemical performance by depositing Co9S8 on porous nickel foams for supercapacitor electrodes. Benefited from the merits of ALD for making high-quality uniform thin films, the ALD-prepared electrodes exhibit remarkable electrochemical performance, with high specific capacitance, great rate performance, and long-term cyclibility, which highlights the broad and promising applications of this ALD process for energy-related electrochemical devices, as well as for fabricating complex 3D nanodevices in general.

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.

Spatiotemporal norepinephrine mapping using a high-density CMOS microelectrode array.

PubMed

Wydallis, John B; Feeny, Rachel M; Wilson, William; Kern, Tucker; Chen, Tom; Tobet, Stuart; Reynolds, Melissa M; Henry, Charles S

2015-10-21

A high-density amperometric electrode array containing 8192 individually addressable platinum working electrodes with an integrated potentiostat fabricated using Complementary Metal Oxide Semiconductor (CMOS) processes is reported. The array was designed to enable electrochemical imaging of chemical gradients with high spatiotemporal resolution. Electrodes are arranged over a 2 mm × 2 mm surface area into 64 subarrays consisting of 128 individual Pt working electrodes as well as Pt pseudo-reference and auxiliary electrodes. Amperometric measurements of norepinephrine in tissue culture media were used to demonstrate the ability of the array to measure concentration gradients in complex media. Poly(dimethylsiloxane) microfluidics were incorporated to control the chemical concentrations in time and space, and the electrochemical response at each electrode was monitored to generate electrochemical heat maps, demonstrating the array's imaging capabilities. A temporal resolution of 10 ms can be achieved by simultaneously monitoring a single subarray of 128 electrodes. The entire 2 mm × 2 mm area can be electrochemically imaged in 64 seconds by cycling through all subarrays at a rate of 1 Hz per subarray. Monitoring diffusional transport of norepinephrine is used to demonstrate the spatiotemporal resolution capabilities of the system.

Highly sensitive electrochemical detection of cocaine on graphene/AuNP modified electrode via catalytic redox-recycling amplification.

PubMed

Jiang, Bingying; Wang, Min; Chen, Ying; Xie, Jiaqing; Xiang, Yun

2012-02-15

We demonstrated a new strategy for highly sensitive electrochemical detection of cocaine by using two engineered aptamers in connection to redox-recycling signal amplification. The graphene/AuNP nanocomposites were electrochemically deposited on a screen printed carbon electrode to enhance the electron transfers. The cocaine primary binding aptamers were self-assembled on the electrode surface through sulfur-Au interactions. The presence of the target cocaine and the biotin-modified secondary binding aptamers leads to the formation of sandwich complexes on the electrode surface. The streptavidin-conjugated alkaline phosphatases (ALPs) were used as labels to generate quantitative signals. The addition of the ALP substrate and the co-reactant NADH results in the formation of a redox cycle between the enzymatic product and the electrochemically oxidized species and the signal is thus significantly amplified. Because of the effective modification of the sensing surface and signal amplification, low nanomolar (1 nM) detection limit for cocaine is achieved. The proposed aptamer-based sandwich sensing approach for amplified detection of cocaine thus opens new opportunities for highly sensitive determination of other small molecules. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrochemical aptamer-based nanosensor fabricated on single Au nanowire electrodes for adenosine triphosphate assay.

PubMed

Wang, Dongmei; Xiao, Xiaoqing; Xu, Shen; Liu, Yong; Li, Yongxin

2018-01-15

In this work, single Au nanowire electrodes (AuNWEs) were fabricated by laser-assisted pulling/hydrofluoric acid (HF) etching process, which then were characterized by transmission electron microscopy (TEM), electrochemical method and finite-element simulation. The as-prepared single AuNWEs were used to construct electrochemical aptamer-based nanosensors (E-AB nanosensors) based on the formation of Au-S bond that duplex DNA tagged with methylene blue (MB) was modified on the surface of electrode. In the presence of adenosine triphosphate (ATP), the MB-labeled aptamer dissociated from the duplex DNA due to the strong specific affinity between aptamer and target, which lead to the reduction of MB electrochemical signals. Moreover, BSA was employed to further passivate electrode surface bonding sites for the stable of the sensor. The as-prepared E-AB nanosensor has been used for ATP assay with excellent sensitivity and selectivity, even in a complex system like cerebrospinal fluid of rat brain. Considering the unique properties of good stability, larger surface area and smaller overall dimensions, this E-AB nanosensor should be an ideal platform for widely sensing applications in living bio-system. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of Thermostabilities of Enzymes, Mediators and Immobilizing Membranes for Enzyme Sensors

NASA Astrophysics Data System (ADS)

Yamada, Yohei; Ohnishi, Yuki; Hayashi, Tetsuya; Isobe, Yoshifumi; Yabutani, Tomoki

The stability of the constituents of electrochemical measurement, electron mediators, enzymes and enzyme-immobilizing membranes was evaluated under high temperature (maximum 75°C) by electrochemical analysis, UV-Vis spectrometry (UV-Vis) and UV circular dichroism (CD). As a result of stability evaluation of mediators at 75°C, electrochemical activity of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid ammonium salt (ABTS), potassium ferricyanide (K3[Fe(CN)6]) and ferrocenemethanol (FcOH) were not changed, but 2,6-dichloroindophenol (DCIP), p-benzoquinone (p-BQ), vitaminK3 (VK3) were greatly decreased. The stability of diaphorase from Bacillus stearothermophilus (DI) were compared between in-solution and in several types of membranes, Agarose H, Poly-L-lysine (PLL) and poly-ion-complex (PIC) by electrochemical analysis. In solution, activity and secondary structure of DI were changed at 65°C or higher. This tendency of activity was not much different in Agarose H but in PLL, the activity was almost kept until 70°C. It was suggested that DI was fixed on the electrodes in high concentration and the elimination of DI seldom arise in PLL from the magnitude of the current response and the results of prolonged stability evaluation.

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

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

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

Electrochemical Impedance Imaging via the Distribution of Diffusion Times.

PubMed

Song, Juhyun; Bazant, Martin Z

2018-03-16

We develop a mathematical framework to analyze electrochemical impedance spectra in terms of a distribution of diffusion times (DDT) for a parallel array of random finite-length Warburg (diffusion) or Gerischer (reaction-diffusion) circuit elements. A robust DDT inversion method is presented based on complex nonlinear least squares regression with Tikhonov regularization and illustrated for three cases of nanostructured electrodes for energy conversion: (i) a carbon nanotube supercapacitor, (ii) a silicon nanowire Li-ion battery, and (iii) a porous-carbon vanadium flow battery. The results demonstrate the feasibility of nondestructive "impedance imaging" to infer microstructural statistics of random, heterogeneous materials.

The Electrochemical Fluorination of Organosilicon Compounds

NASA Technical Reports Server (NTRS)

Seaver, Robert E.

1961-01-01

The electrochemical fluorination of tetramethylsilane, hexamethyl-disiloxane, diethyldichlorosilane, amyltrichlorosilane, and phenyltri-chlorosilane was conducted in an Inconel cell equipped with nickel electrodes. A potential of approximately 5.0 volts and a current of approximately 1.0 ampere were used for the electrolysis reaction. In all cases the fluorinations resulted in considerable scission of the carbon-silicon bonds yielding hydrogen and the various fluorinated decomposition products; no fluoroorganosilicon compounds were identified. The main decomposition products were silicon tetrafluoride, the corresponding fluorinated carbon compounds, and the various organofluorosilanes. It is suggested that this is due to the nucleophilic attack of the fluoride ion (or complex fluoride ion) on the carbon-silicon bond.

Electrochemical sensing of ammonium ion at the water/1,6-dichlorohexane interface.

PubMed

Ribeiro, José A; Silva, F; Pereira, Carlos M

2012-01-15

In this work, ion transfer and facilitated ion transfer of ammonium ion by a lipophilic cyclodextrin is investigated at the water/1,6-dichlorohexane micro-interface, using electrochemical approaches (cyclic voltammetry, differential pulse voltammetry and square wave voltammetry). The association constant has been obtained for the complex between ammonium ion and the cyclodextrin. Experimental conditions for the analytical determination of ammonium ion were established and a detection limit of 0.12 μM was obtained. The amperometric sensor gave a current response proportional to the ammonium ion concentration in the range from 4.2 to 66 μM. Copyright © 2011 Elsevier B.V. All rights reserved.

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex.

PubMed

Weber, Michael D; Garino, Claudio; Volpi, Giorgio; Casamassa, Enrico; Milanesio, Marco; Barolo, Claudia; Costa, Rubén D

2016-06-07

This work provides the synthesis, structural characterization, electrochemical and photophysical features, as well as the application in light-emitting electrochemical cells (LECs) of a novel heteroleptic copper(i) complex - [Cu(impy)(POP)][PF6], where impy is 3-(2-methoxyphenyl)-1-(pyridine-2-yl)imidazo[1,5-a]pyridine and POP is bis{2-(diphenylphosphanyl)phenyl}ether. This compound shows blue photoluminescence (PL, λ = 450 nm) in solution and solid-state and excellent redox stability. Despite these excellent features, the electroluminescence (EL) response is located at ∼550 nm. Although the EL spectrum of LECs is typically red-shifted compared to the PL of the electroluminescent material, a shift of ca. 100 nm represents the largest one reported in LECs. To date, the large shift phenomena have been attributed to (i) a change in the nature of the lowest emitting state due to a concentration effect of the films, (ii) a reversible substitution of the ligands due to the weak coordination to the Cu(i), and (iii) a change in the distribution of the excited states due to polarization effects. After having discarded these along with others like the irreversible degradation of the emitter during device fabrication and/or under operation conditions, driving conditions, active layer composition, and changes in the excited states under different external electrical stimuli, we attribute the origin of this unexpected shift to a lack of a thermally activated delayed fluorescence (TADF) process due to the solely ligand-centered character of the excited states. As such, the lack of a charge transfer character in the excited states leads to a blue-fluorescence and yellow-phosphorescence photo- and electro-responses, respectively. This corroborates recent studies focused on the design of TADF for heteroleptic copper(i) complexes. Overall, this work is a clear insight into the design of new copper(i) complexes towards the preparation of blue LECs, which are still unexplored.

