Electrochemical DNA biosensor based on grafting-to mode of terminal deoxynucleoside transferase-mediated extension.

PubMed

Chen, Jinyuan; Liu, Zhoujie; Peng, Huaping; Zheng, Yanjie; Lin, Zhen; Liu, Ailin; Chen, Wei; Lin, Xinhua

2017-12-15

Previously reported electrochemical DNA biosensors based on in-situ polymerization approach reveal that terminal deoxynucleoside transferase (TdTase) has good amplifying performance and promising application in the design of electrochemical DNA biosensor. However, this method, in which the background is significantly affected by the amount of TdTase, suffers from being easy to produce false positive result and poor stability. Herein, we firstly present a novel electrochemical DNA biosensor based on grafting-to mode of TdTase-mediated extension, in which DNA targets are polymerized in homogeneous solution and then hybridized with DNA probes on BSA-based DNA carrier platform. It is surprising to find that the background in the grafting-to mode of TdTase-based electrochemical DNA biosensor have little interference from the employed TdTase. Most importantly, the proposed electrochemical DNA biosensor shows greatly improved detection performance over the in-situ polymerization approach-based electrochemical DNA biosensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Microelectrode-based technology for the detection of low levels of bacteria

NASA Technical Reports Server (NTRS)

Rogers, Tom D.; Hitchens, G. D.; Mishra, S. K.; Pierson, D. L.

1992-01-01

A microelectrode-based electrochemical detection method was used for quantitation of bacteria in water samples. The redox mediator, benzoquinone, was used to accept electrons from the bacterial metabolic pathway to create a flow of electrons by reducing the mediator. Electrochemical monitoring electrodes detected the reduced mediator as it diffused out of the cells and produced a small electrical current. By using a combination of microelectrodes and monitoring instrumentation, the cumulative current generated by a particular bacterial population could be monitored. Using commercially available components, an electrochemical detection system was assembled and tested to evaluate its potential as an emerging technology for rapid detection and quantitation of bacteria in water samples.

Electrochemically modified dissolved organic matter accelerates the combining photodegradation and biodegradation of 17α-ethinylestradiol in natural aquatic environment.

PubMed

He, Huan; Huang, Bin; Fu, Gen; Xiong, Dan; Xu, Zhixiang; Wu, Xinhao; Pan, Xuejun

2018-06-15

The photochemical conversion and microbial transformation of pollutants mediated by dissolved organic matter (DOM), including 17α-ethinylestradiol (EE2), are often accompanied in natural water. However, there are few studies to explore the connection and mechanism between the two processes. This research aims to investigate the mechanism of DOM after electrochemically modification mediated EE2 combining photodegradation and biodegradation in the environment and it want to explain the natural phenomena of DOM after electrochemical advanced treatment entering the water environment mediated EE2 natural degradation. The results showed that combining photodegradation with biodegradation rates of EE2 mediated by DOM and electrochemically modified DOM (E-DOM) were promoted obviously. The efficiency of EE2 biodegradation was shown to be strongly correlated with electron accepting capacity (EAC) of DOM. Electrochemical modification can increase the EAC of DOM leading to EE2 biodegradation accelerated, and it also can form more triplet-state DOM moieties to promote the EE2 photodegradation in irradiation conditions, due to the increasing of quinone-type structures in DOM. Moreover, cell polymeric secretion (CPS) secreted from the microorganism could be stimulated to an excited state by irradiation, and that also accelerated EE2 degradation. Photolysis combined with biochemical degradation yielded less toxic degradation products. This study shows that the emission of DOM in wastewater after electrochemical treatment could accelerate estrogen degradation and play a positive role on the pollutant transformation in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electrochemical carbon dioxide concentrator advanced technology tasks

NASA Technical Reports Server (NTRS)

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

1975-01-01

Technology advancement studies are reported on the basic electrochemical CO2 removal process to provide a basis for the design of the next generation cell, module and subsystem hardware. An Advanced Electrochemical Depolarized Concentrator Module (AEDCM) is developed that has the characteristics of low weight, low volume, high CO2, removal, good electrical performance and low process air pressure drop. Component weight and noise reduction for the hardware of a six man capacity CO2 collection subsystem was developed for the air revitalization group of the Space Station Prototype (SSP).

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

Underpotential deposition-mediated layer-by-layer growth of thin films

DOEpatents

Wang, Jia Xu; Adzic, Radoslav R.

2017-06-27

A method of depositing contiguous, conformal submonolayer-to-multilayer thin films with atomic-level control is described. The process involves electrochemically exchanging a mediating element on a substrate with a noble metal film by alternatingly sweeping potential in forward and reverse directions for a predetermined number of times in an electrochemical cell. By cycling the applied voltage between the bulk deposition potential for the mediating element and the material to be deposited, repeated desorption/adsorption of the mediating element during each potential cycle can be used to precisely control film growth on a layer-by-layer basis.

Mediated electrochemical oxidation of organic wastes using a Co (III) mediator in a nitric acid based system

DOEpatents

Balazs, G. Bryan; Chiba, Zoher; Lewis, Patricia R.; Nelson, Norvell; Steward, G. Anthony

1999-01-01

An electrochemical cell with a Co(III) mediator and nitric acid electrolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the mediator oxidizes the organics and insoluble transuranic compounds and is regenerated at the anode until the organics are converted to CO.sub.2. The nitric acid is an excellent oxidant that facilitates the destruction of the organic components. The anode is not readily attacked by the nitric acid solution, thus the cell can be used for extended continual operation without electrode replacement.

Dynamic mechanical control of local vacancies in NiO thin films

NASA Astrophysics Data System (ADS)

Seol, Daehee; Yang, Sang Mo; Jesse, Stephen; Choi, Minseok; Hwang, Inrok; Choi, Taekjib; Park, Bae Ho; Kalinin, Sergei V.; Kim, Yunseok

2018-07-01

The manipulation of local ionic behavior via external stimuli in oxide systems is of great interest because it can help in directly tuning material properties. Among external stimuli, mechanical force has attracted intriguing attention as novel stimulus for ionic modulation. Even though effectiveness of mechanical force on local ionic modulation has been validated in terms of static effect, its real-time i.e., dynamic, behavior under an application of the force is barely investigated in spite of its crucial impact on device performance such as force or pressure sensors. In this study, we explore dynamic ionic behavior modulated by mechanical force in NiO thin films using electrochemical strain microscopy (ESM). Ionically mediated ESM hysteresis loops were significantly varied under an application of mechanical force. Based on these results, we were able to investigate relative relationship between the force and voltage effects on ionic motion and, further, control effectively ionic behavior through combination of mechanical and electrical stimuli. Our results can provide comprehensive information on the effect of mechanical forces on ionic dynamics in ionic systems.

Dynamic mechanical control of local vacancies in NiO thin films.

PubMed

Seol, Daehee; Yang, Sang Mo; Jesse, Stephen; Choi, Minseok; Hwang, Inrok; Choi, Taekjib; Park, Bae Ho; Kalinin, Sergei V; Kim, Yunseok

2018-07-06

The manipulation of local ionic behavior via external stimuli in oxide systems is of great interest because it can help in directly tuning material properties. Among external stimuli, mechanical force has attracted intriguing attention as novel stimulus for ionic modulation. Even though effectiveness of mechanical force on local ionic modulation has been validated in terms of static effect, its real-time i.e., dynamic, behavior under an application of the force is barely investigated in spite of its crucial impact on device performance such as force or pressure sensors. In this study, we explore dynamic ionic behavior modulated by mechanical force in NiO thin films using electrochemical strain microscopy (ESM). Ionically mediated ESM hysteresis loops were significantly varied under an application of mechanical force. Based on these results, we were able to investigate relative relationship between the force and voltage effects on ionic motion and, further, control effectively ionic behavior through combination of mechanical and electrical stimuli. Our results can provide comprehensive information on the effect of mechanical forces on ionic dynamics in ionic systems.

Mediated electrochemical oxidation of organic wastes using a Co (III) mediator in a nitric acid based system

DOEpatents

Balazs, G.B.; Chiba, Z.; Lewis, P.R.; Nelson, N.; Steward, G.A.

1999-06-15

An electrochemical cell with a Co(III) mediator and nitric acid electrolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the mediator oxidizes the organics and insoluble transuranic compounds and is regenerated at the anode until the organics are converted to CO[sub 2]. The nitric acid is an excellent oxidant that facilitates the destruction of the organic components. The anode is not readily attacked by the nitric acid solution, thus the cell can be used for extended continual operation without electrode replacement. 2 figs.

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.

Carbon paste electrode with covalently immobilized thionine for electrochemical sensing of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Thenmozhi, K.; Sriman Narayanan, S.

2017-11-01

A water-soluble redox mediator, thionin was covalently immobilized to the functionalized graphite powder and a carbon paste electrode was fabricated from this modified graphite powder. The immobilization procedure proved to be effective in anchoring the thionin mediator in the graphite electrode setup without any leakage problem during the electrochemical studies. The covalent immobilization of the thionin mediator was studied with FT-IR and the electrochemical response of the thionin carbon paste electrode was optimized on varying the supporting electrolyte, pH and scan rate. The modified electrode exhibited well-defined electrocatalytic activity towards the reduction of H2O2 at a lower potential of -0.266 V with good sensitivity. The developed amperometric sensor was efficient towards H2O2 in the linear range from 2.46 × 10-5 M to 4.76 × 10-3 M, with a detection limit of 1.47 × 10-5 M respectively. Important advantages of this sensor are its excellent electrochemical performance, simple fabrication, easy renewability, reproducible analytical results, acceptable accuracy and good operational and long-term stability.

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.

Effect of NaI/I 2 mediators on properties of PEO/LiAlO 2 based all-solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Yin, Yijing; Zhou, Juanjuan; Mansour, Azzam N.; Zhou, Xiangyang

NaI/I 2 mediators and activated carbon were added into poly(ethylene oxide) (PEO)/lithium aluminate (LiAlO 2) electrolyte to fabricate composite electrodes. All solid-state supercapacitors were fabricated using the as prepared composite electrodes and a Nafion 117 membrane as a separator. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements were conducted to evaluate the electrochemical properties of the supercapacitors. With the addition of NaI/I 2 mediators, the specific capacitance increased by 27 folds up to 150 F g -1. The specific capacitance increased with increases in the concentration of mediators in the electrodes. The addition of mediators also reduced the electrode resistance and rendered a higher electron transfer rate between mediator and mediator. The stability of the all-solid-state supercapacitor was tested over 2000 charge/discharge cycles.

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

Co(III) as mediator in phenol destruction using electrochemical oxidation

NASA Astrophysics Data System (ADS)

Herlina, Herlina; Derlini, Derlini; Muhammad, Razali

2017-03-01

Mediated electrochemical oxidation is one of the method for oxidation of organic compound by using a mediator. This method has been developed because have several advantages which low cost and efficient, the exhaust gas does not contain toxic materials and hazardous waste and the process take place at a relatively low temperature. Electrochemical oxidation of organic compounds using metal ion mediator is one alternative method that is appropriate for the treatment of organic waste. Co(III) is a strong oxidizing agent used as a mediator has been prepared in Pt electrodes. The concentration of Co(III) formed during oxidation determined by potentiometric titration where Co(III) aliquot was added into Fe(II) excess solution and the remaining Fe(II) which did not react has been titrated with Ce(IV). In optimum condition, Co(III) was then used to oxidize the organic compound into carbon dioxide. The parameters has been studied are the standard oxidation potential of mediator, acid concentration and temperature. The results obtained at potential of 6 Volt, with nitric acid 4 M and temperature of 25°C give result 23.86% where Co (II) is converted to Co(III) within 2 hours. The addition of silver nitrate can increase the concentration of Co(III). At the optimum conditions, the mediator ion Co(III) can destructed to 66.44% of phenol compound oxidized into carbon dioxide.

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

Electrochemical and genomic analysis of novel electroactive isolates obtained via potentiostatic enrichment from tropical sediment

NASA Astrophysics Data System (ADS)

Doyle, Lucinda E.; Yung, Pui Yi; Mitra, Sumitra D.; Wuertz, Stefan; Williams, Rohan B. H.; Lauro, Federico M.; Marsili, Enrico

2017-07-01

Enrichment of electrochemically-active microorganisms (EAM) to date has mostly relied on microbial fuel cells fed with wastewater. This study aims to enrich novel EAM by exposing tropical sediment, not frequently reported in the literature, to sustained anodic potentials. Voltamperometric techniques and electrochemical impedance spectroscopy, performed over a wide range of potentials, characterise extracellular electron transfer (EET) over time. Applied potential is found to affect biofilm electrochemical signature. Geobacter metallireducens is heavily enriched on the electrodes, as determined by metagenomic and metatranscriptomic analysis, in the first report of the species in a lactate-fed system. Two novel isolates are grown in pure culture from the enrichment, identified by 16S rRNA gene sequencing as Aeromonas and Enterobacter, respectively. The names proposed are Aeromonas sp. CL-1 and Enterobacter sp. EA-1. Both isolates are capable of EET on carbon felt and screen-printed carbon electrodes without the addition of exogenous redox mediators. Enterobacter sp. EA-1 can also perform mediated electron transfer using the soluble redox mediator 2-hydroxy-1,4-naphthoquinone (HNQ). Both isolates are able to use acetate and lactate as electron donors. This work outlines a comprehensive methodology for characterising novel EAM from unconventional inocula.

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

PubMed

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

2013-12-15

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

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.

Electrochemically mediated polymerization for highly sensitive detection of protein kinase activity.

PubMed

Hu, Qiong; Wang, Qiangwei; Jiang, Cuihua; Zhang, Jian; Kong, Jinming; Zhang, Xueji

2018-07-01

Protein kinases play a pivotal role in cellular regulation and signal transduction, the detection of protein kinase activity and inhibition is therefore of great importance to clinical diagnosis and drug discovery. In this work, a novel electrochemical platform using the electrochemically mediated polymerization as an efficient and cost-effective signal amplification strategy is described for the highly sensitive detection of protein kinase activity. This platform involves 1) the phosphorylation of substrate peptide by protein kinase, 2) the attachment of alkyl halide to the phosphorylated sites via the carboxylate-Zr 4+ -phosphate chemistry, and 3) the in situ grafting of electroactive polymers from the phosphorylated sites through the electrochemically mediated atom transfer radical polymerization (eATRP) at a negative potential, in the presence of the surface-attached alkyl halide as the initiator and the electroactive tag-conjugated acrylate as the monomer, respectively. Due to the electrochemically mediated polymerization, a large number of electroactive tags can be linked to each phosphorylated site, thereby greatly improving the detection sensitivity. This platform has been successfully applied to detect the activity of cAMP-dependent protein kinase (PKA) with a detection limit down to 1.63 mU mL -1 . Results also demonstrate that it is highly selective and can be used for the screening of protein kinase inhibitors. The potential application of our platform for protein kinase activity detection in complex biological samples has been further verified using normal human serum and HepG2 cell lysate. Moreover, our platform is operationally simple, highly efficient and cost-effective, thus holding great potential in protein kinase detection and inhibitor screening. Copyright © 2018 Elsevier B.V. All rights reserved.

A highly efficient Li2O2 oxidation system in Li-O2 batteries.

PubMed

Hase, Yoko; Seki, Juntaro; Shiga, Tohru; Mizuno, Fuminori; Nishikoori, Hidetaka; Iba, Hideki; Takechi, Kensuke

2016-10-06

A novel indirect charging system that uses a redox mediator was demonstrated for Li-O 2 batteries. 4-Methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (MeO-TEMPO) was applied as a mediator to enable the oxidation of Li 2 O 2 , even though Li 2 O 2 is electrochemically isolated. This system promotes the oxidation of Li 2 O 2 without parasitic reactions attributed to electrochemical charging and reduces the charging time.

Investigation on electrochemical behavior and its catalytic effect on oxygen reduction reaction of 3-Ferrocenyl dihydropyrazole derivative as electron relay

NASA Astrophysics Data System (ADS)

Zeng, Han; Huo, Wen-Shan; Zhao, Shu-Xian; Zhang, Yu-He

2017-11-01

Amino group surface tailored multi-wall carbon nano-tubes were covalently tethered to the gold disk electrode and Laccase molecules were covalently coupled to nano-tubes to prepare Lac-based electrode. Derivative of 3-ferrocenyl dihydropyrazole (FDPFFP) was proposed to be electron mediator for mediated oxygen reduction reaction. Investigation in electro-chemical behavior and catalytic performance to enzymatic reaction of FDPFFP indicated that it displayed quasi-reversible characteristics of electro-chemical reaction with rapid dynamics of electron shuttle and had apparent catalytic effect in oxygen reduction (onset potential for catalysis at 450 mV vs NHE). This enzymatic catalysis was restrained by the step in diffusion of substrate.

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.

Toxin detection using a tyrosinase-coupled oxygen electrode.

PubMed

Smit, M H; Rechnitz, G A

1993-02-15

An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical properties.

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.

Methods for performing electrochemical nitration reactions

DOEpatents

Lister, Tedd Edward; Fox, Robert Vincent

2010-05-11

A method for the electrochemical synthesis of dinitro compounds is disclosed. The method comprises using an anode to oxidize an inactive chemical mediator, such as a ferrocyanide (Fe(CN).sub.6.sup.-4) ion, to an active chemical mediator or oxidizing agent, such as a ferricyanide (Fe(CN).sub.6.sup.-3) ion, in the presence of a differential voltage. The oxidizing agent reacts with a nitro compound and a nitrite ion to form a geminal dinitro compound. The anode may continuously oxidize ferrocyanide to regenerate active ferricyanide, thus keeping sufficient amounts of ferricyanide available for reaction..

High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

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

Gerken, James B.; Stahl, Shannon S.

2015-07-15

Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalystmore » drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Facile synthesis of carbon-mediated porous nanocrystallite anatase TiO2 for improved sodium insertion capabilities as an anode for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Wu, Feng; Luo, Rui; Xie, Man; Li, Li; Zhang, Xiaoxiao; Zhao, Luzi; Zhou, Jiahui; Wang, KangKang; Chen, Renjie

2017-09-01

Porous carbon-mediated nanocrystallite anatase TiO2 composites are synthesized successfully via a simple dilatory hydrolysis-calcination method. The structural and morphological characterizations reveal that carbon-mediated TiO2 with a carbon content of 9.9 wt % (C2-TiO2) shows a combination of mesoporous and macroporous structures with a pore volume of 0.20 cm3 g-1 and surface area of 40.3 m2 g-1. Notably, C2-TiO2 delivered enhanced electrochemical performances of a high charge capacity of 259 mA h g-1 at 0.1 C and a high rate performance of 110 mA h g-1 after 150 cycles, even at 1 C. A significant decrease is also observed in the electrochemical impedance of the carbon-mediated samples, which explains superior electrochemical performance. Compared with the bare anatase TiO2 (B-TiO2), improved sodium storage capabilities of carbon-mediated samples are attributed to the participation of carbon to form a symbiotic structure with TiO2, which not only increases pore volume of the samples but serves as highly conductive network to provide a Na+ diffusion path during the insertion/de-insertion of sodium ions. All of these encouraging results suggest that carbon-mediated TiO2 has a great potential for improving sodium insertion capabilities with a facile and low-cost synthesis process.

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.

Electrochemically mediated electrodeposition/electropolymerization to yield a glucose microbiosensor with improved characteristics.

PubMed

Chen, Xiaohong; Matsumoto, Norio; Hu, Yibai; Wilson, George S

2002-01-15

A procedure is described that provides for electrochemically mediated deposition of enzyme and a polymer layer permselective for endogenous electroactive species. Electrodeposition was first employed for the direct immobilization of glucose oxidase to produce a uniform, thin, and compact film on a Pt electrode. Electropolymerization of phenol was then employed to form an anti-interference and protective polyphenol film within the enzyme layer. In addition, a stability-reinforcing membrane derived from (3-aminopropyl)trimethoxysilane was constructed by electrochemically assisted cross-linking. This hybrid film outside the enzyme layer contributed to the improved stability and permselectivity. The resulting glucose sensor was characterized by a short response time (<4 s), high sensitivity (1200 nA/mM x cm2), low interference from endogenous electroactive species, and working lifetime of more than 50 days.

Redefining the modular organization of the core Mediator complex.

PubMed

Wang, Xuejuan; Sun, Qianqian; Ding, Zhenrui; Ji, Jinhua; Wang, Jianye; Kong, Xiao; Yang, Jianghong; Cai, Gang

2014-07-01

The Mediator complex plays an essential role in the regulation of eukaryotic transcription. The Saccharomyces cerevisiae core Mediator comprises 21 subunits, which are organized into Head, Middle and Tail modules. Previously, the Head module was assigned to a distinct dense domain at the base, and the Middle and Tail modules were identified to form a tight structure above the Head module, which apparently contradicted findings from many biochemical and functional studies. Here, we compared the structures of the core Mediator and its subcomplexes, especially the first 3D structure of the Head + Middle modules, which permitted an unambiguous assignment of the three modules. Furthermore, nanogold labeling pinpointing four Mediator subunits from different modules conclusively validated the modular assignment, in which the Head and Middle modules fold back on one another and form the upper portion of the core Mediator, while the Tail module forms a distinct dense domain at the base. The new modular model of the core Mediator has reconciled the previous inconsistencies between the structurally and functionally defined Mediator modules. Collectively, these analyses completely redefine the modular organization of the core Mediator, which allow us to integrate the structural and functional information into a coherent mechanism for the Mediator's modularity and regulation in transcription initiation.

Redefining the modular organization of the core Mediator complex

PubMed Central

Wang, Xuejuan; Sun, Qianqian; Ding, Zhenrui; Ji, Jinhua; Wang, Jianye; Kong, Xiao; Yang, Jianghong; Cai, Gang

2014-01-01

The Mediator complex plays an essential role in the regulation of eukaryotic transcription. The Saccharomyces cerevisiae core Mediator comprises 21 subunits, which are organized into Head, Middle and Tail modules. Previously, the Head module was assigned to a distinct dense domain at the base, and the Middle and Tail modules were identified to form a tight structure above the Head module, which apparently contradicted findings from many biochemical and functional studies. Here, we compared the structures of the core Mediator and its subcomplexes, especially the first 3D structure of the Head + Middle modules, which permitted an unambiguous assignment of the three modules. Furthermore, nanogold labeling pinpointing four Mediator subunits from different modules conclusively validated the modular assignment, in which the Head and Middle modules fold back on one another and form the upper portion of the core Mediator, while the Tail module forms a distinct dense domain at the base. The new modular model of the core Mediator has reconciled the previous inconsistencies between the structurally and functionally defined Mediator modules. Collectively, these analyses completely redefine the modular organization of the core Mediator, which allow us to integrate the structural and functional information into a coherent mechanism for the Mediator's modularity and regulation in transcription initiation. PMID:24810298

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.

Polyarene mediators for mediated redox flow battery

DOEpatents

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

Anodic Oxidative Modification of Egg White for Heat Treatment.

PubMed

Takahashi, Masahito; Handa, Akihiro; Yamaguchi, Yusuke; Kodama, Risa; Chiba, Kazuhiro

2016-08-31

A new functionalization of egg white was achieved by an electrochemical reaction. The method involves electron transfer from thiol groups of egg white protein to form disulfide bonds. The oxidized egg white produced less hydrogen sulfide during heat treatment; with sufficient application of electricity, almost no hydrogen sulfide was produced. In addition, gels formed by heating electrochemically oxidized egg white exhibited unique properties, such as a lower gelation temperature and a softened texture, presumably due to protein aggregation and electrochemically mediated intramolecular disulfide bond formation.

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.

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.

High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode

DOE PAGES

Song, Yang; Peng, Rui; Hensley, Dale K.; ...

2016-09-28

Carbon dioxide is a pollutant, but also a potential carbon source provided an efficient means to convert it to useful products. Herein we report a nanostructured catalyst for the direct electrochemical reduction of dissolved CO 2 to ethanol with high Faradaic efficiency (63%) and high selectivity (84%). The catalyst is comprised of Cu nanoparticle on a highly textured, N-doped graphene film. Detailed electrochemical analysis and complementary DFT calculations indicate a novel mechanism in which multiple active sites, working sequentially, control the coupling of carbon monoxide radicals and mediate the subsequent electrochemical reduction to alcohol.

Label-free electrochemical biosensing of small-molecule inhibition on O-GlcNAc glycosylation.