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

Giattino, L.R.; Irwin, L.J.

Recently, reserve batteries utilizing other electrochemical systems have gained acceptance in missiles, especially for those of longer than a five-minute mission time, and in others of increasing complexity and power requirements. Recent developments at GTE have proven the feasibility of using the lithium thionyl chloride electrochemistry in these latter applications.

Electrochemical, Spectroscopic and 1O2 Sensitization Characteristics of 10,10-Dimethylbiladiene Complexes of Zinc and Copper

DOE PAGES

Pistner, Allen; Pupillo, Rachel C.; Yapp, Glenn P. A.; ...

2014-09-04

The synthesis, electrochemistry and photophysical characterization of a 10,10- dimethylbiladiene tetrapyrrole bearing ancillary pentafluorophenyl groups at the 5 and 15-meso positions (DMBil1) is presented. This non-macrocyclic tetrapyrrole platform is robust and can serve as an excellent ligand scaffold for Zn 2+ and Cu 2+ centers. X-ray diffraction studies conducted for DMBil1 along with the corresponding Zn[DMBil1] and Cu[DMBil1] complexes show that this ligand scaffold binds a single metal ion within the tetrapyrrole core. Additionally, electrochemical experiments revealed that all three of the aforementioned compounds display an interesting redox chemistry, as the DMBil1 framework can be both oxidized and reduced bymore » two electrons. Spectroscopic and photophysical experiments carried out for DMBil1, Zn[DMBil1] and Cu[DMBil1] provide a basic picture of the electronic properties of these platforms. All three biladiene derivatives strongly absorb light in the visible region and are weakly emissive. The ability of these compounds to sensitize the formation of 1O 2 at wavelengths longer than 500 nm was probed. Both the freebase and Zn 2+ 10,10-dimethylbiladiene architectures show modest efficiencies for 1O 2 sensitization. The combination of structural, electrochemical and photophysical data detailed herein, provides a basis for the design of additional biladiene constructs for the activation of O 2 and other small molecules.« less

The green hemoproteins of bovine erythrocytes. II. Spectral, ligand-binding, and electrochemical properties.

PubMed

DeFilippi, L J; Hultquist, D E

1978-05-10

The two green hemoproteins isolated from bovine erythrocytes (form I and form II) have been characterized as to spectral, electrochemical, and chemical properties. The absorption spectra of the isolated hemoproteins are typical of high spin ferric states. Reduction of the hemoproteins yields high spin ferrohemoproteins. Complexation of the ferrohemoproteins with CO and the ferrihemoproteins with cyanide yields low spin complexes, demonstrating the presence of an exchangeable weak field ligand in both the ferrous and ferric states of the hemoproteins. The differences in position and intensity of the absorption peaks of the visible spectra allow the two forms to be distinguished from one another. The midpoint potential of forms I and II were found to be +0.075 and +0.019 V, respectively, at pH 6.4 and +0.038 and -0.005 V, respectively, at pH 7.0. This is consistent with the gaining of 1 proton/electron during the reduction. The Nernst plot reveals an unusual 0.5-electron transfer, whereas a quantitative titration demonstrates a 1-electron transfer. Form I binds cyanide more tightly than form II (KD of 84 and 252 micrometer, respectively). The observed spectral, electrochemical, and ligand-binding differences between forms I and II can be explained in terms of a greater electron-withdrawing ability of the side chains of the heme of form I relative to the heme of form II.

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

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

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

DOE PAGES

Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu; ...

2017-12-05

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysismore » shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.« less

Electrolyte additive for improved battery performance

DOEpatents

Bellows, Richard J.; Kantner, Edward

1989-04-04

In one embodiment of the present invention, there is provided an electrochemical cell having a metal bromine couple. The cell includes an electrode structure on which to deposit the metal of the couple and a counterelectrode at which to generate bromine. A microporous membrane separates the electrode and counterelectrode. Importantly, the aqueous electrolyte comprises an aqueous metal bromide solution containing a water soluble bromine complexing agent capable of forming a water immiscible complex with bromine and an additive capable of decreasing the wettability of the microporous separators employed in such cells by such water immiscible bromine complexes.

Basic Research in Microplasmas

DTIC Science & Technology

2012-03-29

concentrations of nitrate anions (NO3-) and nitrite anions (NO2-) in sterile water were measured with a high-performance liquid chromatography , HPLC ( Dionex ...ICS-2500 equipped with an ED50 electrochemical detector and a DIONEX ASRS 4-mm suppressor module). 25 μL samples were injected into the system for...the very few of He* atoms were used for the Penning ionization of the N2 molecule(reaction 6), because no N2 + ion (391nm) were detected in side-on

A Thermally Powered ISFET Array for On-Body pH Measurement.

PubMed

Douthwaite, Matthew; Koutsos, Ermis; Yates, David C; Mitcheson, Paul D; Georgiou, Pantelis

2017-12-01

Recent advances in electronics and electrochemical sensors have led to an emerging class of next generation wearables, detecting analytes in biofluids such as perspiration. Most of these devices utilize ion-selective electrodes (ISEs) as a detection method; however, ion-sensitive field-effect transistors (ISFETs) offer a solution with improved integration and a low power consumption. This work presents a wearable, thermoelectrically powered system composed of an application-specific integrated circuit (ASIC), two commercial power management integrated circuits and a network of commercial thermoelectric generators (TEGs). The ASIC is fabricated in 0.35 m CMOS and contains an ISFET array designed to read pH as a current, a processing module which averages the signal to reduce noise and encodes it into a frequency, and a transmitter. The output frequency has a measured sensitivity of 6 to 8 kHz/pH for a pH range of 7-5. It is shown that the sensing array and processing module has a power consumption 6 W and, therefore, can be entirely powered by body heat using a TEG. Array averaging is shown to reduce noise at these low power levels to 104 V (input referred integrated noise), reducing the minimum detectable limit of the ASIC to 0.008 pH units. The work forms the foundation and proves the feasibility of battery-less, on-body electrochemical for perspiration analysis in sports science and healthcare applications.

An efficient signal-on aptamer-based biosensor for adenosine triphosphate detection using graphene oxide both as an electrochemical and electrochemiluminescence signal indicator.

PubMed

Huang, Xiang; Li, Yuqin; Zhang, Xiaoshan; Zhang, Xin; Chen, Yaowen; Gao, Wenhua

2015-09-07

An efficient aptasensor was developed in which graphene oxide (GO) was employed as an indicator for both electrochemical impedance spectroscopy and electrochemiluminescence (ECL) signal generation. The aptasensor was fabricated by self-assembling the ECL probe of a thiolated adenosine triphosphate binding aptamer (ABA) tagged with a Ru complex (Ru(bpy)3(2+) derivatives) onto the surface of gold nanoparticle (AuNP) modified glassy carbon electrode (GCE). ABA immobilized onto AuNP modified GCE could strongly adsorb GO due to the strong π-π interaction between ABA and graphene oxide; ECL quenching of the Ru complex then takes place because of energy transfer and electron transfer, and a large increase of the electron transfer resistance (Ret) of the electrode. While in the presence of target adenosine triphosphate (ATP), the ABA prefers to form ABA-ATP bioaffinity complexes, which have weak affinity to graphene oxide and keep the graphene oxide away from the electrode surface, thus allowing the ECL signal enhancement, and in conjunction with the decrease of the Ret. Because of the high ECL quenching efficiency, unique structure, and electronic properties of graphene oxide, the Ret and ECL intensity versus the logarithm of ATP concentration was linear in the wide range from 10 pM to 10 nM with an ultra-low detection limit of 6.7 pM to 4.8 pM, respectively. The proposed aptasensor exhibited excellent reproducibility, stability, and outstanding selectivity, and ATP could be effectively distinguished from its analogues. More significantly, this efficient ECL aptasensor strategy based on GO acting both as an electrochemical and ECL signal indicator is general and can be easily extended to other biological binding events.

Static Feed Water Electrolysis Subsystem Testing and Component Development

NASA Technical Reports Server (NTRS)

Koszenski, E. P.; Schubert, F. H.; Burke, K. A.

1983-01-01

A program was carried out to develop and test advanced electrochemical cells/modules and critical electromechanical components for a static feed (alkaline electrolyte) water electrolysis oxygen generation subsystem. The accomplishments were refurbishment of a previously developed subsystem and successful demonstration for a total of 2980 hours of normal operation; achievement of sustained one-person level oxygen generation performance with state-of-the-art cell voltages averaging 1.61 V at 191 ASF for an operating temperature of 128F (equivalent to 1.51V when normalized to 180F); endurance testing and demonstration of reliable performance of the three-fluid pressure controller for 8650 hours; design and development of a fluid control assembly for this subsystem and demonstration of its performance; development and demonstration at the single cell and module levels of a unitized core composite cell that provides expanded differential pressure tolerance capability; fabrication and evaluation of a feed water electrolyte elimination five-cell module; and successful demonstration of an electrolysis module pressurization technique that can be used in place of nitrogen gas during the standby mode of operation to maintain system pressure and differential pressures.