PubMed

Yang, Yu; Gu, Yuxin; Wan, Bin; Ren, Xiaomin; Guo, Liang-Hong

2017-09-15

O-linked N-acetylglucosamine (O-GlcNAc) transferase (OGT) plays a critical role in modulating protein function in many cellular processes and human diseases such as Alzheimer's disease and type II diabetes, and has emerged as a promising new target. Specific inhibitors of OGT could be valuable tools to probe the biological functions of O-GlcNAcylation, but a lack of robust nonradiometric assay strategies to detect glycosylation, has impeded efforts to identify such compounds. Here we have developed a novel label-free electrochemical biosensor for the detection of peptide O-GlcNAcylation using protease-protection strategy and electrocatalytic oxidation of tyrosine mediated by osmium bipyridine as a signal reporter. There is a large difference in the abilities of proteolysis of the glycosylated and the unglycosylated peptides by protease, thus providing a sensing mechanism for OGT activity. When the O-GlcNAcylation is achieved, the glycosylated peptides cannot be cleaved by proteinase K and result in a high current response on indium tin oxide (ITO) electrode. However, when the O-GlcNAcylation is successfully inhibited using a small molecule, the unglycosylated peptides can be cleaved easily and lead to low current signal. Peptide O-GlcNAcylation reaction was performed in the presence of a well-defined small-molecule OGT inhibitor. The results indicated that the biosensor could be used to screen the OGT inhibitors effectively. Our label-free electrochemical method is a promising candidate for protein glycosylation pathway research in screening small-molecule inhibitors of OGT. Copyright © 2017 Elsevier B.V. All rights reserved.

Biochip for Real-Time Monitoring of Hepatitis B Virus (HBV) by Combined Loop-Mediated Isothermal Amplification and Solution-Phase Electrochemical Detection

NASA Astrophysics Data System (ADS)

Tien, Bui Quang; Ngoc, Nguyen Thy; Loc, Nguyen Thai; Thu, Vu Thi; Lam, Tran Dai

2017-06-01

Accurate in situ diagnostic tests play a key role in patient management and control of most infectious diseases. To achieve this, use of handheld biochips that implement sample handling, sample analysis, and result readout together is an ideal approach. We present herein a fluid-handling biochip for real-time electrochemical monitoring of nucleic acid amplification based on loop-mediated isothermal amplification and real-time electrochemical detection on a microfluidic platform. Intercalation between amplifying DNA and free redox probe in solution phase was used to monitor the number of DNA copies. The whole diagnostic process is completed within 70 min. Our platform offers a fast and easy tool for quantification of viral pathogens in shorter time and with limited risk of all potential forms of cross-contamination. Such diagnostic tools have potential to make a huge difference to the lives of millions of people worldwide.

Ligand Field Strength Mediates Electron Delocalization in Octahedral [((H)L)2Fe6(L')m](n+) Clusters.

PubMed

Hernández Sánchez, Raúl; Zheng, Shao-Liang; Betley, Theodore A

2015-09-02

To assess the impact of terminal ligand binding on a variety of cluster properties (redox delocalization, ground-state stabilization, and breadth of redox state accessibility), we prepared three electron-transfer series based on the hexanuclear iron cluster [((H)L)2Fe6(L')m](n+) in which the terminal ligand field strength was modulated from weak to strong (L' = DMF, MeCN, CN). The extent of intracore M-M interactions is gauged by M-M distances, spin ground state persistence, and preference for mixed-valence states as determined by electrochemical comproportionation constants. Coordination of DMF to the [((H)L)2Fe6] core leads to weaker Fe-Fe interactions, as manifested by the observation of ground states populated only at lower temperatures (<100 K) and by the greater evidence of valence trapping within the mixed-valence states. Comproportionation constants determined electrochemically (Kc = 10(4)-10(8)) indicate that the redox series exhibits electronic delocalization (class II-III), yet no intervalence charge transfer (IVCT) bands are observable in the near-IR spectra. Ligation of the stronger σ donor acetonitrile results in stabilization of spin ground states to higher temperatures (∼300 K) and a high degree of valence delocalization (Kc = 10(2)-10(8)) with observable IVCT bands. Finally, the anionic cyanide-bound series reveals the highest degree of valence delocalization with the most intense IVCT bands (Kc = 10(12)-10(20)) and spin ground state population beyond room temperature. Across the series, at a given formal oxidation level, the capping ligand on the hexairon cluster dictates the overall properties of the aggregate, modulating the redox delocalization and the persistence of the intracore coupling of the metal sites.

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.

BF 3-promoted electrochemical properties of quinoxaline in propylene carbonate

DOE PAGES

Carino, Emily V.; Diesendruck, Charles E.; Moore, Jeffrey S.; ...

2015-02-04

Electrochemical and density functional studies demonstrate that coordination of electrolyte constituents to quinoxalines modulates their electrochemical properties. Quinoxalines are shown to be electrochemically inactive in most electrolytes in propylene carbonate, yet the predicted reduction potential is shown to match computational estimates in acetonitrile. We find that in the presence of LiBF 4 and trace water, an adduct is formed between quinoxaline and the Lewis acid BF3, which then displays electrochemical activity at 1–1.5 V higher than prior observations of quinoxaline electrochemistry in non-aqueous media. Direct synthesis and testing of a bis-BF 3 quinoxaline complex further validates the assignment of themore » electrochemically active species, presenting up to a ~26-fold improvement in charging capacity, demonstrating the advantages of this adduct over unmodified quinoxaline in LiBF 4-based electrolyte. The use of Lewis acids to effectively “turn on” the electrochemical activity of organic molecules may lead to the development of new active material classes for energy storage applications.« less

Alleviation of membrane fouling in a submerged membrane bioreactor with electrochemical oxidation mediated by in-situ free chlorine generation.

PubMed

Chung, Chong Min; Tobino, Tomohiro; Cho, Kangwoo; Yamamoto, Kazuo

2016-06-01

The control of membrane fouling is still the biggest challenge that membrane bioreactor (MBR) for wastewater treatment faces with. In this report, we evince that an in-situ electrochemical free chlorine generation is effective for membrane fouling mitigation. An electrochemical oxidation (EO) apparatus with perforated Ti/IrO2 anodes and Ti/Pt cathodes was integrated into a conventional MBR with microfiltration module (EO-MBR). The membrane fouling characteristics of EO-MBR fed with synthetic wastewater were monitored for about 2 months in comparison to control MBRs. In the EO-MBR at a direct current density of 0.4 mA/cm(2), the frequency of membrane fouling when the trans-membrane pressure (TMP) reached 30 kPa was effectively reduced by 40% under a physical membrane cleaning regime. The evolution patterns of TMP together with hydraulic resistance analysis based on resistance-in-series model indicated that the electrochemically generated active chlorine alleviated the physically irremovable membrane fouling. Further analysis on extracellular polymeric substances (EPS) of sludge cake layer (SCL) revealed significant reductions of protein contents in soluble EPS and fluorescence emission intensities from humic acids and other fluorophores in bound EPS, which in-turn would decrease the hydrophobic accumulation of organic foulants on membrane pores. The chlorine dosage from the EO apparatus was estimated to be 4.7 mg Cl2/g MLVSS/day and the overall physicochemical properties (bio-solids concentration, floc diameter, zeta-potential) as well as the microbial activity in terms of specific oxygen utilization rate and removal efficiency of dissolved organic carbon (>97%) were not affected significantly. A T-RFLP (terminal restriction fragment length polymorphism) analysis suggested noticeable shifts in microbial community both in mixed liquor and sludge cake layer. Consequently, our electrochemical chlorination would be an efficient fouling control strategy in membrane-based water treatment processes where additional electricity consumption and cathodic scale deposition are not of serious concerns. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

Electrochemical detection of glutathione based on Hg(2+)-mediated strand displacement reaction strategy.

PubMed

Lv, Yun; Yang, Lili; Mao, Xiaoxia; Lu, Mengjia; Zhao, Jing; Yin, Yongmei

2016-11-15

Glutathione (GSH) plays an important role in numerous cellular functions, and the abnormal GSH expression is closely related with many dangerous human diseases. In this work, we have proposed a simple but sensitive electrochemical method for quantitative detection of GSH based on an Hg(2+)-mediated strand displacement reaction. Owing to the specific binding of Hg(2+) with T-T mismatches, helper DNA can bind to 3' terminal of probe DNA 1 and initiate the displacement of probe DNA 2 immobilized on an electrode surface. However, Hg(2+)-mediated strand displacement reaction can be inhibited by the chelation of GSH with Hg(2+), thereby leading to an obvious electrochemical response obtained from methylene blue that is modified onto the probe DNA. Our method can sensitively detect GSH in a wide linear range from 0.5nM to 5μM with a low detection limit of 0.14nM, which can also easily distinguish target molecules in complex serum samples and even cell extractions. Therefore, this method may have great potential to monitor GSH in the physiological and pathological condition in the future. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Ferrocene-Modified Linear Poly(ethylenimine) for Enzymatic Immobilization and Electron Mediation.

PubMed

Hickey, David P

2017-01-01

Enzymatic glucose biosensors and biofuel cells make use of the electrochemical transduction between an oxidoreductase enzyme, such as glucose oxidase (GOx), and an electrode to either quantify the amount of glucose in a solution or generate electrical energy. However, many enzymes including GOx are not able to electrochemically interact with an electrode surface directly, but require an external electrochemical relay to shuttle electrons to the electrode. Ferrocene-modified linear poly(ethylenimine) (Fc-LPEI) redox polymers have been designed to simultaneously immobilize glucose oxidase (GOx) at an electrode and mediate electron transfer from their flavin adenine dinucleotide (FAD) active site to the electrode surface. Cross-linked films of Fc-LPEI create hydrogel networks that allow for rapid transport of glucose, while the covalently bound ferrocene moieties are able to facilitate rapid electron transfer due to the ability of ferrocene to exchange electrons between adjacent ferrocene residues. For these reasons, Fc-LPEI films have been widely used in the development of high current density bioanode materials. This chapter describes the synthesis of a commonly used dimethylferrocene-modified linear poly(ethylenimine), as well as the subsequent preparation and electrochemical characterization of a GOx bioanode film utilizing the synthesized polymer.

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.

Nanoparticle-based sandwich electrochemical immunoassay for carbohydrate antigen 125 with signal enhancement using enzyme-coated nanometer-sized enzyme-doped silica beads.

PubMed

Tang, Dianping; Su, Biling; Tang, Juan; Ren, Jingjing; Chen, Guonan

2010-02-15

A novel nanoparticle-based electrochemical immunoassay of carbohydrate antigen 125 (CA125) as a model was designed to couple with a microfluidic strategy using anti-CA125-functionalized magnetic beads as immunosensing probes. To construct the immunoassay, thionine-horseradish peroxidase conjugation (TH-HRP) was initially doped into nanosilica particles using the reverse micelle method, and then HRP-labeled anti-CA125 antibodies (HRP-anti-CA125) were bound onto the surface of the synthesized nanoparticles, which were used as recognition elements. Different from conventional nanoparticle-based electrochemical immunoassays, the recognition elements of the immunoassay simultaneously contained electron mediator and enzyme labels and simplified the electrochemical measurement process. The sandwich-type immunoassay format was used for the online formation of the immunocomplex in an incubation cell and captured in the detection cell with an external magnet. The electrochemical signals derived from the carried HRP toward the reduction of H(2)O(2) using the doped thionine as electron mediator. Under optimal conditions, the electrochemical immunoassay exhibited a wide working range from 0.1 to 450 U/mL with a detection limit of 0.1 U/mL CA125. The precision, reproducibility, and stability of the immunoassay were acceptable. The assay was evaluated for clinical serum samples, receiving in excellent accordance with results obtained from the standard enzyme-linked immunosorbent assay (ELISA) method. Concluding, the nanoparticle-based assay format provides a promising approach in clinical application and thus represents a versatile detection method.

Voltammetric Determination of Penicillamine Using a Carbon Paste Electrode Modified with Multiwall Carbon Nanotubes In the Presence of Methyldopa as a Mediator.

PubMed

Safari, Fardin; Keyvanfard, Mohsen; Karimi-Maleh, Hassan; Alizad, Khadijeh

2017-01-01

A multiwall carbon nanotubes-modified carbon paste electrode (MWCNTs/MCPE) was fabricated and used to study the electrooxidation of penicillamine (PA) by electrochemical methods in the presence of methyldopa (MDOP) as a homogeneous mediator. The electrochemical oxidation of PA on the new sensor has been carefully studied. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, K / h , were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of PA showed a linear dependent on the PA concentrations and linear calibration curves were obtained in the ranges of 0.2-250.0 µM of PA concentration with square wave voltammetry (SWV) method. The detection limit (3σ) was determined as 0.1 µM. This sensor was also examined as a fast, selective, simple and precise new sensor for voltammetric determination of PA in real samples such as drug and urine.

A novel electrochemical biosensor for ultrasensitive and specific detection of DNA based on molecular beacon mediated circular strand displacement and rolling circle amplification.

PubMed

Cheng, Wei; Zhang, Wei; Yan, Yurong; Shen, Bo; Zhu, Dan; Lei, Pinhua; Ding, Shijia

2014-12-15

A novel electrochemical biosensing strategy was developed for ultrasensitive and specific detection of target DNA using a cascade signal amplification based on molecular beacon (MB) mediated circular strand displacement (CSD), rolling circle amplification (RCA), biotin-strepavidin system, and enzymatic amplification. The target DNA hybridized with the loop portion of MB probe immobilized on the gold electrode and triggered the CSD, leading to multiple biotin-tagged DNA duplex. Furthermore, via biotin-streptavidin interaction, the RCA was implemented, producing long massive tandem-repeat DNA sequences for binding numerous biotinylated detection probes. This enabled an ultrasensitive electrochemical readout by further employing the streptavidin-alkaline phosphatase. The proposed biosensor showed very high sensitivity and selectivity with a dynamic response range from 1 fM to 100 pM. The proposed strategy could have the potential for applying in clinical molecular diagnostics and environmental monitoring. Copyright © 2014 Elsevier B.V. All rights reserved.

Voltammetric Determination of Penicillamine Using a Carbon Paste Electrode Modified with Multiwall Carbon Nanotubes In the Presence of Methyldopa as a Mediator

PubMed Central

Safari, Fardin; Keyvanfard, Mohsen; Karimi-Maleh, Hassan; Alizad, Khadijeh

2017-01-01

A multiwall carbon nanotubes-modified carbon paste electrode (MWCNTs/MCPE) was fabricated and used to study the electrooxidation of penicillamine (PA) by electrochemical methods in the presence of methyldopa (MDOP) as a homogeneous mediator. The electrochemical oxidation of PA on the new sensor has been carefully studied. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, K/h, were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of PA showed a linear dependent on the PA concentrations and linear calibration curves were obtained in the ranges of 0.2-250.0 µM of PA concentration with square wave voltammetry (SWV) method. The detection limit (3σ) was determined as 0.1 µM. This sensor was also examined as a fast, selective, simple and precise new sensor for voltammetric determination of PA in real samples such as drug and urine. PMID:29201090

Cooperative Electrocatalytic O 2 Reduction Involving Co(salophen) with p- Hydroquinone as an Electron–Proton Transfer Mediator

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

Anson, Colin W.; Stahl, Shannon S.

2017-12-01

The molecular cobalt complex, Co(salophen), and para-hydroquinone (H2Q) serve as effective cocatalysts for the electrochemical reduction of O2 to water. Mechanistic studies reveal redox cooperativity between Co(salophen) and H2Q. H2Q serves as an electron-proton transfer mediator (EPTM) that enables electrochemical O2 reduction at higher potentials and with faster rates than is observed with Co(salophen) alone. Replacement of H2Q with the higher potential EPTM, 2-chloro-H2Q, allows for faster O2 reduction rates at higher applied potential. These results demonstrate a unique strategy to achieve improved performance with molecular electrocatalyst systems.

Responsive hairpin DNA aptamer switch to program the strand displacement reaction for the enhanced electrochemical assay of ATP.

PubMed

Wang, Li; Fang, Li; Liu, Shufeng

2015-09-07

A responsive hairpin DNA aptamer switch was ingeniously designed for enzyme-free, sensitive and selective electrochemical detection of ATP. It takes full advantage of the target-triggered liberation effect of the toehold region and the concomitant proximity effect with the branch-migration region to execute the toehold-mediated strand displacement reaction on the electrode surface.

Simultaneous determination of hydroxylamine and phenol using a nanostructure-based electrochemical sensor.

PubMed

Moghaddam, Hadi Mahmoudi; Beitollahi, Hadi; Tajik, Somayeh; Malakootian, Mohammad; Maleh, Hassan Karimi

2014-11-01

The electrochemical oxidation of hydroxylamine on the surface of a carbon paste electrode modified with carbon nanotubes and 2,7-bis(ferrocenyl ethyl)fluoren-9-one is studied. The electrochemical response characteristics of the modified electrode toward hydroxylamine and phenol were investigated. The results showed an efficient catalytic activity of the electrode for the electro-oxidation of hydroxylamine, which leads to lowering its overpotential. The modified electrode exhibits an efficient electron-mediating behavior together with well-separated oxidation peaks for hydroxylamine and phenol. Also, the modified electrode was used for determination of hydroxylamine and phenol in some real samples.

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.

Ferritin-Triggered Redox Cycling for Highly Sensitive Electrochemical Immunosensing of Protein.

PubMed

Akanda, Md Rajibul; Ju, Huangxian

2018-06-04

Electrochemical immunoassay amplified with redox cycling has become a challenging topic in highly sensitive analysis of biomarkers. Here a ferritin-triggered redox cycling is reported by using a highly outersphere reaction-philic (OSR-philic) redox mediator ruthenium hexamine (Ru(NH3)63+) to perform the OSR-philic/innersphere reaction-philic (ISR-philic) controlled signal amplification. The screened mediator can meet the needs of lower E0 than ferritin, low reactivity with ISR-philic species, and quick electron exchange with ferritin redox couple. The ferritin-labeled antibody is firstly bounded to immunosensor surface by recognizing the target antigen capured by the immobilized primary antibody. The ferritin then mediates OSR-philic/ISR-philic transfer from Ru(NH3)63+/2+/immunosensor to ferritin-H2O2 redox system. The fast mediation and excellent resistant of highly OSR-philic Ru(NH3)63+ against radical oxygen species lead to highly sensitive electrochemical readout and high signal-to-background ratio. The proposed redox cycling greatly enhances the readout signal and the sensitivity of traditional ferritin-labelled sandwich immunoassay. Using Enteropathogenic Coli (E. Coli) antigen as a model analyte, the developed method shows excellent linearity over the concentration range from 10.0 pg/mL to 0.1 µg/mL and a detection limit of 10.0 fg/mL. The acceptable accuracy, good reproducibility and selectivity of the proposed immunoassay method in real samples indicate the superior practicability of the ferritin-triggered redox cycling.

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 %.

Mast cell-based electrochemical biosensor for quantification of the major shrimp allergen Pen a 1 (tropomyosin).

PubMed

Jiang, Donglei; Ji, Jian; An, Lu; Sun, Xiulan; Zhang, Yinzhi; Zhang, Genyi; Tang, Lili

2013-12-15

A novel cell-based electrochemical biosensor was developed to quantify major shrimp allergen Pen a 1 (tropomyosin) and to assess its immunoglobulin E (IgE)-mediated hypersensitivity. Rat basophilic leukemia (RBL-2H3) mast cells, encapsulated in type I collagen, were immobilized on a self-assembled l-cysteine/gold nanoparticle (AuNPsCys)-modified gold electrode to monitor IgE-mediated mast cell sensitization and activation. The exposure of dinitrophenol-bovine serum albumin (DNP-BSA), as a model antigen that stimulates mast cells, induced a robust and long-lasting electrochemical impedance signal in a dose-dependent manner which efficiently measured degranulation of anti-DNP IgE-stimulated mast cells. Then this mast cell-based biosensor was applied into quantification for the shrimp allergen with anti-shrimp tropomyosin IgE-sensitization. The electrochemical impedance spectroscopy (EIS) results showed that the impedance value (Ret) increased with the concentration of purified shrimp allergen Pen a 1 (tropomyosin) in range of 0.5-0.25 μg mL(-1) with the detection limit as 0.15 μg mL(-1), and the electrochemical result was confirmed by β-hexosaminidase assay and scanning electron microscopic morphological (SEM) analysis. Thus, a simple, label-free, and sensitive method for the determination of shrimp allergens was proposed and demonstrated here, implying a highly versatile biosensor for food allergen detection and prediction. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Bodipy-C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer.

PubMed

Guo, Song; Xu, Liang; Xu, Kejing; Zhao, Jianzhang; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-07-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives ( B-1 , B-2 and B-3 , which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C 60 was used as the complementary hydrogen bonding module ( C-1 ), in which the C 60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references ( B-1-Me , B-2-Me and B-3-Me ), which are unable to form strong H-bonds with C-1 . Triple H-bonds are formed between each Bodipy antenna ( B-1 , B-2 and B-3 ) and the C 60 module ( C-1 ). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C 60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C 60 module (for assembly B-1·C-1 ), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1 ). Intra-assembly forward-backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet-triplet annihilation upconversion.

Electrochemically Active Soluble Mediators from Shewanella oneidensis: Relevance to Microbial Fuel Cells and Extracellular Electron Transfer

DTIC Science & Technology

2008-05-01

A second approach is the use of soluble mediators such as, quinones, phenazines , and riboflavin, which are able to shuttle electrons from the cell...done using the equivalent graphite felt or graphite felt coated with platinum nanoparticles . Fuel cell chambers were separated using a gas-permeable

Voltammetric determination of homocysteine using multiwall carbon nanotube paste electrode in the presence of chlorpromazine as a mediator.

PubMed

Gholami-Orimi, Fathali; Taleshi, Farshad; Biparva, Pourya; Karimi-Maleh, Hassan; Beitollahi, Hadi; Ebrahimi, Hamid R; Shamshiri, Mohamad; Bagheri, Hasan; Fouladgar, Masoud; Taherkhani, Ali

2012-01-01

We propose chlorpromazine (CHP) as a new mediator for the rapid, sensitive, and highly selective voltammetric determination of homocysteine (Hcy) using multiwall carbon nanotube paste electrode (MWCNTPE). The experimental results showed that the carbon nanotube paste electrode has a highly electrocatalytic activity for the oxidation of Hcy in the presence of CHP as a mediator. Cyclic voltammetry, double potential step chronoamperometry, and square wave voltammetry (SWV) are used to investigate the suitability of CHP at the surface of MWCNTPE as a mediator for the electrocatalytic oxidation of Hcy in aqueous solutions. The kinetic parameters of the system, including electron transfer coefficient, and catalytic rate constant were also determined using the electrochemical approaches. In addition, SWV was used for quantitative analysis. SWV showed wide linear dynamic range (0.1-210.0 μM Hcy) with a detection limit of 0.08 μM Hcy. Finally, this method was also examined as a selective, simple, and precise electrochemical sensor for the determination of Hcy in real samples.

Voltammetric Determination of Homocysteine Using Multiwall Carbon Nanotube Paste Electrode in the Presence of Chlorpromazine as a Mediator

PubMed Central

Gholami-Orimi, Fathali; Taleshi, Farshad; Biparva, Pourya; Karimi-Maleh, Hassan; Beitollahi, Hadi; Ebrahimi, Hamid R.; Shamshiri, Mohamad; Bagheri, Hasan; Fouladgar, Masoud; Taherkhani, Ali

2012-01-01

We propose chlorpromazine (CHP) as a new mediator for the rapid, sensitive, and highly selective voltammetric determination of homocysteine (Hcy) using multiwall carbon nanotube paste electrode (MWCNTPE). The experimental results showed that the carbon nanotube paste electrode has a highly electrocatalytic activity for the oxidation of Hcy in the presence of CHP as a mediator. Cyclic voltammetry, double potential step chronoamperometry, and square wave voltammetry (SWV) are used to investigate the suitability of CHP at the surface of MWCNTPE as a mediator for the electrocatalytic oxidation of Hcy in aqueous solutions. The kinetic parameters of the system, including electron transfer coefficient, and catalytic rate constant were also determined using the electrochemical approaches. In addition, SWV was used for quantitative analysis. SWV showed wide linear dynamic range (0.1–210.0 μM Hcy) with a detection limit of 0.08 μM Hcy. Finally, this method was also examined as a selective, simple, and precise electrochemical sensor for the determination of Hcy in real samples. PMID:22675657

Scanning electrochemical microscopy based evaluation of influence of pH on bioelectrochemical activity of yeast cells - Saccharomyces cerevisiae.

PubMed

Ramanavicius, A; Morkvenaite-Vilkonciene, I; Kisieliute, A; Petroniene, J; Ramanaviciene, A

2017-01-01

In this research scanning electrochemical microscopy was applied for the investigation of immobilized yeast Saccharomyces cerevisiae cells. Two redox mediators based system was applied in order to increase the efficiency of charge transfer from yeast cells. 9,10-phenanthrenequinone (PQ) was applied as a lipophilic redox mediator, which has the ability to cross the cell's membrane; another redox mediator was ferricyanide, which acted as a hydrophylic electron acceptor able to transfer electrons from the PQ to the working electrode of SECM. Hill's function was applied to determine the optimal pH for this described SECM-based system. The influence of pH on cell viability could be well described by Hill's function. It was determined that at pH 6.5 the PQ has a minimal toxic influence on yeast cells, and the kinetics of metabolic processes in cells as well as electron transfer rate achieved in consecutive action of both redox mediators were appropriate to achieve optimal current signals. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

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

Liezers, Martin; Lehn, Scott A; Olsen, Khris B

2009-10-01

Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO 3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by themore » applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.« less

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.