Aluminum doped nickel oxide thin film with improved electrochromic performance from layered double hydroxides precursor in situ pyrolytic route

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

Shi, Jingjing; Lai, Lincong; Zhang, Ping

Electrochromic materials with unique performance arouse great interest on account of potential application values in smart window, low-power display, automobile anti-glare rearview mirror, and e-papers. In this paper, high-performing Al-doped NiO porous electrochromic film grown on ITO substrate has been prepared via a layered double hydroxides(LDHs) precursor in situ pyrolytic route. The Al{sup 3+} ions distributed homogenously within the NiO matrix can significantly influence the crystallinity of Ni-Al LDH and NiO:Al{sup 3+} films. The electrochromic performance of the films were evaluated by means of UV–vis absorption spectroscopy, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry(CA) measurements. In addition, themore » ratio of Ni{sup 3+}/Ni{sup 2+} also varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range (58.4%), fast switching speed (bleaching/coloration times are 1.8/4.2 s, respectively) and excellent durability (30% decrease after 2000 cycles). The improved performance was owed to the synergy of large NiO film specific surface area and porous morphology, as well as Al doping stifled the formation of Ni{sup 3+} making bleached state more pure. This LDHs precursor pyrolytic method is simple, low-cost and environmental benign and is feasible for the preparation of NiO:Al and other Al-doped oxide thin film. - Graphical abstract: The ratio of Ni{sup 3+}/Ni{sup 2+} varies with Al content which can lead to different electrochemical performances. Among the as-prepared films, NiO film prepared from Ni-Al (19:1) LDH show the best electrochromic performance with a high transparency of 96%, large optical modulation range, fast switching speed and excellent durability. Display Omitted.« less

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

PubMed

Badalyan, Artavazd; Stahl, Shannon S

2016-07-21

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1–2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2′-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2′-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

NASA Astrophysics Data System (ADS)

Badalyan, Artavazd; Stahl, Shannon S.

2016-07-01

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

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

Matheu, Roc; Francàs, Laia; Chernev, Petko

Electrochemical reduction of the dizaonium complex, [Ru II(bda)(NO)(N–N 2) 2] 3+, 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid materialmore » has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2, is a very fast and rugged heterogeneous water oxidation catalyst with TOF is of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

DOE PAGES

Matheu, Roc; Francàs, Laia; Chernev, Petko; ...

2015-05-07

Electrochemical reduction of the dizaonium complex, [Ru II(bda)(NO)(N–N 2) 2] 3+, 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid materialmore » has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2, is a very fast and rugged heterogeneous water oxidation catalyst with TOF is of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

Large Size Color-tunable Electroluminescence from Cationic Iridium Complexes-based Light-emitting Electrochemical Cells

PubMed Central

Zeng, Qunying; Li, Fushan; Guo, Tailiang; Shan, Guogang; Su, Zhongmin

2016-01-01

Solution-processable light-emitting electrochemical cells (LECs) with simple device architecture have become an attractive candidate for application in next generation lighting and flat-panel displays. Herein, single layer LECs employing two cationic Ir(III) complexes showing highly efficient blue-green and yellow electroluminescence with peak current efficiency of 31.6 cd A−1 and 40.6 cd A−1, respectively, have been reported. By using both complexes in the device, color-tunable LECs with a single spectral peak in the wavelength range from 499 to 570 nm were obtained by varying their rations. In addition, the fabrication of efficient LECs was demonstrated based on low cost doctor-blade coating technique, which was compatible with the roll to roll fabrication process for the large size production. In this work, for the first time, 4 inch LEC devices by doctor-blade coating were fabricated, which exhibit the efficiencies of 23.4 cd A−1 and 25.4 cd A−1 for the blue-green and yellow emission, respectively. The exciting results indicated that highly efficient LECs with controllable color could be realized and find practical application in large size lighting and displays. PMID:27278527

Structural, electrochemical characterization and SOD mimic activities of 1D chain or 3D network encouraged by unique μ2-bridging by adipate ion in mixed ligand complexes containing α-diimine as auxiliary ligand

NASA Astrophysics Data System (ADS)

Siddiqi, Zafar A.; Sharma, Prashant K.; Shahid, M.; Kumar, Sarvendra; Anjuli; Siddique, Armeen

The present ternary complexes [Cu(ada)(phen)(H2O)]·2H2O (1), [Co2(ada)2(phen)2(H2O)2] (2) and [{Cu(ada)3(bipy)}n·3nH2O] (3) (H2ada = adipic acid, phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine) obtained under varying experimental conditions were characterized by spectral, electrochemical and thermal studies. The bonding modes and the spatial arrangements of the carboxylate dianion around the metal ions have been investigated employing FTIR, EPR and X-ray crystallographic studies. Present data revealed a six coordinate distorted octahedral geometry for 2 with a = 8.068, b = 9.788, c = 11.788 Å, α = 70.464, β = 75.109, γ = 72.063° and a five coordinate square pyramidal geometry for 3 with a = 9.509, b = 9.912, c = 12.656 Å, α = 70.486, β = 73.604, γ = 75.162°. The superoxide dismutase (SOD) mimic activities of the complexes are in the order 1 > 3 > 2.

Combined Spectroscopic and Electrochemical Detection of a Ni I ---H-N Bonding Interaction with Relevance to Electrocatalytic H 2 Production

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

Kochem, Amélie; O'Hagan, Molly; Wiedner, Eric S.

2015-06-03

The [Ni(P R 2N R' 2) 2] 2+ family of complexes are exceptionally active catalysts for proton reduction to H 2. In this manuscript, we explore the first protonation step of the proposed catalytic cycle by using a catalytically inactive Ni I complex possessing a sterically demanding variation of the ligand. Due to the paramagnetic nature of the Ni I oxidation state, the protonated Ni I intermediate has been characterized through a combination of cyclic voltammetry, electron nuclear double resonance (ENDOR) spectroscopy, and hyperfine sublevel correlation (HYSCORE) spectroscopy. Both the electrochemical and spectroscopic studies indicate that the NiI complex ismore » protonated at a pendant amine that is endo to Ni, which suggests the presence of an intramolecular Ni I---HN bonding interaction. Using density functional theory, the hydrogen bond was found to involve three doubly-occupied, localized molecular orbitals: the 3d xz, 3d z2, and 3d yz orbitals of nickel. These studies provide the first direct experimental evidence for this critical catalytic intermediate, and implications for catalytic H 2 production are discussed.« less

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

NASA Astrophysics Data System (ADS)

Frasconi, Marco; Mazzei, Franco

2009-07-01

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

Modulating the Electrochemical Performances of Layered Cathode Materials for Sodium Ion Batteries through Tuning Coulombic Repulsion between Negatively Charged TMO2 Slabs.

PubMed

Li, Zheng-Yao; Wang, Huibo; Yang, Wenyun; Yang, Jinbo; Zheng, Lirong; Chen, Dongfeng; Sun, Kai; Han, Songbai; Liu, Xiangfeng

2018-01-17

Exploiting advanced layered transition metal oxide cathode materials is of great importance to rechargeable sodium batteries. Layered oxides are composed of negatively charged TMO 2 slabs (TM = transition metal) separated by Na + diffusion layers. Herein, we propose a novel insight, for the first time, to control the electrochemical properties by tuning Coulombic repulsion between negatively charged TMO 2 slabs. Coulombic repulsion can finely tailor the d-spacing of Na ion layers and material structural stability, which can be achieved by employing Na + cations to serve as effective shielding layers between TMO 2 layers. A series of O3-type Na x Mn 1/3 Fe 1/3 Cu 1/6 Mg 1/6 O 2 (x = 1.0, 0.9, 0.8, and 0.7) have been prepared, and Na 0.7 Mn 1/3 Fe 1/3 Cu 1/6 Mg 1/6 O 2 shows the largest Coulombic repulsion between TMO 2 layers, the largest space for Na ion diffusion, the best structural stability, and also the longest Na-O chemical bond with weaker Coulombic attraction, thus leading to the best electrochemical performance. Meanwhile, the thermal stability depends on the Na concentration in pristine materials. Ex situ X-ray absorption (XAS) analysis indicates that Mn, Fe, and Cu ions are all electrochemically active components during insertion and extraction of sodium ion. This study enables some new insights to promote the development of advanced layered Na x TMO 2 materials for rechargeable sodium batteries in the future.

High performance Sb2S3/carbon composite with tailored artificial interface as an anode material for sodium ion batteries

NASA Astrophysics Data System (ADS)

Choi, Jeong-Hee; Ha, Chung-Wan; Choi, Hae-Young; Shin, Heon-Cheol; Lee, Sang-Min

2017-11-01

The electrochemical comparison between Sb2S3 and its composite with carbon (Sb2S3/C) involved by sodium ion carrier are explained by enhanced kinetics, particularly with respect to improved interfacial conductivity by surface modulation by carbon. Sb2S3 and Sb2S3/C are synthesized by a high energy mechanical milling process. The successful synthesis of these materials is confirmed with X-ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM). As an anode material for sodium ion batteries, Sb2S3 exhibits an initial sodiation/desodiation capacity of 1,021/523 mAh g-1 whereas the Sb2S3/C composite exhibits a higher reversible capacity (642 mAh g-1). Furthermore, the cycle performance and rate capability of the Sb2S3/C composite are estimated to be much better than those of Sb and Sb2S3. Electrochemical impedance spectroscopy analysis shows that the Sb2S3/C composite exhibited charge transfer resistance and surface film resistance much lower than Sb2S3. X-ray photoelectron spectroscopy analyses of both electrodes demonstrate that NaF layer on Sb2S3/C composite electrode leads to the better electrochemical performances. In order to clarify the electrochemical reaction mechanism, ex-situ XRD based on differential capacity plots and ex-situ HR-TEM analyses of the Sb2S3/C composite electrode are carried out and its reaction mechanism was established.

Exhaled nitric oxide monitoring by quantum cascade laser: comparison with chemiluminescent and electrochemical sensors

NASA Astrophysics Data System (ADS)

Mandon, Julien; Högman, Marieann; Merkus, Peter J. F. M.; van Amsterdam, Jan; Harren, Frans J. M.; Cristescu, Simona M.

2012-01-01

Fractional exhaled nitric oxide (FENO) is considered an indicator in the diagnostics and management of asthma. In this study we present a laser-based sensor for measuring FENO. It consists of a quantum cascade laser (QCL) combined with a multi-pass cell and wavelength modulation spectroscopy for the detection of NO at the sub-part-per-billion by volume (ppbv, 1∶10-9) level. The characteristics and diagnostic performance of the sensor were assessed. A detection limit of 0.5 ppbv was demonstrated with a relatively simple design. The QCL-based sensor was compared with two market sensors, a chemiluminescent analyzer (NOA 280, Sievers) and a portable hand-held electrochemical analyzer (MINO®, Aerocrine AB, Sweden). FENO from 20 children diagnosed with asthma and treated with inhaled corticosteroids were measured. Data were found to be clinically acceptable within 1.1 ppbv between the QCL-based sensor and chemiluminescent sensor and within 1.7 ppbv when compared to the electrochemical sensor. The QCL-based sensor was tested on healthy subjects at various expiratory flow rates for both online and offline sampling procedures. The extended NO parameters, i.e. the alveolar region, airway wall, diffusing capacity, and flux were calculated and showed a good agreement with the previously reported values.

Numerical Study on the Effect of Electrode Polarity on Desulfurization in Direct Current Electroslag Remelting Process

NASA Astrophysics Data System (ADS)

Wang, Qiang; Liu, Yu; Wang, Fang; Li, Guangqiang; Li, Baokuan; Qiao, Wenwei

2017-10-01

In order to clarify the influence of electrode polarity on desulfurization in direct current (DC) electroslag remelting process, a transient three-dimensional coupled mathematical model has been established. The finite volume method was invoked to simultaneously solve the mass, momentum, energy, and species conservation equations. The Joule heating and Lorentz force were fully coupled through calculating Maxwell's equations with the assistance of the magnetic potential vector. The motion of the metal-slag interface was described by using the volume of fluid approach. An auxiliary metallurgical kinetics module was introduced to determine the thermochemical and the electrochemical reaction rates. A reasonable agreement between the measured data and the simulated results are observed. A longer time and a larger area for the desulfurization can be provided by the metal pool-slag interface when compared with the metal droplet-slag interface. The electrochemical transfer rate at the metal pool-slag interface is positive in the DC reverse polarity (DCRP) remelting, while in the DC straight polarity (DCSP) remelting, the electrochemical transfer rate is negative at this interface. The desulfurization progress in the DCSP remelting thus is fall behind that in the DCRP remelting. The desulfurization rate of the DCRP remelting is around 70 pct and the rate of the DCSP remelting is about 40 pct.

Direct electrical control of IgG conformation and functional activity at surfaces

NASA Astrophysics Data System (ADS)

Ghisellini, Paola; Caiazzo, Marialuisa; Alessandrini, Andrea; Eggenhöffner, Roberto; Vassalli, Massimo; Facci, Paolo

2016-11-01

We have devised a supramolecular edifice involving His-tagged protein A and antibodies to yield surface immobilized, uniformly oriented, IgG-type, antibody layers with Fab fragments exposed off an electrode surface. We demonstrate here that we can affect the conformation of IgGs, likely pushing/pulling electrostatically Fab fragments towards/from the electrode surface. A potential difference between electrode and solution acts on IgGs’ charged aminoacids modulating the accessibility of the specific recognition regions of Fab fragments by antigens in solution. Consequently, antibody-antigen affinity is affected by the sign of the applied potential: a positive potential enables an effective capture of antigens; a negative one pulls the fragments towards the electrode, where steric hindrance caused by neighboring molecules largely hampers the capture of antigens. Different experimental techniques (electrochemical quartz crystal microbalance, electrochemical impedance spectroscopy, fluorescence confocal microscopy and electrochemical atomic force spectroscopy) were used to evaluate binding kinetics, surface coverage, effect of the applied electric field on IgGs, and role of charged residues on the phenomenon described. These findings expand the concept of electrical control of biological reactions and can be used to gate electrically specific recognition reactions with impact in biosensors, bioactuators, smart biodevices, nanomedicine, and fundamental studies related to chemical reaction kinetics.

Exhaled nitric oxide monitoring by quantum cascade laser: comparison with chemiluminescent and electrochemical sensors.

PubMed

Mandon, Julien; Högman, Marieann; Merkus, Peter J F M; van Amsterdam, Jan; Harren, Frans J M; Cristescu, Simona M

2012-01-01

Fractional exhaled nitric oxide (F(E)NO) is considered an indicator in the diagnostics and management of asthma. In this study we present a laser-based sensor for measuring F(E)NO. It consists of a quantum cascade laser (QCL) combined with a multi-pass cell and wavelength modulation spectroscopy for the detection of NO at the sub-part-per-billion by volume (ppbv, 110(-9)) level. The characteristics and diagnostic performance of the sensor were assessed. A detection limit of 0.5 ppbv was demonstrated with a relatively simple design. The QCL-based sensor was compared with two market sensors, a chemiluminescent analyzer (NOA 280, Sievers) and a portable hand-held electrochemical analyzer (MINO, Aerocrine AB, Sweden). F(E)NO from 20 children diagnosed with asthma and treated with inhaled corticosteroids were measured. Data were found to be clinically acceptable within 1.1 ppbv between the QCL-based sensor and chemiluminescent sensor and within 1.7 ppbv when compared to the electrochemical sensor. The QCL-based sensor was tested on healthy subjects at various expiratory flow rates for both online and offline sampling procedures. The extended NO parameters, i.e. the alveolar region, airway wall, diffusing capacity, and flux were calculated and showed a good agreement with the previously reported values.

In Touch With the Mechanosensitive Piezo Channels: Structure, Ion Permeation, and Mechanotransduction.

PubMed

Geng, J; Zhao, Q; Zhang, T; Xiao, B

2017-01-01

Mechanotransduction, the conversion of mechanical forces into biological signals, plays critical roles in various physiological and pathophysiological processes in mammals, such as conscious sensing of touch, pain, and sound, as well as unconscious sensing of blood flow-associated shear stress, urine flow, and bladder distention. Among the various molecules involved in mechanotransduction, mechanosensitive (MS) cation channels have long been postulated to represent one critical class of mechanotransducers that directly and rapidly converts mechanical force into electrochemical signals. Despite the awareness of their functional significance, the molecular identities of MS cation channels in mammals had remained elusive for decades till the groundbreaking finding that the Piezo family of genes, including Piezo1 and Piezo2, constitutes their essential components. Since their identification about 6years ago, tremendous progress has been made in understanding their physiological and pathophysiological importance in mechanotransduction and their structure-function relationships of being the prototypic class of mammalian MS cation channels. On the one hand, Piezo proteins have been demonstrated to serve as physiologically and pathophysiologically important mechanotransducers for most, if not all, mechanotransduction processes. On the other hand, they have been shown to form a remarkable three-bladed, propeller-shaped homotrimeric channel complex comprising a separable ion-conducting pore module and mechanotransduction modules. In this chapter, we review the major advancements, with a particular focus on the structural and biophysical features that enable Piezo proteins to serve as sophisticated MS cation channels for force sensing, transduction, and ion conduction. Copyright © 2017 Elsevier Inc. All rights reserved.

Silica Aerogels Doped with Ru(II) Tris 1,l0-Phenanthro1ine)-Electron Acceptor Dyads: Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Oxygen Sensors

NASA Technical Reports Server (NTRS)

Kevebtusm Bucgikas; Rawashdeh, Abdel M.; Elder, Ian A.; Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia

2005-01-01

Complexes 1 and 2 were characterized in fluid and frozen solution and as dopants of silica aerogels. The intramolecular quenching efficiency of pendant 4-benzoyl-N-methylpyridinium group (4BzPy) is solvent dependent: emission is quenched completely in acetonitrile but not in alcohols. On the other hand, N-benzyl-N'-methylviologen (BzMeV) quenches the emission in all solvents completely. The differences are traced electrochemically to a stronger solvation effect by the alcohol in the case of 1. In fiozen matrices or absorbed on the surfaces of silica aerogel, both 1 and 2 are photoluminescent. The lack of quenching has been traced to the environmental rigidity. When doped aerogels are cooled to 77K, the emission shifts to the blue and its intensity increases in analogy to what is observed with Ru(II) complexes in media undergoing fluid-to-rigid transition. The photoluminescence of 1 and 2 from the aerogel is quenched by oxygen diffusing through the pores. In the presence of oxygen, aerogels doped with 1 can modulate their emission over a wider dynamic range than aerogels doped with 2, and both are more sensitive than aerogels doped with Ru(II) tris(1,l0- phenanthroline). In contrast to frozen solutions, the luminescent moieties in the bulk of aerogels kept at 77K are still accessible, leading to more sensitive platforms for oxygen sensors than other ambient temperature configurations.

Push or Pull? Proton Responsive Ligand Effects in Rhenium Tricarbonyl CO 2 Reduction Catalysts

DOE PAGES

Manbeck, Gerald F.; Muckerman, James T.; Szalda, David J.; ...