Scanning electrochemical microscopy (SECM) as a tool in biosensor research.

PubMed

Stoica, Leonard; Neugebauer, Sebastian; Schuhmann, Wolfgang

2008-01-01

Scanning electrochemical microscopy (SECM) is discussed as a versatile tool to provide localized (electro)chemical information in the context of biosensor research. Advantages of localized electrochemical measurements will be discussed and a brief introduction to SECM and its operation modes will be given. Experimental challenges of the different detection modes of SECM and its applicability for different fields in biosensor research are discussed. Among these are the evaluation of immobilization techniques by probing the local distribution of biological activity, the visualization of diffusion profiles of reactants, cofactors, mediators, and products, and the elucidation of (local) kinetic parameters. The combination of SECM with other scanning-probe techniques allows to maximize the information on a given biosensing system. The potential of SECM as a tool in micro-fabrication aiming for the fabrication of microstructured biosensors will be shortly discussed.

Mediator kinase module and human tumorigenesis.

PubMed

Clark, Alison D; Oldenbroek, Marieke; Boyer, Thomas G

2015-01-01

Mediator is a conserved multi-subunit signal processor through which regulatory informatiosn conveyed by gene-specific transcription factors is transduced to RNA Polymerase II (Pol II). In humans, MED13, MED12, CDK8 and Cyclin C (CycC) comprise a four-subunit "kinase" module that exists in variable association with a 26-subunit Mediator core. Genetic and biochemical studies have established the Mediator kinase module as a major ingress of developmental and oncogenic signaling through Mediator, and much of its function in signal-dependent gene regulation derives from its resident CDK8 kinase activity. For example, CDK8-targeted substrate phosphorylation impacts transcription factor half-life, Pol II activity and chromatin chemistry and functional status. Recent structural and biochemical studies have revealed a precise network of physical and functional subunit interactions required for proper kinase module activity. Accordingly, pathologic change in this activity through altered expression or mutation of constituent kinase module subunits can have profound consequences for altered signaling and tumor formation. Herein, we review the structural organization, biological function and oncogenic potential of the Mediator kinase module. We focus principally on tumor-associated alterations in kinase module subunits for which mechanistic relationships as opposed to strictly correlative associations are established. These considerations point to an emerging picture of the Mediator kinase module as an oncogenic unit, one in which pathogenic activation/deactivation through component change drives tumor formation through perturbation of signal-dependent gene regulation. It follows that therapeutic strategies to combat CDK8-driven tumors will involve targeted modulation of CDK8 activity or pharmacologic manipulation of dysregulated CDK8-dependent signaling pathways.

Mediator kinase module and human tumorigenesis

PubMed Central

Clark, Alison D.; Oldenbroek, Marieke; Boyer, Thomas G.

2016-01-01

Mediator is a conserved multi-subunit signal processor through which regulatory informatiosn conveyed by gene-specific transcription factors is transduced to RNA Polymerase II (Pol II). In humans, MED13, MED12, CDK8 and Cyclin C (CycC) comprise a four-subunit “kinase” module that exists in variable association with a 26-subunit Mediator core. Genetic and biochemical studies have established the Mediator kinase module as a major ingress of developmental and oncogenic signaling through Mediator, and much of its function in signal-dependent gene regulation derives from its resident CDK8 kinase activity. For example, CDK8-targeted substrate phosphorylation impacts transcription factor half-life, Pol II activity and chromatin chemistry and functional status. Recent structural and biochemical studies have revealed a precise network of physical and functional subunit interactions required for proper kinase module activity. Accordingly, pathologic change in this activity through altered expression or mutation of constituent kinase module subunits can have profound consequences for altered signaling and tumor formation. Herein, we review the structural organization, biological function and oncogenic potential of the Mediator kinase module. We focus principally on tumor-associated alterations in kinase module subunits for which mechanistic relationships as opposed to strictly correlative associations are established. These considerations point to an emerging picture of the Mediator kinase module as an oncogenic unit, one in which pathogenic activation/deactivation through component change drives tumor formation through perturbation of signal-dependent gene regulation. It follows that therapeutic strategies to combat CDK8-driven tumors will involve targeted modulation of CDK8 activity or pharmacologic manipulation of dysregulated CDK8-dependent signaling pathways. PMID:26182352

Architecture of the RNA polymerase II-Mediator core initiation complex.

PubMed

Plaschka, C; Larivière, L; Wenzeck, L; Seizl, M; Hemann, M; Tegunov, D; Petrotchenko, E V; Borchers, C H; Baumeister, W; Herzog, F; Villa, E; Cramer, P

2015-02-19

The conserved co-activator complex Mediator enables regulated transcription initiation by RNA polymerase (Pol) II. Here we reconstitute an active 15-subunit core Mediator (cMed) comprising all essential Mediator subunits from Saccharomyces cerevisiae. The cryo-electron microscopic structure of cMed bound to a core initiation complex was determined at 9.7 Å resolution. cMed binds Pol II around the Rpb4-Rpb7 stalk near the carboxy-terminal domain (CTD). The Mediator head module binds the Pol II dock and the TFIIB ribbon and stabilizes the initiation complex. The Mediator middle module extends to the Pol II foot with a 'plank' that may influence polymerase conformation. The Mediator subunit Med14 forms a 'beam' between the head and middle modules and connects to the tail module that is predicted to bind transcription activators located on upstream DNA. The Mediator 'arm' and 'hook' domains contribute to a 'cradle' that may position the CTD and TFIIH kinase to stimulate Pol II phosphorylation.

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.

Core Mediator structure at 3.4 Å extends model of transcription initiation complex.

PubMed

Nozawa, Kayo; Schneider, Thomas R; Cramer, Patrick

2017-05-11

Mediator is a multiprotein co-activator that binds the transcription pre-initiation complex (PIC) and regulates RNA polymerase (Pol) II. The Mediator head and middle modules form the essential core Mediator (cMed), whereas the tail and kinase modules play regulatory roles. The architecture of Mediator and its position on the PIC are known, but atomic details are limited to Mediator subcomplexes. Here we report the crystal structure of the 15-subunit cMed from Schizosaccharomyces pombe at 3.4 Å resolution. The structure shows an unaltered head module, and reveals the intricate middle module, which we show is globally required for transcription. Sites of known Mediator mutations cluster at the interface between the head and middle modules, and in terminal regions of the head subunits Med6 (ref. 16) and Med17 (ref. 17) that tether the middle module. The structure led to a model for Saccharomyces cerevisiae cMed that could be combined with the 3.6 Å cryo-electron microscopy structure of the core PIC (cPIC). The resulting atomic model of the cPIC-cMed complex informs on interactions of the submodules forming the middle module, called beam, knob, plank, connector, and hook. The hook is flexibly linked to Mediator by a conserved hinge and contacts the transcription initiation factor IIH (TFIIH) kinase that phosphorylates the carboxy (C)-terminal domain (CTD) of Pol II and was recently positioned on the PIC. The hook also contains residues that crosslink to the CTD and reside in a previously described cradle. These results provide a framework for understanding Mediator function, including its role in stimulating CTD phosphorylation by TFIIH.

From Two-Phase to Three-Phase: The New Electrochemical Interface by Oxide Electrocatalysts

NASA Astrophysics Data System (ADS)

Xu, Zhichuan J.

2018-03-01

Electrochemical reactions typically occur at the interface between a solid electrode and a liquid electrolyte. The charge exchange behaviour between these two phases determines the kinetics of electrochemical reactions. In the past few years, significant advances have been made in the development of metal oxide electrocatalysts for fuel cell and electrolyser reactions. However, considerable gaps remain in the fundamental understanding of the charge transfer pathways and the interaction between the metal oxides and the conducting substrate on which they are located. In particular, the electrochemical interfaces of metal oxides are significantly different from the traditional (metal) ones, where only a conductive solid electrode and a liquid electrolyte are considered. Oxides are insulating and have to be combined with carbon as a conductive mediator. This electrode configuration results in a three-phase electrochemical interface, consisting of the insulating oxide, the conductive carbon, and the liquid electrolyte. To date, the mechanistic insights into this kind of non-traditional electrochemical interface remain unclear. Consequently conventional electrochemistry concepts, established on classical electrode materials and their two-phase interfaces, are facing challenges when employed for explaining these new electrode materials. [Figure not available: see fulltext.

Real-time electrochemical LAMP: a rational comparative study of different DNA intercalating and non-intercalating redox probes.

PubMed

Martin, Alexandra; Bouffier, Laurent; Grant, Kathryn B; Limoges, Benoît; Marchal, Damien

2016-06-20

We present a comparative study of ten redox-active probes for use in real-time electrochemical loop-mediated isothermal amplification (LAMP). Our main objectives were to establish the criteria that need to be fulfilled for minimizing some of the current limitations of the technique and to provide future guidelines in the search for ideal redox reporters. To ensure a reliable comparative study, each redox probe was tested under similar conditions using the same LAMP reaction and the same entirely automatized custom-made real-time electrochemical device (designed for electrochemically monitoring in real-time and in parallel up to 48 LAMP samples). Electrochemical melt curve analyses were recorded immediately at the end of each LAMP reaction. Our results show that there are a number of intercalating and non-intercalating redox compounds suitable for real-time electrochemical LAMP and that the best candidates are those able to intercalate strongly into ds-DNA but not too much to avoid inhibition of the LAMP reaction. The strongest intercalating redox probes were finally shown to provide higher LAMP sensitivity, speed, greater signal amplitude, and cleaner-cut DNA melting curves than the non-intercalating molecules.

Electrochemical Biosensor Composed of Silver Ion-Mediated dsDNA on Au-Encapsulated Bi2 Se3 Nanoparticles for the Detection of H2 O2 Released from Breast Cancer Cells.

PubMed

Mohammadniaei, Mohsen; Yoon, Jinho; Lee, Taek; Bharate, Bapurao G; Jo, Jinhee; Lee, Donghyun; Choi, Jeong-Woo

2018-04-01

A newly developed electrochemical biosensor composed of a topological insulator (TI) and metallic DNA (mDNA) is fabricated. The bismuth selenide nanoparticle (Bi 2 Se 3 NP) is synthesized and sandwiched between the gold electrode and another Au-deposited thin layer (Bi 2 Se 3 @Au). Then, eight-silver-ion mediated double-stranded DNA (mDNA) is immobilized onto the substrate (Bi 2 Se 3 @Au-mDNA) for the further detection of hydrogen peroxide. The Bi 2 Se 3 NP acts as the electrochemical-signal booster, while unprecedentedly its encapsulation by the Au thin layer keeps the TI surface states protected, improves its electrochemical-signal stability and provides an excellent platform for the subsequent covalent immobilization of the mDNA through Au-thiol interaction. Electrochemical results show that the fabricated biosensor represents much higher Ag + redox current (≈10 times) than those electrodes prepared without Bi 2 Se 3 @Au. The characterization of the Bi 2 Se 3 @Au-mDNA film is confirmed by atomic force microscopy, scanning tunneling microscopy, and cyclic voltammetry. The proposed biosensor shows a dynamic range of 00.10 × 10 -6 m to 27.30 × 10 -6 m, very low detection limit (10 × 10 -9 m), unique current response (1.6 s), sound H 2 O 2 recovery in serum, and substantial capability to classify two breast cancer subtypes (MCF-7 and MDA-MB-231) based on their difference in the H 2 O 2 generation, offering potential applications in the biomedicine and pharmacology fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An ultrasensitive electrochemical biosensor for polynucleotide kinase assay based on gold nanoparticle-mediated lambda exonuclease cleavage-induced signal amplification.