2015-02-19

Proton responsive ligands offer control of catalytic reactions through modulation of pH-dependent properties, second coordination sphere stabilization of transition states, or by providing a local proton source for multi-proton, multi-electron reactions. Two fac-[ReI(α-diimine)(CO)₃Cl] complexes with α-diimine = 4,4'- (or 6,6'-) dihydroxy-2,2'-bipyridine (4DHBP and 6DHBP) have been prepared and analyzed as electrocatalysts for reduction of carbon dioxide. Consecutive electrochemical reduction of these complexes yields species identical to those obtained by chemical deprotonation. An energetically feasible mechanism for reductive deprotonation is proposed in which the bpy anion is protonated followed by loss of H₂ and 2H⁺. Cyclic voltammetry reveals a two-electron, three-wavemore » system owing to competing EEC and ECE pathways. The chemical step of the ECE pathway might be attributed to the reductive deprotonation. but cannot be distinguished from chloride dissociation. The rate obtained by digital simulation is approximately 8 s⁻¹. Under CO₂, these competing reactions generate a two-slope catalytic waveform with onset potential of –1.65 V vs Ag/AgCl. Reduction of CO₂ to CO by the [ReI (4DHBP–2H⁺)(CO)₃]⁻ suggests the interaction of CO₂ with the deprotonated species or a third reduction followed by catalysis. Conversely, the reduced form of [Re(6DHBP)(CO)₃Cl] converts CO₂ to CO with a single turnover.« less

Elliptic complexes over C∗-algebras of compact operators

NASA Astrophysics Data System (ADS)

Krýsl, Svatopluk

2016-03-01

For a C∗-algebra A of compact operators and a compact manifold M, we prove that the Hodge theory holds for A-elliptic complexes of pseudodifferential operators acting on smooth sections of finitely generated projective A-Hilbert bundles over M. For these C∗-algebras and manifolds, we get a topological isomorphism between the cohomology groups of an A-elliptic complex and the space of harmonic elements of the complex. Consequently, the cohomology groups appear to be finitely generated projective C∗-Hilbert modules and especially, Banach spaces. We also prove that in the category of Hilbert A-modules and continuous adjointable Hilbert A-module homomorphisms, the property of a complex of being self-adjoint parametrix possessing characterizes the complexes of Hodge type.

Electrochemical and spectroscopic study on the interaction between isoprenaline and DNA using multivariate curve resolution-alternating least squares.

PubMed

Ni, Yongnian; Wei, Min; Kokot, Serge

2011-11-01

Interaction of isoprenaline (ISO) with calf-thymus DNA was studied by spectroscopic and electrochemical methods. The behavior of ISO was investigated at a glassy carbon electrode (GCE) by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV); ISO was oxidized and an irreversible oxidation peak was observed. The binding constant K and the stoichiometric coefficient m of ISO with DNA were evaluated. Also, with the addition of DNA, hyperchromicity of the UV-vis absorption spectra of ISO was noted, while the fluorescence intensity decreased significantly. Multivariate curve resolution-alternating least squares (MCR-ALS) chemometrics method was applied to resolve the combined spectroscopic data matrix, which was obtained by the UV-vis and fluorescence methods. Pure spectra of ISO, DNA and ISO-DNA complex, and their concentration profiles were then successfully obtained. The results indicated that the ISO molecule intercalated into the base-pairs of DNA, and the complex of ISO-DNA was formed. Copyright © 2011 Elsevier B.V. All rights reserved.

Optical Dark-Field and Electron Energy Loss Imaging and Spectroscopy of Symmetry-Forbidden Modes in Loaded Nanogap Antennas.

PubMed

Brintlinger, Todd; Herzing, Andrew A; Long, James P; Vurgaftman, Igor; Stroud, Rhonda; Simpkins, B S

2015-06-23

We have produced large numbers of hybrid metal-semiconductor nanogap antennas using a scalable electrochemical approach and systematically characterized the spectral and spatial character of their plasmonic modes with optical dark-field scattering, electron energy loss spectroscopy with principal component analysis, and full wave simulations. The coordination of these techniques reveal that these nanostructures support degenerate transverse modes which split due to substrate interactions, a longitudinal mode which scales with antenna length, and a symmetry-forbidden gap-localized transverse mode. This gap-localized transverse mode arises from mode splitting of transverse resonances supported on both antenna arms and is confined to the gap load enabling (i) delivery of substantial energy to the gap material and (ii) the possibility of tuning the antenna resonance via active modulation of the gap material's optical properties. The resonant position of this symmetry-forbidden mode is sensitive to gap size, dielectric strength of the gap material, and is highly suppressed in air-gapped structures which may explain its absence from the literature to date. Understanding the complex modal structure supported on hybrid nanosystems is necessary to enable the multifunctional components many seek.

Electrochemical Biosensors - Sensor Principles and Architectures

PubMed Central

Grieshaber, Dorothee; MacKenzie, Robert; Vörös, Janos; Reimhult, Erik

2008-01-01

Quantification of biological or biochemical processes are of utmost importance for medical, biological and biotechnological applications. However, converting the biological information to an easily processed electronic signal is challenging due to the complexity of connecting an electronic device directly to a biological environment. Electrochemical biosensors provide an attractive means to analyze the content of a biological sample due to the direct conversion of a biological event to an electronic signal. Over the past decades several sensing concepts and related devices have been developed. In this review, the most common traditional techniques, such as cyclic voltammetry, chronoamperometry, chronopotentiometry, impedance spectroscopy, and various field-effect transistor based methods are presented along with selected promising novel approaches, such as nanowire or magnetic nanoparticle-based biosensing. Additional measurement techniques, which have been shown useful in combination with electrochemical detection, are also summarized, such as the electrochemical versions of surface plasmon resonance, optical waveguide lightmode spectroscopy, ellipsometry, quartz crystal microbalance, and scanning probe microscopy. The signal transduction and the general performance of electrochemical sensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. New nanotechnology-based approaches, such as the use of engineered ion-channels in lipid bilayers, the encapsulation of enzymes into vesicles, polymersomes, or polyelectrolyte capsules provide additional possibilities for signal amplification. In particular, this review highlights the importance of the precise control over the delicate interplay between surface nano-architectures, surface functionalization and the chosen sensor transducer principle, as well as the usefulness of complementary characterization tools to interpret and to optimize the sensor response. PMID:27879772

Transportation and Accumulation of Redox Active Species at the Buried Interfaces of Plasticized Membrane Electrodes.

PubMed

Sohail, Manzar; De Marco, Roland; Jarolímová, Zdeňka; Pawlak, Marcin; Bakker, Eric; He, Ning; Latonen, Rose-Marie; Lindfors, Tom; Bobacka, Johan

2015-09-29

The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.

Sensitive electrochemical aptamer cytosensor for highly specific detection of cancer cells based on the hybrid nanoelectrocatalysts and enzyme for signal amplification.

PubMed

Sun, Duanping; Lu, Jing; Zhong, Yuwen; Yu, Yanyan; Wang, Yu; Zhang, Beibei; Chen, Zuanguang

2016-01-15

Human cancer is becoming a leading cause of death in the world and the development of a straightforward strategy for early detection of cancer is urgently required. Herein, a sandwich-type electrochemical aptamer cytosensor was developed for detection of human liver hepatocellular carcinoma cells (HepG2) based on the hybrid nanoelectrocatalysts and enzyme for signal amplification. The thiolated TLS11a aptamers were used as a selective bio-recognition element, attached to the gold nanoparticles (AuNPs) modified the glassy carbon electrode (GCE) surface. Meanwhile, the electrochemical nanoprobes were fabricated through the G-quadruplex/hemin/aptamer complexes and horseradish peroxidase (HRP) immobilized on the surfaces of Au@Pd core-shell nanoparticle-modified magnetic Fe3O4/MnO2 beads (Fe3O4/MnO2/Au@Pd). After the target cells were captured, the hybrid nanoprobes were further assembled to form an aptamer-cell-nanoprobes sandwich-like system on the electrode surface. Then, hybrid Fe3O4/MnO2/Au@Pd nanoelectrocatalysts, G-quadruplex/hemin HRP-mimicking DNAzymes and the natural HRP enzyme efficiently catalyzed the oxidation of hydroquinone (HQ) with H2O2, amplifying the electrochemical signals and improving the detection sensitivity. This electrochemical cytosensor delivered a wide detection range of 1×10(2)-1×10(7)cellsmL(-1), high sensitivity with a low detection limit of 15cellsmL(-1), good selectivity and repeatability. Finally, an electrochemical reductive desorption method was performed to break gold-thiol bond and desorb the components on the AuNPs/GCE for regenerating the cytosensor. These results have demonstrated that the electrochemical cytosensor has the potential to be a feasible tool for cost-effective cancer cell detection in early cancer diagnosis. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis and CV Studies of Dithiol-terminated Metal Terpyridine Complexes

NASA Technical Reports Server (NTRS)

Asano, Sylvia; Fan, Wendy; Ng, Hou-Tee; Han, Jie; Meyyappan, M.

2003-01-01

Transition metal coordination complexes possess unique electronic structures that should be a good model for studying electronic transport behavior at a molecular level. The discrete, multiple redox states, low redox potential and the superb ability to establish contact with other molecular and electronic components by coordination chemistry have made this a subject of investigation for their possible application as active electronic components in molecular devices. We present the synthesis and electrochemical characterization of 4'-thioacetylphenyl-2'2:6',2"-terpyridine iron(II) complex and compare it with a model bis-terpyridine iron(II) complex by cyclic voltammetry. With the use of different working electrodes, the behavior of these complexes show different electron transfer rates.

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

DOE PAGES

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.; ...

2015-08-10

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Electrochemical immunoassay for the detection of IgM antibodies using polydopamine particles loaded with PbS quantum dots as labels.

PubMed

Ortega, Greter A; Zuaznabar-Gardona, Julio C; Reguera, Edilso

2018-09-30

Here, we report for the first time, an electrochemical immunoassay to detect IgM antibodies using lead sulfide quantum dots (PbS QDs) as electrochemical labels. In this sense, dendritic-like polydopamine particles loaded with PbS QDs were synthesized by the self-polymerization of dopamine in basic media in the presence of QDs (PbS@PDA) and further tagged with anti-IgM antibodies, dengue specific antigens, and streptavidin moieties. The analytical features of the sandwich immunoassay on ELISA microplate were carried out with the PbS@PDA-labeled anti-IgM as secondary antibody. The system was interrogated by acid dissolution of PbS@PDA, followed by differential pulse anodic stripping voltammetry in the presence of Bi(III) ions using carbon screen-printed electrodes. The results indicate that the voltammetric current increased with the increasing of the concentration of target IgM within a range of 0-0.5 mg mL -1 . The limit of detection of this electrochemical immunoassay was evaluated to 130 ng. The measures of satisfactory recoveries from 88.5% to 114% of spiked samples indicate that such a method has good specificity and is applicable to the quantification of IgM antibodies in complex biological samples. No significant differences at the 0.05 significance level were encountered in the analysis of IgM samples between the electrochemical immunoassay and a Bradford assay. Copyright © 2018 Elsevier B.V. All rights reserved.

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

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

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

PubMed

Wetzel, David J; Malone, Marvin A; Haasch, Richard T; Meng, Yifei; Vieker, Henning; Hahn, Nathan T; Gölzhäuser, Armin; Zuo, Jian-Min; Zavadil, Kevin R; Gewirth, Andrew A; Nuzzo, Ralph G

2015-08-26

Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

Low-complexity and modulation-format-independent carrier phase estimation scheme using linear approximation for elastic optical networks

NASA Astrophysics Data System (ADS)

Yang, Tao; Chen, Xue; Shi, Sheping; Sun, Erkun; Shi, Chen

2018-03-01

We propose a low-complexity and modulation-format-independent carrier phase estimation (CPE) scheme based on two-stage modified blind phase search (MBPS) with linear approximation to compensate the phase noise of arbitrary m-ary quadrature amplitude modulation (m-QAM) signals in elastic optical networks (EONs). Comprehensive numerical simulations are carried out in the case that the highest possible modulation format in EONs is 256-QAM. The simulation results not only verify its advantages of higher estimation accuracy and modulation-format independence, i.e., universality, but also demonstrate that the implementation complexity is significantly reduced by at least one-fourth in comparison with the traditional BPS scheme. In addition, the proposed scheme shows similar laser linewidth tolerance with the traditional BPS scheme. The slightly better OSNR performance of the scheme is also experimentally validated for PM-QPSK and PM-16QAM systems, respectively. The coexistent advantages of low-complexity and modulation-format-independence could make the proposed scheme an attractive candidate for flexible receiver-side DSP unit in EONs.

Electrochemical, photoelectrochemical, and surface plasmon resonance detection of cocaine using supramolecular aptamer complexes and metallic or semiconductor nanoparticles.

PubMed

Golub, Eyal; Pelossof, Gilad; Freeman, Ronit; Zhang, Hong; Willner, Itamar

2009-11-15

Metallic or semiconductor nanoparticles (NPs) are used as labels for the electrochemical, photoelectrochemical, or surface plasmon resonance (SPR) detection of cocaine using a common aptasensor configuration. The aptasensors are based on the use of two anticocaine aptamer subunits, where one subunit is assembled on a Au support, acting as an electrode or a SPR-active surface, and the second aptamer subunit is labeled with Pt-NPs, CdS-NPs, or Au-NPs. In the different aptasensor configurations, the addition of cocaine results in the formation of supramolecular complexes between the NPs-labeled aptamer subunits and cocaine on the metallic surface, allowing the quantitative analysis of cocaine. The supramolecular Pt-NPs-aptamer subunits-cocaine complex allows the detection of cocaine by the electrocatalyzed reduction of H(2)O(2). The photocurrents generated by the CdS-NPs-labeled aptamer subunits-cocaine complex, in the presence of triethanol amine as a hole scavenger, allows the photoelectrochemical detection of cocaine. The supramolecular Au-NPs-aptamer subunits-cocaine complex generated on the Au support allows the SPR detection of cocaine through the reflectance changes stimulated by the electronic coupling between the localized plasmon of the Au-NPs and the surface plasmon wave. All aptasensor configurations enable the analysis of cocaine with a detection limit in the range of 10(-6) to 10(-5) M. The major advantage of the sensing platform is the lack of background interfering signals.

Heterobimetallic complexes of palladium and platinum containing a redox-active W[SNS]2 metalloligand.

PubMed

Rosenkoetter, Kyle E; Ziller, Joseph W; Heyduk, Alan F

2017-05-02

Complexes of the general formula W[SNS] 2 M(dppe) (M = Pd, Pt; [SNS]H 3 = bis(2-mercapto-p-tolyl)amine; dppe = 1,2-bis(diphenylphosphino)ethane) were prepared by combining the corresponding (dppe)MCl 2 synthon with W[SNS] 2 under reducing conditions. X-ray diffraction studies revealed the formation of a heterobimetallic complex supported by a single thiolate bridging ligand and a short metal-metal bond between the tungsten and palladium or platinum. Electrochemical and computational results show that the frontier orbitals lie predominantly on the W[SNS] 2 fragment suggesting that it behaves as a redox-active metalloligand in these complexes.

Synthesis and characterization of poly(phenylacetylene)s with Ru(II) bis-terpyridine complexes in the side-chain.

PubMed

Breul, Alexander M; Kübel, Joachim; Häupler, Bernhard; Friebe, Christian; Hager, Martin D; Winter, Andreas; Dietzek, Benjamin; Schubert, Ulrich S

2014-04-01

An alkyne-functionalized ruthenium(II) bis-terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size-exclusion chromatography (SEC), (1) H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV-vis absorption spectroscopy. In addition, spectro-electrochemical measurements are carried out. Time-resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)2 (2+) model complex. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance graphdiyne-based electrochemical actuators.

PubMed

Lu, Chao; Yang, Ying; Wang, Jian; Fu, Ruoping; Zhao, Xinxin; Zhao, Lei; Ming, Yue; Hu, Ying; Lin, Hongzhen; Tao, Xiaoming; Li, Yuliang; Chen, Wei

2018-02-21

Electrochemical actuators directly converting electrical energy to mechanical energy are critically important for artificial intelligence. However, their energy transduction efficiency is always lower than 1.0% because electrode materials lack active units in microstructure, and their assembly systems can hardly express the intrinsic properties. Here, we report a molecular-scale active graphdiyne-based electrochemical actuator with a high electro-mechanical transduction efficiency of up to 6.03%, exceeding that of the best-known piezoelectric ceramic, shape memory alloy and electroactive polymer reported before, and its energy density (11.5 kJ m -3 ) is comparable to that of mammalian skeletal muscle (~8 kJ m -3 ). Meanwhile, the actuator remains responsive at frequencies from 0.1 to 30 Hz with excellent cycling stability over 100,000 cycles. Furthermore, we verify the alkene-alkyne complex transition effect responsible for the high performance through in situ sum frequency generation spectroscopy. This discovery sheds light on our understanding of actuation mechanisms and will accelerate development of smart actuators.

Dual-Mode Electro-Optical Techniques for Biosensing Applications: A Review

PubMed Central

Johnson, Steven

2017-01-01

The monitoring of biomolecular interactions is a key requirement for the study of complex biological processes and the diagnosis of disease. Technologies that are capable of providing label-free, real-time insight into these interactions are of great value for the scientific and clinical communities. Greater understanding of biomolecular interactions alongside increased detection accuracy can be achieved using technology that can provide parallel information about multiple parameters of a single biomolecular process. For example, electro-optical techniques combine optical and electrochemical information to provide more accurate and detailed measurements that provide unique insights into molecular structure and function. Here, we present a comparison of the main methods for electro-optical biosensing, namely, electrochemical surface plasmon resonance (EC-SPR), electrochemical optical waveguide lightmode spectroscopy (EC-OWLS), and the recently reported silicon-based electrophotonic approach. The comparison considers different application spaces, such as the detection of low concentrations of biomolecules, integration, the tailoring of light-matter interaction for the understanding of biomolecular processes, and 2D imaging of biointeractions on a surface. PMID:28880211

Influence of electrode preparation on the electrochemical performance of LiNi0.8Co0.15Al0.05O2 composite electrodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tran, Hai Yen; Greco, Giorgia; Täubert, Corina; Wohlfahrt-Mehrens, Margret; Haselrieder, Wolfgang; Kwade, Arno

2012-07-01

The electrode manufacturing for lithium-ion batteries is based on a complex process chain with several influencing factors. A proper tailoring of the electrodes can greatly improve both the electrochemical performances and the energy density of the battery. In the present work, some significant parameters during the preparation of LiNi0.8Co0.15Al0.05O2-based cathodes were investigated. The active material was mixed with a PVDF-binder and two conductive additives in different ratios. The electrode thickness, the degree of compacting and the conductive agent type and mixing ratio have proven to have a strong impact on the electrochemical performances of the composite electrodes, especially on their behaviour at high C-rates. Further it has been shown that the compacting has an essential influence on the mechanical properties of NCA coatings, according to their total, ductile and elastic deformation behaviour.

A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

DOE PAGES

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.; ...

2018-01-17

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less

Fingerprinting Green Curry: An Electrochemical Approach to Food Quality Control.

PubMed

Chaibun, Thanyarat; La-O-Vorakiat, Chan; O'Mullane, Anthony P; Lertanantawong, Benchaporn; Surareungchai, Werasak

2018-06-07

The detection and identification of multiple components in a complex sample such as food in a cost-effective way is an ongoing challenge. The development of on-site and rapid detection methods to ensure food quality and composition is of significant interest to the food industry. Here we report that an electrochemical method can be used with an unmodified glassy carbon electrode for the identification of the key ingredients found within Thai green curries. It was found that green curry presents a fingerprint electrochemical response that contains four distinct peaks when differential pulse voltammetry is performed. The reproducibility of the sensor is excellent as no surface modification is required and therefore storage is not an issue. By employing particle swarm optimization algorithms the identification of ingredients within a green curry could be obtained. In addition, the quality and freshness of the sample could be monitored by detecting a change in the intensity of the peaks in the fingerprint response.

Primary and secondary electrical space power based on advanced PEM systems

NASA Technical Reports Server (NTRS)

Vanderborgh, N. E.; Hedstrom, J. C.; Stroh, K. R.; Huff, J. R.