PubMed

Cui, Lin; Li, Yueying; Lu, Mengfei; Tang, Bo; Zhang, Chun-Yang

2018-01-15

Polynucleotide kinase (PNK) plays an essential role in cellular nucleic acid metabolism and the cellular response to DNA damage. However, conventional methods for PNK assay suffer from low sensitivity and involve multiple steps. Herein, we develop a simply electrochemical method for sensitive detection of PNK activity on the basis of Au nanoparticle (AuNP)-mediated lambda exonuclease cleavage-induced signal amplification. We use [Ru(NH 3 ) 6 ] 3+ as the electrochemically active indicator and design two DNA strands (i.e., strand 1 and strand 2) to sense PNK. The assembly of strand 2 on the AuNP surface leads to the formation of AuNP-strand 2 conjugates which can be subsequently immobilized on the gold electrode through the hybridization of strand 1 with strand 2 for the generation of a high electrochemical signal. The presence of PNK induces the phosphorylation of the strand 2-strand 1 hybrid and the subsequent cleavage of double-stranded DNA (dsDNA) by lambda exonuclease, resulting in the release of AuNP-strand 2 conjugates and [Ru(NH 3 ) 6 ] 3+ from the gold electrode surface and consequently the decrease of electrochemical signal. The PNK activity can be simply monitored by the measurement of [Ru(NH 3 ) 6 ] 3+ peak current signal. This assay is very sensitive with a detection limit of as low as 7.762 × 10 -4 UmL -1 and exhibits a large dynamic range from 0.001 to 10UmL -1 . Moreover, this method can be used to screen the PNK inhibitors, and it shows excellent performance in real sample analysis, thus holding great potential for further applications in biological researches and clinic diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

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.

Electrochemical Detection of Circadian Redox Rhythm in Cyanobacterial Cells via Extracellular Electron Transfer.

PubMed

Nishio, Koichi; Pornpitra, Tunanunkul; Izawa, Seiichiro; Nishiwaki-Ohkawa, Taeko; Kato, Souichiro; Hashimoto, Kazuhito; Nakanishi, Shuji

2015-06-01

Recent research on cellular circadian rhythms suggests that the coupling of transcription-translation feedback loops and intracellular redox oscillations is essential for robust circadian timekeeping. For clarification of the molecular mechanism underlying the circadian rhythm, methods that allow for the dynamic and simultaneous detection of transcription/translation and redox oscillations in living cells are needed. Herein, we report that the cyanobacterial circadian redox rhythm can be electrochemically detected based on extracellular electron transfer (EET), a process in which intracellular electrons are exchanged with an extracellular electrode. As the EET-based method is non-destructive, concurrent detection with transcription/translation rhythm using bioluminescent reporter strains becomes possible. An EET pathway that electrochemically connected the intracellular region of cyanobacterial cells with an extracellular electrode was constructed via a newly synthesized electron mediator with cell membrane permeability. In the presence of the mediator, the open circuit potential of the culture medium exhibited temperature-compensated rhythm with approximately 24 h periodicity. Importantly, such circadian rhythm of the open circuit potential was not observed in the absence of the electron mediator, indicating that the EET process conveys the dynamic information regarding the intracellular redox state to the extracellular electrode. These findings represent the first direct demonstration of the intracellular circadian redox rhythm of cyanobacterial cells. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Suppression of Mediator is regulated by Cdk8-dependent Grr1 turnover of the Med3 coactivator.

PubMed

Gonzalez, Deyarina; Hamidi, Nurul; Del Sol, Ricardo; Benschop, Joris J; Nancy, Thomas; Li, Chao; Francis, Lewis; Tzouros, Manuel; Krijgsveld, Jeroen; Holstege, Frank C P; Conlan, R Steven

2014-02-18

Mediator, an evolutionary conserved large multisubunit protein complex with a central role in regulating RNA polymerase II-transcribed genes, serves as a molecular switchboard at the interface between DNA binding transcription factors and the general transcription machinery. Mediator subunits include the Cdk8 module, which has both positive and negative effects on activator-dependent transcription through the activity of the cyclin-dependent kinase Cdk8, and the tail module, which is required for positive and negative regulation of transcription, correct preinitiation complex formation in basal and activated transcription, and Mediator recruitment. Currently, the molecular mechanisms governing Mediator function remain largely undefined. Here we demonstrate an autoregulatory mechanism used by Mediator to repress transcription through the activity of distinct components of different modules. We show that the function of the tail module component Med3, which is required for transcription activation, is suppressed by the kinase activity of the Cdk8 module. Med3 interacts with, and is phosphorylated by, Cdk8; site-specific phosphorylation triggers interaction with and degradation by the Grr1 ubiquitin ligase, thereby preventing transcription activation. This active repression mechanism involving Grr1-dependent ubiquitination of Med3 offers a rationale for the substoichiometric levels of the tail module that are found in purified Mediator and the corresponding increase in tail components seen in cdk8 mutants.

Aptamer-aided target capturing with biocatalytic metal deposition: an electrochemical platform for sensitive detection of cancer cells.

PubMed

Yi, Zi; Li, Xiao-Yan; Gao, Qing; Tang, Li-Juan; Chu, Xia

2013-04-07

A novel aptamer biosensor for cancer cell assay has been reported on the basis of ultrasensitive electrochemical detection. Cancer cell capturing is first accomplished via aptamer-aided recognition, and the cell-aptamer binding events then mediate an alkaline phosphatase-catalyzed silver deposition reaction which can be probed by electrochemical detection. Following biocatalytic silver deposition, an efficient amplification approach for sensitive electrochemical measurements is demonstrated, for cell detection with high sensitivity. Ramos cell are used as a model case, a typical biomarker of the acute blood cell cancer, Burkitt's lymphoma. The results reveal that the developed technique displays desirable selectivity in Ramos cell discrimination, and linear response range from 10 to 10(6) cells with a detection limit as low as 10 cells. Due to the simple procedures, label-free and electrochemistry based detection format, this technique is simple and cost-effective, and exhibits excellent compatibility with miniaturization technologies. The electrochemical cell detection strategy may create an intrinsically specific and sensitive platform for cancer cell assay and associated studies.

Fabrication of an electrochemical sensor based on spiropyran for sensitive and selective detection of fluoride ion.

PubMed

Tao, Jia; Zhao, Peng; Li, Yinhui; Zhao, Wenjie; Xiao, Yue; Yang, Ronghua

2016-04-28

In the past decades, numerous electrochemical sensors based on exogenous electroactive substance have been reported. Due to non-specific interaction between the redox mediator and the target, the instability caused by false signal may not be avoided. To address this issue, in this paper, a new electrochemical sensor based on spiropyran skeleton, namely SPOSi, was designed for specific electrochemical response to fluoride ions (F(-)). The breakage of Si-O induced by F(-) based on the specific nucleophilic substitution reaction between F(-) and silica would directly produce a hydroquinone structure for electrochemical signal generation. To improve the sensitivity, SPOSi probe was assembled on the single-walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE) through the π-π conjugating interaction. This electrode was successfully applied to monitor F(-) with a detection limit of 8.3 × 10(-8) M. Compared with the conventional F(-) ion selected electrode (ISE) which utilized noncovalent interaction, this method displays higher stability and a comparable sensitivity in the urine samples. Copyright © 2016 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

Tail and Kinase Modules Differently Regulate Core Mediator Recruitment and Function In Vivo.

PubMed

Jeronimo, Célia; Langelier, Marie-France; Bataille, Alain R; Pascal, John M; Pugh, B Franklin; Robert, François

2016-11-03

Mediator is a highly conserved transcriptional coactivator organized into four modules, namely Tail, Middle, Head, and Kinase (CKM). Previous work suggests regulatory roles for Tail and CKM, but an integrated model for these activities is lacking. Here, we analyzed the genome-wide distribution of Mediator subunits in wild-type and mutant yeast cells in which RNA polymerase II promoter escape is blocked, allowing detection of transient Mediator forms. We found that although all modules are recruited to upstream activated regions (UAS), assembly of Mediator within the pre-initiation complex is accompanied by the release of CKM. Interestingly, our data show that CKM regulates Mediator-UAS interaction rather than Mediator-promoter association. In addition, although Tail is required for Mediator recruitment to UAS, Tailless Mediator nevertheless interacts with core promoters. Collectively, our data suggest that the essential function of Mediator is mediated by Head and Middle at core promoters, while Tail and CKM play regulatory roles. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Energize Electrochemical Double Layer Capacitor by Introducing an Ambipolar Organic Redox Radical in Electrolyte.

PubMed

Wang, Yonggang; Hu, Lintong; Zhang, Yue; Shi, Chao; Guo, Kai; Zhai, Tianyou; Li, Huiqiao

2018-05-24

Carbon based electrochemical double layer capacitors (EDLCs) generally exhibit high power and long life, but low energy density/capacitance. Pore/morphology optimization and pseudocapacitive materials modification of carbon materials have been used to improve electrode capacitance, but leading to the consumption of tap density, conductivity and stability. Introducing soluble redox mediators into electrolyte is a promising alternative to improve the capacitance of electrode. However, it is difficult to find one redox mediator that can provide additional capacitance for both positive and negative electrodes simultaneously. Here, an ambipolar organic radical, 2, 2, 6, 6-tetramethylpiperidinyloxyl (TEMPO) is first introduced to the electrolyte, which can substantially contribute additional pseudocapacitance by oxidation at the positive electrode and reduction at the negative electrode simultaneously. The EDLC with TEMPO mediator delivers an energy density as high as 51 Wh kg-1, 2.4 times of the capacitor without TEMPO, and a long cycle stability over 4000 cycles. The achieved results potentially point a new way to improve the energy density of EDLCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mediator Undergoes a Compositional Change during Transcriptional Activation.

PubMed

Petrenko, Natalia; Jin, Yi; Wong, Koon Ho; Struhl, Kevin

2016-11-03

Mediator is a transcriptional co-activator recruited to enhancers by DNA-binding activators, and it also interacts with RNA polymerase (Pol) II as part of the preinitiation complex (PIC). We demonstrate that a single Mediator complex associates with the enhancer and core promoter in vivo, indicating that it can physically bridge these transcriptional elements. However, the Mediator kinase module associates strongly with the enhancer, but not with the core promoter, and it dissociates from the enhancer upon depletion of the TFIIH kinase. Severing the kinase module from Mediator by removing the connecting subunit Med13 does not affect Mediator association at the core promoter but increases occupancy at enhancers. Thus, Mediator undergoes a compositional change in which the kinase module, recruited via Mediator to the enhancer, dissociates from Mediator to permit association with Pol II and the PIC. As such, Mediator acts as a dynamic bridge between the enhancer and core promoter. Copyright © 2016 Elsevier Inc. All rights reserved.

Role for the MED21-MED7 Hinge in Assembly of the Mediator-RNA Polymerase II Holoenzyme*

PubMed Central

Sato, Shigeo; Tomomori-Sato, Chieri; Tsai, Kuang-Lei; Yu, Xiaodi; Sardiu, Mihaela; Saraf, Anita; Washburn, Michael P.; Florens, Laurence; Asturias, Francisco J.; Conaway, Ronald C.

2016-01-01

Mediator plays an integral role in activation of RNA polymerase II (Pol II) transcription. A key step in activation is binding of Mediator to Pol II to form the Mediator-Pol II holoenzyme. Here, we exploit a combination of biochemistry and macromolecular EM to investigate holoenzyme assembly. We identify a subset of human Mediator head module subunits that bind Pol II independent of other subunits and thus probably contribute to a major Pol II binding site. In addition, we show that binding of human Mediator to Pol II depends on the integrity of a conserved “hinge” in the middle module MED21-MED7 heterodimer. Point mutations in the hinge region leave core Mediator intact but lead to increased disorder of the middle module and markedly reduced affinity for Pol II. These findings highlight the importance of Mediator conformation for holoenzyme assembly. PMID:27821593

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.

Auxin-dependent compositional change in Mediator in ARF7- and ARF19-mediated transcription.

PubMed

Ito, Jun; Fukaki, Hidehiro; Onoda, Makoto; Li, Lin; Li, Chuanyou; Tasaka, Masao; Furutani, Masahiko

2016-06-07

Mediator is a multiprotein complex that integrates the signals from transcription factors binding to the promoter and transmits them to achieve gene transcription. The subunits of Mediator complex reside in four modules: the head, middle, tail, and dissociable CDK8 kinase module (CKM). The head, middle, and tail modules form the core Mediator complex, and the association of CKM can modify the function of Mediator in transcription. Here, we show genetic and biochemical evidence that CKM-associated Mediator transmits auxin-dependent transcriptional repression in lateral root (LR) formation. The AUXIN/INDOLE 3-ACETIC ACID 14 (Aux/IAA14) transcriptional repressor inhibits the transcriptional activity of its binding partners AUXIN RESPONSE FACTOR 7 (ARF7) and ARF19 by making a complex with the CKM-associated Mediator. In addition, TOPLESS (TPL), a transcriptional corepressor, forms a bridge between IAA14 and the CKM component MED13 through the physical interaction. ChIP assays show that auxin induces the dissociation of MED13 but not the tail module component MED25 from the ARF7 binding region upstream of its target gene. These findings indicate that auxin-induced degradation of IAA14 changes the module composition of Mediator interacting with ARF7 and ARF19 in the upstream region of their target genes involved in LR formation. We suggest that this regulation leads to a quick switch of signal transmission from ARFs to target gene expression in response to auxin.

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

PubMed Central

Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-01-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

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.

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.

Mediator independently orchestrates multiple steps of preinitiation complex assembly in vivo

PubMed Central

Eyboulet, Fanny; Wydau-Dematteis, Sandra; Eychenne, Thomas; Alibert, Olivier; Neil, Helen; Boschiero, Claire; Nevers, Marie-Claire; Volland, Hervé; Cornu, David; Redeker, Virginie; Werner, Michel; Soutourina, Julie

2015-01-01

Mediator is a large multiprotein complex conserved in all eukaryotes, which has a crucial coregulator function in transcription by RNA polymerase II (Pol II). However, the molecular mechanisms of its action in vivo remain to be understood. Med17 is an essential and central component of the Mediator head module. In this work, we utilised our large collection of conditional temperature-sensitive med17 mutants to investigate Mediator's role in coordinating preinitiation complex (PIC) formation in vivo at the genome level after a transfer to a non-permissive temperature for 45 minutes. The effect of a yeast mutation proposed to be equivalent to the human Med17-L371P responsible for infantile cerebral atrophy was also analyzed. The ChIP-seq results demonstrate that med17 mutations differentially affected the global presence of several PIC components including Mediator, TBP, TFIIH modules and Pol II. Our data show that Mediator stabilizes TFIIK kinase and TFIIH core modules independently, suggesting that the recruitment or the stability of TFIIH modules is regulated independently on yeast genome. We demonstrate that Mediator selectively contributes to TBP recruitment or stabilization to chromatin. This study provides an extensive genome-wide view of Mediator's role in PIC formation, suggesting that Mediator coordinates multiple steps of a PIC assembly pathway. PMID:26240385

ESM of ionic and electrochemical phenomena on the nanoscale

DOE PAGES

Kalinin, Sergei V.; Kumar, Amit; Balke, Nina; ...

2011-01-01

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum ofmore » length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.« less

A label-free electrochemical sensor for detection of mercury(II) ions based on the direct growth of guanine nanowire.

PubMed

Huang, Yan Li; Gao, Zhong Feng; Jia, Jing; Luo, Hong Qun; Li, Nian Bing

2016-05-05

A simple, sensitive and label-free electrochemical sensor is developed for detection of Hg(2+) based on the strong and stable T-Hg(2+)-T mismatches. In the presence of Mg(2+), the parallel G-quadruplex structures could be specifically recognized and precipitated in parallel conformation. Therefore, the guanine nanowire was generated on the electrode surface, triggering the electrochemical H2O2-mediated oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). In this research, a new method of signal amplification for the quantitative detection of Hg(2+) was described based on the direct growth of guanine nanowire via guanine nanowire. Under optimum conditions, Hg(2+) was detected in the range of 100 pM-100 nM, and the detection limit is 33 pM. Compared to the traditional single G-quadruplex label unit, this electrochemical sensor showed high sensitivity and selectivity for detecting Hg(2+). Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of electrochemical redox reaction on growth and metabolism of Saccharomyces cerevisiae as an environmental factor.

PubMed

Na, Kwan Byung; Hwang, Tae Sik; Lee, Sung Hun; Ahn, Dae Hee; Park, Doo Hyun

2007-03-01

The effect of an electrochemically generated oxidation-reduction potential and electric pulse on ethanol production and growth of Saccharomyces cerevisiae ATCC 26603 was experimented and compared with effects of electron mediators (neutral red, benzyl viologen, and thionine), chemical oxidants (hydrogen peroxide and hypochlorite), chemical reductants (sulfite and nitrite), oxygen, and hydrogen. The oxidation (anodic) and reduction (cathodic) potential and electric pulse activated ethanol production and growth, and changed the total soluble protein pattern of the test strain. Neutral red electrochemically reduced activated ethanol production and growth of the test strain, but benzyl viologen and thionine did not. Nitrite inhibited ethanol production but did not influence growth of the test strain. Hydrogen peroxide, hypochlorite, and sulfite did not influence ethanol production and growth of the test strain. Hydrogen and oxygen also did not influence the growth and ethanol production. It shows that the test strain may perceive electrochemically generated oxidation-reduction potential and electric pulse as an environmental factor.

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.

Spectroelectrochemical Sensors: New Polymer Films for Improved Sensitivity

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

Morris, Laura K.; Seliskar, Carl J.; Bryan, Samuel A.

2014-10-31

The selectivity of an optical sensor can be improved by combining optical detection with electrochemical oxidation or reduction of the target analyte to change its spectral properties. The changing signal can distinguish the analyte from interferences with similar spectral properties that would otherwise interfere. The analyte is detected by measuring the intensity of the electrochemically modulated signal. In one form this spectroelectrochemical sensor consists of an optically transparent electrode (OTE) coated with a film that preconcentrates the target analyte. The OTE functions as an optical waveguide for attenuated total reflectance (ATR) spectroscopy, which detects the analyte by absorption. Sensitivity reliesmore » in part on a large change in molar absorptivity between the two oxidation states used for electrochemical modulation of the optical signal. A critical part of the sensor is the ion selective film. It should preconcentrate the analyte and exclude some interferences. At the same time the film must not interfere with the electrochemistry or the optical detection. Therefore, since the debut of the sensor’s concept one major focus of our group has been developing appropriate films for different analytes. Here we report the development of a series of quaternized poly(vinylpyridine)-co-styrene (QPVP-co-S) anion exchange films for use in spectroelectrochemical sensors to enable sensitive detection of target anionic analytes in complex samples. The films were either 10% or 20% styrene and were prepared with varying degrees of quaternized pyridine groups, up to 70%. Films were characterized with respect to thickness with spectroscopic ellipsometry, degree of quaternization with FTIR, and electrochemically and spectroelectrochemically using the anions ferrocyanide and pertechnetate.« less

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.

Genome-wide association of mediator and RNA polymerase II in wild-type and mediator mutant yeast.

PubMed

Paul, Emily; Zhu, Z Iris; Landsman, David; Morse, Randall H

2015-01-01

Mediator is a large, multisubunit complex that is required for essentially all mRNA transcription in eukaryotes. In spite of the importance of Mediator, the range of its targets and how it is recruited to these is not well understood. Previous work showed that in Saccharomyces cerevisiae, Mediator contributes to transcriptional activation by two distinct mechanisms, one depending on the tail module triad and favoring SAGA-regulated genes, and the second occurring independently of the tail module and favoring TFIID-regulated genes. Here, we use chromatin immunoprecipitation sequencing (ChIP-seq) to show that dependence on tail module subunits for Mediator recruitment and polymerase II (Pol II) association occurs preferentially at SAGA-regulated over TFIID-regulated genes on a genome-wide scale. We also show that recruitment of tail module subunits to active gene promoters continues genome-wide when Mediator integrity is compromised in med17 temperature-sensitive (ts) yeast, demonstrating the modular nature of the Mediator complex in vivo. In addition, our data indicate that promoters exhibiting strong and stable occupancy by Mediator have a wide range of activity and are enriched for targets of the Tup1-Cyc8 repressor complex. We also identify a number of strong Mediator occupancy peaks that overlap dubious open reading frames (ORFs) and are likely to include previously unrecognized upstream activator sequences. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Genome-Wide Association of Mediator and RNA Polymerase II in Wild-Type and Mediator Mutant Yeast

PubMed Central

Paul, Emily; Zhu, Z. Iris

2014-01-01

Mediator is a large, multisubunit complex that is required for essentially all mRNA transcription in eukaryotes. In spite of the importance of Mediator, the range of its targets and how it is recruited to these is not well understood. Previous work showed that in Saccharomyces cerevisiae, Mediator contributes to transcriptional activation by two distinct mechanisms, one depending on the tail module triad and favoring SAGA-regulated genes, and the second occurring independently of the tail module and favoring TFIID-regulated genes. Here, we use chromatin immunoprecipitation sequencing (ChIP-seq) to show that dependence on tail module subunits for Mediator recruitment and polymerase II (Pol II) association occurs preferentially at SAGA-regulated over TFIID-regulated genes on a genome-wide scale. We also show that recruitment of tail module subunits to active gene promoters continues genome-wide when Mediator integrity is compromised in med17 temperature-sensitive (ts) yeast, demonstrating the modular nature of the Mediator complex in vivo. In addition, our data indicate that promoters exhibiting strong and stable occupancy by Mediator have a wide range of activity and are enriched for targets of the Tup1-Cyc8 repressor complex. We also identify a number of strong Mediator occupancy peaks that overlap dubious open reading frames (ORFs) and are likely to include previously unrecognized upstream activator sequences. PMID:25368384

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.

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)

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.

Role for the MED21-MED7 Hinge in Assembly of the Mediator-RNA Polymerase II Holoenzyme.

PubMed

Sato, Shigeo; Tomomori-Sato, Chieri; Tsai, Kuang-Lei; Yu, Xiaodi; Sardiu, Mihaela; Saraf, Anita; Washburn, Michael P; Florens, Laurence; Asturias, Francisco J; Conaway, Ronald C; Conaway, Joan W

2016-12-23

Mediator plays an integral role in activation of RNA polymerase II (Pol II) transcription. A key step in activation is binding of Mediator to Pol II to form the Mediator-Pol II holoenzyme. Here, we exploit a combination of biochemistry and macromolecular EM to investigate holoenzyme assembly. We identify a subset of human Mediator head module subunits that bind Pol II independent of other subunits and thus probably contribute to a major Pol II binding site. In addition, we show that binding of human Mediator to Pol II depends on the integrity of a conserved "hinge" in the middle module MED21-MED7 heterodimer. Point mutations in the hinge region leave core Mediator intact but lead to increased disorder of the middle module and markedly reduced affinity for Pol II. These findings highlight the importance of Mediator conformation for holoenzyme assembly. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

Plasmon-mediated electrochemical reactions: the influence of nanoparticle structure

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

Willets, Katherine A.

2015-09-25

This document describes research performed at the University of Texas at Austin under award DE-SC0010307. This award has been transferred to Temple University upon the move of the PI from her original institution to a new institution.

Single particle electrochemical sensors and methods of utilization

DOEpatents

Schoeniger, Joseph [Oakland, CA; Flounders, Albert W [Berkeley, CA; Hughes, Robert C [Albuquerque, NM; Ricco, Antonio J [Los Gatos, CA; Wally, Karl [Lafayette, CA; Kravitz, Stanley H [Placitas, NM; Janek, Richard P [Oakland, CA

2006-04-04

The present invention discloses an electrochemical device for detecting single particles, and methods for using such a device to achieve high sensitivity for detecting particles such as bacteria, viruses, aggregates, immuno-complexes, molecules, or ionic species. The device provides for affinity-based electrochemical detection of particles with single-particle sensitivity. The disclosed device and methods are based on microelectrodes with surface-attached, affinity ligands (e.g., antibodies, combinatorial peptides, glycolipids) that bind selectively to some target particle species. The electrodes electrolyze chemical species present in the particle-containing solution, and particle interaction with a sensor element modulates its electrolytic activity. The devices may be used individually, employed as sensors, used in arrays for a single specific type of particle or for a range of particle types, or configured into arrays of sensors having both these attributes.

Mediator independently orchestrates multiple steps of preinitiation complex assembly in vivo.

PubMed

Eyboulet, Fanny; Wydau-Dematteis, Sandra; Eychenne, Thomas; Alibert, Olivier; Neil, Helen; Boschiero, Claire; Nevers, Marie-Claire; Volland, Hervé; Cornu, David; Redeker, Virginie; Werner, Michel; Soutourina, Julie

2015-10-30

Mediator is a large multiprotein complex conserved in all eukaryotes, which has a crucial coregulator function in transcription by RNA polymerase II (Pol II). However, the molecular mechanisms of its action in vivo remain to be understood. Med17 is an essential and central component of the Mediator head module. In this work, we utilised our large collection of conditional temperature-sensitive med17 mutants to investigate Mediator's role in coordinating preinitiation complex (PIC) formation in vivo at the genome level after a transfer to a non-permissive temperature for 45 minutes. The effect of a yeast mutation proposed to be equivalent to the human Med17-L371P responsible for infantile cerebral atrophy was also analyzed. The ChIP-seq results demonstrate that med17 mutations differentially affected the global presence of several PIC components including Mediator, TBP, TFIIH modules and Pol II. Our data show that Mediator stabilizes TFIIK kinase and TFIIH core modules independently, suggesting that the recruitment or the stability of TFIIH modules is regulated independently on yeast genome. We demonstrate that Mediator selectively contributes to TBP recruitment or stabilization to chromatin. This study provides an extensive genome-wide view of Mediator's role in PIC formation, suggesting that Mediator coordinates multiple steps of a PIC assembly pathway. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

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.