1993-01-01

For new space ventures, power continues to be a pacing function for mission planning and experiment endurance. Although electrochemical power is a well demonstrated space power technology, current hardware limitations impact future mission viability. In order to document and augment electrochemical technology, a series of experiments for the National Aeronautics and Space Administration Lewis Research Center (NASA LeRC) are underway at the Los Alamos National Laboratory that define operational parameters on contemporary proton exchange membrane (PEM) hardware operating with hydrogen and oxygen reactants. Because of the high efficiency possible for water electrolysis, this hardware is also thought part of a secondary battery design built around stored reactants - the so-called regenerative fuel cell. An overview of stack testing at Los Alamos and of analyses related to regenerative fuel cell systems are provided in this paper. Finally, this paper describes work looking at innovative concepts that remove complexity from stack hardware with the specific intent of higher system reliability. This new concept offers the potential for unprecedented electrochemical power system energy densities.

A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

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

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less

Attachment chemistry of aromatic compounds on a Silicon(100) surface

NASA Astrophysics Data System (ADS)

Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

2018-03-01

A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.

Dual-Mode Electro-Optical Techniques for Biosensing Applications: A Review.

PubMed

Juan-Colás, José; Johnson, Steven; Krauss, Thomas F

2017-09-07

The monitoring of biomolecular interactions is a key requirement for the study of complex biological processes and the diagnosis of disease. Technologies that are capable of providing label-free, real-time insight into these interactions are of great value for the scientific and clinical communities. Greater understanding of biomolecular interactions alongside increased detection accuracy can be achieved using technology that can provide parallel information about multiple parameters of a single biomolecular process. For example, electro-optical techniques combine optical and electrochemical information to provide more accurate and detailed measurements that provide unique insights into molecular structure and function. Here, we present a comparison of the main methods for electro-optical biosensing, namely, electrochemical surface plasmon resonance (EC-SPR), electrochemical optical waveguide lightmode spectroscopy (EC-OWLS), and the recently reported silicon-based electrophotonic approach. The comparison considers different application spaces, such as the detection of low concentrations of biomolecules, integration, the tailoring of light-matter interaction for the understanding of biomolecular processes, and 2D imaging of biointeractions on a surface.

A new hexanuclear iron-selenium nitrosyl cluster: primary exploration of the preparation methods, structure, and spectroscopic and electrochemical properties.

PubMed

Wang, Rongming; Xu, Wei; Zhang, Jian; Li, Lijuan

2010-06-07

A new hexanuclear iron-selenium nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)Se(6)(NO)(6)] (1), and a hexanuclear iron-sulfur nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)S(6)(NO)(6)] (2), were synthesized by the solvent-thermal reactions of [(n-Bu)(4)N][Fe(CO)(3)NO] with selenium or sulfur in methanol, while a tetranuclear iron-sulfur nitrosyl cluster, (Me(4)N)[Fe(4)S(3)(NO)(7)] (3), was also prepared by the solvent-thermal reaction of FeCl(2).4H(2)O with thiourea in the presence of (CH(3))(4)NCl, NaNO(2), and methanol. Complexes 1-3 were characterized by IR, UV-vis, (1)H NMR, electrochemistry, and single-crystal X-ray diffraction analysis. IR spectra of complexes 1 and 2 show the characteristic NO stretching frequencies at 1694 and 1698 cm(-1), respectively, while the absorptions of complex 3 appear at 1799, 1744, and 1710 cm(-1). The UV-vis spectra of complexes 1-3 show different bands in the range of 259-562 nm, which are assigned to the transitions between orbitals delocalized over the Fe-S cluster, the ligand-to-metal charge transfer, pi*(NO)-d(Fe), and the metal-to-ligand charge transfer, d(Fe)-pi*(NO). Single-crystal X-ray structural analysis reveals that complex 1 crystallizes in the monoclinic P2(1)/n space group with two molecules per unit cell. Two parallel "chair-shaped" structures, consisting of three iron and three selenium atoms, are connected by Fe-Se bonds with an average distance of 2.341 A; each iron center is bonded to three selenium atoms and a nitrogen atom from the nitrosyl ligand with a pseudotetrahedral center geometry. Cyclic voltammograms of complexes 1 and 2 display two cathodic and three anodic current peaks with an unusually strong cathodic peak. Further electrochemical investigations demonstrated that the intensity of the unusually strong peak is a result of at least three processes. One is the quasi-reversible reduction, and the other two are from an irreversible electrochemical process, in which the compound goes through a typical electron transfer and chemical reaction mechanism. Compound 3 shows three quasi-reversible reductions.

Subunits of ADA-two-A-containing (ATAC) or Spt-Ada-Gcn5-acetyltrasferase (SAGA) Coactivator Complexes Enhance the Acetyltransferase Activity of GCN5.

PubMed

Riss, Anne; Scheer, Elisabeth; Joint, Mathilde; Trowitzsch, Simon; Berger, Imre; Tora, László

2015-11-27

Histone acetyl transferases (HATs) play a crucial role in eukaryotes by regulating chromatin architecture and locus specific transcription. GCN5 (KAT2A) is a member of the GNAT (Gcn5-related N-acetyltransferase) family of HATs. In metazoans this enzyme is found in two functionally distinct coactivator complexes, SAGA (Spt Ada Gcn5 acetyltransferase) and ATAC (Ada Two A-containing). These two multiprotein complexes comprise complex-specific and shared subunits, which are organized in functional modules. The HAT module of ATAC is composed of GCN5, ADA2a, ADA3, and SGF29, whereas in the SAGA HAT module ADA2b is present instead of ADA2a. To better understand how the activity of human (h) hGCN5 is regulated in the two related, but different, HAT complexes we carried out in vitro HAT assays. We compared the activity of hGCN5 alone with its activity when it was part of purified recombinant hATAC or hSAGA HAT modules or endogenous hATAC or hSAGA complexes using histone tail peptides and full-length histones as substrates. We demonstrated that the subunit environment of the HAT complexes into which GCN5 incorporates determines the enhancement of GCN5 activity. On histone peptides we show that all the tested GCN5-containing complexes acetylate mainly histone H3K14. Our results suggest a stronger influence of ADA2b as compared with ADA2a on the activity of GCN5. However, the lysine acetylation specificity of GCN5 on histone tails or full-length histones was not changed when incorporated in the HAT modules of ATAC or SAGA complexes. Our results thus demonstrate that the catalytic activity of GCN5 is stimulated by subunits of the ADA2a- or ADA2b-containing HAT modules and is further increased by incorporation of the distinct HAT modules in the ATAC or SAGA holo-complexes. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Immobilization free electrochemical biosensor for folate receptor in cancer cells based on terminal protection.

PubMed

Ni, Jiancong; Wang, Qingxiang; Yang, Weiqiang; Zhao, Mengmeng; Zhang, Ying; Guo, Longhua; Qiu, Bin; Lin, Zhenyu; Yang, Huang-Hao

2016-12-15

The determination of folate receptor (FR) that over expressed in vast quantity of cancerous cells frequently is significant for the clinical diagnosis and treatment of cancers. Many DNA-based electrochemical biosensors have been developed for FR detection with high selectivity and sensitivity, but most of them need complicated immobilization of DNA on the electrode surface firstly, which is tedious and therefore results in the poor reproducibility. In this study, a simple, sensitive, and selective electrochemical FR biosensor in cancer cells has been proposed, which combines the advantages of the convenient immobilization-free homogeneous indium tin oxide (ITO)-based electrochemical detection strategy and the high selectivity of the terminal protection of small molecule linked DNA. The small molecule of folic acid (FA) and an electroactive molecule of ferrocence (Fc) were tethered to 3'- and 5'-end of an arbitrary single-stranded DNA (ssDNA), respectively, forming the FA-ssDNA-Fc complex. In the absence of the target FR, the FA-ssDNA-Fc was degraded by exonuclease I (Exo I) from 3'-end and produced a free Fc, diffusing freely to the ITO electrode surface and resulting in strong electrochemical signal. When the target FR was present, the FA-ssDNA-Fc was bound to FR through specific interaction with FA anchored at the 3'-end, effectively protecting the ssDNA strand from hydrolysis by Exo I. The FR-FA-ssDNA-Fc could not diffuse easily to the negatively charged ITO electrode surface due to the electrostatic repulsion between the DNA strand and the negatively charged ITO electrode, so electrochemical signal reduced. The decreased electrochemical signal has a linear relationship with the logarithm of FR concentration in range of 10fM to 10nM with a detection limit of 3.8fM (S/N=3). The proposed biosensor has been applied to detect FR in HeLa cancer cells, and the decreased electrochemical signal has a linear relationship with the logarithm of cell concentration ranging from 100-10000cell/mL. Compared with the traditional heterogeneous electrochemical FR biosensors, the proposed biosensor owns the merits of the simplicity and high specificity, presenting the great potential application in the area of early diagnosis of cancers. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface plasmons based terahertz modulator consisting of silicon-air-metal-dielectric-metal layers

NASA Astrophysics Data System (ADS)

Wang, Wei; Yang, Dongxiao; Qian, Zhenhai

2018-05-01

An optically controlled modulator of the terahertz wave, which is composed of a metal-dielectric-metal structure etched with circular loop arrays on both the metal layers and a photoexcited silicon wafer separated by an air layer, is proposed. Simulation results based on experimentally measured complex permittivities predict that modification of complex permittivity of the silicon wafer through excitation laser leads to a significant tuning of transmission characteristics of the modulator, forming the modulation depths of 59.62% and 96.64% based on localized surface plasmon peak and propagating surface plasmon peak, respectively. The influences of the complex permittivity of the silicon wafer and the thicknesses of both the air layer and the silicon wafer are numerically studied for better understanding the modulation mechanism. This study proposes a feasible methodology to design an optically controlled terahertz modulator with large modulation depth, high speed and suitable insertion loss, which is useful for terahertz applications in the future.

Material Characterization in the Electro-Analytic Approach for Applications in Chemical Mechanical Planarization and Electrochemical Energy Systems

NASA Astrophysics Data System (ADS)

Rock, Simon E.

The work presented in this thesis covers electro-analytical characterization for multiple applications in material science. Electrochemical techniques were used to investigate soluble film formation on metals used in chemical mechanical planarization in order to better understand the removal rate process by studying new chemicals proposed by groups in industry. Second, an ionic liquid was used as an electrolyte in a lithium ion cathode half cell to show the essential functionality of the IL and the temperature advantage over traditional electrolytes. Lastly, a comprehensive measurement for charge recombination in dye-sensitized solar cells was performed using both open-circuit voltage decay and impedance spectroscopy, which may be used to better understand the limiting factors that affect the cell's efficiently. Electrochemical techniques were applied to new methods and materials to extend the development of material manufacturing and advance the measurement process. The fabrication of interconnect structures for semiconductor devices requires low down-pressure chemical mechanical planarization (CMP) of Ta barrier layers. Guanidine carbonate (GC) serves as an effective surface-complexing agent for such CMP applications, where the rate of Ta removal can be chemically controlled through pH-tuned selectivity with respect to the removal of Cu lines. Electrochemical techniques are employed in this work to study the surface-modifying roles of GC that make this chemical an attractive complexing agent for Ta CMP. In addition, the effects of including H2O2 (an oxidizer) and dodecyl benzene sulfonic acid (DBSA, a dissolution inhibitor for Cu) in GC-based CMP solutions are investigated to examine the selective CMP mechanisms of Ta and Cu in these solutions. The results suggest that the removal of Ta is supported in part by structurally weak guanidinium-tantalic-acid surface complexes formed on Ta/Ta2O5. The bicarbonate/carbonate anions of GC also facilitate Ta removal through the generation of ion-incorporated tantalum pentoxide. DBSA strongly affects the CMP chemistry of Cu, but exhibits relatively weaker effects on the surface activity of Ta, and thus plays a vital role in dictating the selectivity of Ta:Cu polish rates. CMP of tantalum nitride is also an essential step of material processing in the fabrication of integrated circuits, which is looked separately in this thesis. The present work investigates certain chemical aspects of this strategy of TaN-CMP by also using guanidine carbonate (GC) as a surface complexing agent, and employing electrochemical experiments. The experiments are designed to study the chemical and electrochemical origins of the CMP-specific surface complex films formed on a TaN wafer in acidic solutions of GC and hydrogen peroxide. Open circuit potential, polarization resistance, and electrochemical impedance measurements are employed to probe the surface effects that facilitate material removal in chemically prevailing CMP of TaN. The results are discussed in view of designing slurry variables to support barrier layer planarization with reduced roles of mechanical abrasion. Nonvolatile and nonflammable ionic liquids (ILs) have distinct thermal advantages over the traditional organic solvent electrolytes of lithium ion batteries. However, this beneficial feature of ILs is often counterbalanced by their high viscosity (a limiting factor for ionic conductivity) and, sometimes, by their unsuitable electrochemistry for generating protective layers on electrode surfaces. In an effort to alleviate these limiting Aspects of ILs, we have synthesized a PEGylated imidazolium bis(triflouromethylsulfonyl)amide (bistriflamide) IL that exhibited better thermal and electrochemical stability than a conventional electrolyte based on a blend of ethylene carbonate and diethyl carbonate. The electrochemical performance of this IL has been demonstrated using a cathode consisting of ball-milled LiMn2O4 particles. A direct comparison of the ionic liquid electrolyte with the nonionic low-viscosity conventional solvent blend is presented. Charge recombination at the electrolyte-photoanode interface of a dye sensitized solar cell (DSSC) is a major efficiency-limiting factor of the cell. To mitigate this recombination effect it is necessary to ensure that the effective electron lifetime in the DSSC is longer than the electron's transit time across the photoanode of mesoporous TiO2. While the efforts aimed at accomplishing this goal are often based on new materials/designs of photoanodes, a quantitative evaluation of these designs relies on the precision of the benchmarking measurements of electron lifetimes. The open circuit voltage decay (OCVD) technique offers an effective yet straightforward method for such measurements. The present work focuses on certain experimental criteria for ensuring the accuracy of these experiments, and probes the associated effects of temperature variations in the solar cell. The results demonstrate that, a high rate of data sampling is essential for adequately resolving the fast initial stages of charge recombination. The results also show the effects of nonlinear recombination where second order OCV variations are operative. The findings of the OCVD experiments are compared with a parallel set of tests carried out using impedance spectroscopy. The relative roles of the two sets of analytical measurements are examined.

Extending the Diffuse Layer Model of Surface Acidity Behavior: III. Estimating Bound Site Activity Coefficients

EPA Science Inventory

Although detailed thermodynamic analyses of the 2-pK diffuse layer surface complexation model generally specify bound site activity coefficients for the purpose of accounting for those non-ideal excess free energies contributing to bound site electrochemical potentials, in applic...

Pharmacologic Effects on Mitochondrial Function

ERIC Educational Resources Information Center

Cohen, Bruce H.

2010-01-01

The vast majority of energy necessary for cellular function is produced in mitochondria. Free-radical production and apoptosis are other critical mitochondrial functions. The complex structure, electrochemical properties of the inner mitochondrial membrane (IMM), and genetic control from both mitochondrial DNA (mtDNA) and nuclear DNA (nDNA) are…

Developments in ICP-MS: electrochemically modulated liquid chromatography for the clean-up of ICP-MS blanks and reduction of matrix effects by flow injection ICP-MS

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

Gross, Cory Thomas

2008-01-01

The focus of this dissertation is the development of techniques with which to enhance the existing abilities of inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS is a powerful technique for trace metal analysis in samples of many types, but like any technique it has certain strengths and weaknesses. Attempts are made to improve upon those strengths and to overcome certain weaknesses.

An improved classification tree analysis of high cost modules based upon an axiomatic definition of complexity

NASA Technical Reports Server (NTRS)

Tian, Jianhui; Porter, Adam; Zelkowitz, Marvin V.

1992-01-01

Identification of high cost modules has been viewed as one mechanism to improve overall system reliability, since such modules tend to produce more than their share of problems. A decision tree model was used to identify such modules. In this current paper, a previously developed axiomatic model of program complexity is merged with the previously developed decision tree process for an improvement in the ability to identify such modules. This improvement was tested using data from the NASA Software Engineering Laboratory.

Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

2007-05-14

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

Photoinitiated Electron Collection in Mixed-Metal Supramolecular Complexes: Development of Photocatalysts for Hydrogen Production. Final Report of Progress August 2017

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

Tanko, James M.

Mixed-metal supramolecular complexes containing one or two RuII light absorbing subunits coupled through polyazine bridging ligands to a RhIII reactive metal center were prepared for use as photocatalysts for the production of solar H 2 fuel from H 2O. The electrochemical, photophysical, and photochemical properties upon variation of the monodentate, labile ligands coordinated to the Rh reactive metal center were investigated.

A Heterobimetallic W-Ni Complex Containing a Redox-Active W[SNS]2 Metalloligand.

PubMed

Rosenkoetter, Kyle E; Ziller, Joseph W; Heyduk, Alan F

2016-07-05

The tungsten complex W[SNS]2 ([SNS]H3 = bis(2-mercapto-4-methylphenyl)amine) was bound to a Ni(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane] fragment to form the new heterobimetallic complex W[SNS]2Ni(dppe). Characterization of the complex by single-crystal X-ray diffraction revealed the presence of a short W-Ni bond, which renders the complex diamagnetic despite formal tungsten(V) and nickel(I) oxidation states. The W[SNS]2 unit acts as a redox-active metalloligand in the bimetallic complex, which displays four one-electron redox processes by cyclic voltammetry. In the presence of the organic acid 4-cyanoanilinium tetrafluoroborate, W[SNS]2Ni(dppe) catalyzes the electrochemical reduction of protons to hydrogen coincident with the first reduction of the complex.

Enhanced electrochromic and energy storage performance in mesoporous WO3 film and its application in a bi-functional smart window.

PubMed

Wang, Wei-Qi; Wang, Xiu-Li; Xia, Xin-Hui; Yao, Zhu-Jun; Zhong, Yu; Tu, Jiang-Ping

2018-05-03

Construction of multifunctional photoelectrochemical energy devices is of great importance to energy saving. In this study, we have successfully prepared a mesoporous WO3 film on FTO glass via a facile dip-coating sol-gel method; the designed mesoporous WO3 film exhibited advantages including high transparency, good adhesion and high porosity. Also, multifunctional integrated energy storage and optical modulation ability are simultaneously achieved by the mesoporous WO3 film. Impressively, the mesoporous WO3 film exhibits a noticeable electrochromic energy storage performance with a large optical modulation up to 75.6% at 633 nm, accompanied by energy storage with a specific capacity of 75.3 mA h g-1. Furthermore, a full electrochromic energy storage window assembled with the mesoporous WO3 anode and PANI nanoparticle cathode is demonstrated with large optical modulation and good long-term stability. Our research provides a new route to realize the coincident utilization of optical-electrochemical energy.

Resonant tunneling modulation in quasi-2D Cu(2)O/SnO(2) p-n horizontal-multi-layer heterostructure for room temperature H(2)S sensor application.

PubMed

Cui, Guangliang; Zhang, Mingzhe; Zou, Guangtian

2013-01-01

Heterostructure material that acts as resonant tunneling system is a major scientific challenge in applied physics. Herein, we report a resonant tunneling system, quasi-2D Cu(2)O/SnO(2) p-n heterostructure multi-layer film, prepared by electrochemical deposition in a quasi-2D ultra-thin liquid layer. By applying a special half-sine deposition potential across the electrodes, Cu(2)O and SnO(2) selectively and periodically deposited according to their reduction potentials. The as-prepared heterostructure film displays excellent sensitivity to H(2)S at room temperature due to the resonant tunneling modulation. Furthermore, it is found that the laser illumination could enhance the gas response, and the mechanism with laser illumination is discussed. It is the first report on gas sensing application of resonant tunneling modulation. Hence, heterostructure material act as resonant tunneling system is believed to be an ideal candidate for further improvement of room temperature gas sensing.