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

Elucidating the role of methyl viologen as a scavenger of photoactivated electrons from photosystem I under aerobic and anaerobic conditions.

PubMed

Bennett, Tyler; Niroomand, Hanieh; Pamu, Ravi; Ivanov, Ilia; Mukherjee, Dibyendu; Khomami, Bamin

2016-03-28

We present detailed electrochemical investigations into the role of dissolved O2 in electrolyte solutions in scavenging photoactivated electrons from a uniform photosystem I (PS I) monolayer assembled on alkanethiolate SAM (self-assembled monolayer)/Au surfaces while using methyl viologen (MV(2+)) as the redox mediator. To this end, we report results for direct measurements of light induced photocurrent from uniform monolayer assemblies of PS I on C9 alkanethiolate SAM/Au surfaces. These measurements, apart from demonstrating the ability of dissolved O2 in the electrolyte medium to act as an electron scavenger, also reveal its essential role in driving the solution-phase methyl viologen to initiate light-induced directional electron transfer from an electron donor surface (Au) via surface assembled PS I trimers. Specifically, our systematic electrochemical measurements have revealed that the dissolved O2 in aqueous electrolyte solutions form a complex intermediate species with MV that plays the essential role in mediating redox pathways for unidirectional electron transfer processes. This critical insight into the redox-mediated electron transfer pathways allows for rational design of electron scavengers through systematic tuning of mediator combinations that promote such intermediate formation. Our current findings facilitate the incorporation of PS I-based bio-hybrid constructs as photo-anodes in future photoelectrochemical cells and bio-electronic devices.

Novel electrochemical biosensor based on cationic peptide modified hemin/G-quadruples enhanced peroxidase-like activity.

PubMed

Yu, Qian; Wu, Yongmei; Liu, Zi; Lei, Sheng; Li, Gaiping; Ye, Baoxian

2018-06-01

This work designed an artificial substrate peptide to synthesize peptide-hemin/G-quadruplex (peptide-DNAzyme) conjugates. In addition to enhancing catalytic activity of hemin/G-quadruplex, the peptide could also be induced and cleaved by prostate specific antigen (PSA). It was the first report on peptide-DNAzyme conjugates in application of the peptide biosensor. The polyethyleneimine-reduced graphene oxide@hollow platinum nanotubes (PEI-rGO@PtNTs) nanocomposites were cast on the glassy carbon electrode in order to form the interface of biocompatibility and huge surface area for bioprobes immobilization. In absence of PSA, the peptide-DNAzyme conjugates retained intact on the surface of the electrode to produce a strong response signal. But in presence of PSA, the peptide-DNAzyme conjugates were destroyed to release electron mediators, resulting in dramatical decrease of the electrochemicl signal. Therefore, the method had high sensitivity and super selectivity with the limit of detection calculated as 2.0 fg/mL. Furthermore, the strategy would be promising to apply for other proteases by transforming the synthetic peptide module of target. Copyright © 2018 Elsevier B.V. All rights reserved.

An Unusual Strong Visible-Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen-Occupied Oxygen Vacancies.

PubMed

Yang, Yongqiang; Yin, Li-Chang; Gong, Yue; Niu, Ping; Wang, Jian-Qiang; Gu, Lin; Chen, Xingqiu; Liu, Gang; Wang, Lianzhou; Cheng, Hui-Ming

2018-02-01

Increasing visible light absorption of classic wide-bandgap photocatalysts like TiO 2 has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible-light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail-like absorption band in hydrogen-free oxygen-deficient TiO 2 , an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO 2 by intentionally introducing atomic hydrogen-mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo-electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide-bandgap semiconductors to fully capture solar light. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantifying Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction.

PubMed

Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh

2018-05-15

We quantify changes in the interfacial pH local to the electrochemical double layer during electrocatalysis, using a concurrent non-faradaic probe reaction. In the absence of electrocatalysis, nanostructured Pt/C surfaces mediate the reaction of H2 with cis-2-butene-1,4-diol to form a mixture of 1,4-butanediol and n-butanol with a selectivity that is linearly dependent on the bulk solution pH. We show that kinetic branching occurs from a common surface-bound intermediate, ensuring that this probe reaction is uniquely sensitive to the interfacial pH within molecular length scales of the surface. We use the pH-dependent selectivity of this reaction to track changes in interfacial pH during concurrent hydrogen oxidation electrocatalysis and find that the local pH can vary dramatically, > 3 units, relative to the bulk value even at modest current densities in well-buffered electrolytes. This work highlights the key role that interfacial pH variation plays in modulating inner-sphere electrocatalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A conserved Mediator–CDK8 kinase module association regulates Mediator–RNA polymerase II interaction

PubMed Central

Tsai, Kuang-Lei; Sato, Shigeo; Tomomori-Sato, Chieri; Conaway, Ronald C.; Conaway, Joan W.; Asturias, Francisco J.

2013-01-01

The CDK8 kinase module (CKM) is a conserved, dissociable Mediator subcomplex whose component subunits were genetically linked to the RNA polymerase II (RNAPII) carboxy-terminal domain (CTD) and individually recognized as transcriptional repressors before Mediator was identified as a preeminent complex in eukaryotic transcription regulation. We used macromolecular electron microscopy and biochemistry to investigate the subunit organization, structure, and Mediator interaction of the Saccharomyces cerevisiae CKM. We found that interaction of the CKM with Mediator’s Middle module interferes with CTD-dependent RNAPII binding to a previously unknown Middle module CTD-binding site targeted early on in a multi-step holoenzyme formation process. Taken together, our results reveal the basis for CKM repression, clarify the origin of the connection between CKM subunits and the CTD, and suggest that a combination of competitive interactions and conformational changes that facilitate holoenzyme formation underlie the Mediator mechanism. PMID:23563140

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.

Differential Electrochemical Conductance Imaging at the Nanoscale.

PubMed

López-Martínez, Montserrat; Artés, Juan Manuel; Sarasso, Veronica; Carminati, Marco; Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau

2017-09-01

Electron transfer in proteins is essential in crucial biological processes. Although the fundamental aspects of biological electron transfer are well characterized, currently there are no experimental tools to determine the atomic-scale electronic pathways in redox proteins, and thus to fully understand their outstanding efficiency and environmental adaptability. This knowledge is also required to design and optimize biomolecular electronic devices. In order to measure the local conductance of an electrode surface immersed in an electrolyte, this study builds upon the current-potential spectroscopic capacity of electrochemical scanning tunneling microscopy, by adding an alternating current modulation technique. With this setup, spatially resolved, differential electrochemical conductance images under bipotentiostatic control are recorded. Differential electrochemical conductance imaging allows visualizing the reversible oxidation of an iron electrode in borate buffer and individual azurin proteins immobilized on atomically flat gold surfaces. In particular, this method reveals submolecular regions with high conductance within the protein. The direct observation of nanoscale conduction pathways in redox proteins and complexes enables important advances in biochemistry and bionanotechnology. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

EDTA assisted synthesis of hydroxyapatite nanoparticles for electrochemical sensing of uric acid.

PubMed

Kanchana, P; Sekar, C

2014-09-01

Hydroxyapatite nanoparticles have been synthesized using EDTA as organic modifier by a simple microwave irradiation method and its application for the selective determination of uric acid (UA) has been demonstrated. Electrochemical behavior of uric acid at HA nanoparticle modified glassy carbon electrode (E-HA/GCE) has been investigated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometry. The E-HA modified electrode exhibits efficient electrochemical activity towards uric acid sensing without requiring enzyme or electron mediator. Amperometry studies revealed that the fabricated electrode has excellent sensitivity for uric acid with the lowest detection limit of 142 nM over a wide concentration range from 1 × 10(-7) to 3 × 10(-5)M. Moreover, the studied E-HA modified GC electrode exhibits a good reproducibility and long-term stability and an admirable selectivity towards the determination of UA even in the presence of potential interferents. The analytical performance of this sensor was evaluated for the detection of uric acid in human urine and blood serum samples. Copyright © 2014. Published by Elsevier B.V.

Microfluidic electrochemical assay for rapid detection and quantification of Escherichia coli.

PubMed

Safavieh, Mohammadali; Ahmed, Minhaz Uddin; Tolba, Mona; Zourob, Mohammed

2012-01-15

Microfluidic electrochemical biosensor for performing Loop-mediated isothermal amplification (LAMP) was developed for the detection and quantification of Escherichia coli. The electrochemical detection for detecting the DNA amplification was achieved using Hoechst 33258 redox molecule and linear sweep voltametry (LSV). The DNA aggregation and minor groove binding with redox molecule cause a significant drop in the anodic oxidation of LSV. Unlike other electrochemical techniques, this method does not require the probe immobilization and the detection of the bacteria can be accomplished in a single chamber without DNA extraction and purification steps. The isothermal amplification time has a major role in the quantification of the bacteria. We have shown that we could detect and quantify 24 CFU/ml of bacteria and 8.6 fg/μl DNA in 60 min and 48 CFU/ml of bacteria in 35 min in LB media and urine samples. We believe that this microfluidic chip has great potential to be used as a point of care diagnostic (POC) device in the clinical/hospital application. Copyright © 2011 Elsevier B.V. All rights reserved.

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell

PubMed Central

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-01-01

In this work, Cu2O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode. PMID:28335366

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell.

PubMed

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-12-09

In this work, Cu₂O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode.

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.

Electrochemical studies of biocatalytic anode of sulfonated graphene/ferritin/glucose oxidase layer-by-layer biocomposite films for mediated electron transfer.

PubMed

Inamuddin; Haque, Sufia Ul; Naushad, Mu

2016-06-01

In this study, a bioanode was developed by using layer-by-layer (LBL) assembly of sulfonated graphene (SG)/ferritin (Frt)/glucose oxidase (GOx). The SG/Frt biocomposite was used as an electron transfer elevator and mediator, respectively. Glucose oxidase (GOx) from Aspergillus niger was applied as a glucose oxidation biocatalyst. The electrocatalytic oxidation of glucose using GOx modified electrode increases with an increase in the concentration of glucose in the range of 10-50mM. The electrochemical measurements of the electrode was carried out by using cyclic voltammetry (CV) at different scan rates (20-100mVs(-1)) in 30mM of glucose solution prepared in 0.3M potassium ferrocyanide (K4Fe(CN)6) and linear sweep voltammetry (LSV). A saturation current density of 50±2mAcm(-2) at a scan rate of 100mVs(-1) for the oxidation of 30Mm glucose is achieved. Copyright © 2016 Elsevier Inc. All rights reserved.

Construction and electrochemical characterization of microelectrodes for improved sensitivity in paper-based analytical devices

PubMed Central

Santhiago, Murilo; Wydallis, John B.; Kubota, Lauro T.; Henry, Charles S.

2013-01-01

This work presents a simple, low cost method for creating microelectrodes for electrochemical paper-based analytical devices (ePADs). The microelectrodes were constructed by backfilling small holes made in polyester sheets using a CO2 laser etching system. To make electrical connections, the working electrodes were combined with silver screen-printed paper in a sandwich type two-electrode configuration. The devices were characterized using linear sweep voltammetry and the results are in good agreement with theoretical predictions for electrode size and shape. As a proof-of-concept, cysteine was measured using cobalt phthalocyanine as a redox mediator. The rate constant (kobs) for the chemical reaction between cysteine and the redox mediator was obtained by chronoamperometry and found to be on the order of 105 s−1 M−1. Using a microelectrode array, it was possible to reach a limit of detection of 4.8 μM for cysteine. The results show that carbon paste microelectrodes can be easily integrated with paper-based analytical devices. PMID:23581428

Construction and electrochemical characterization of microelectrodes for improved sensitivity in paper-based analytical devices.

PubMed

Santhiago, Murilo; Wydallis, John B; Kubota, Lauro T; Henry, Charles S

2013-05-21

This work presents a simple, low cost method for creating microelectrodes for electrochemical paper-based analytical devices (ePADs). The microelectrodes were constructed by backfilling small holes made in polyester sheets using a CO2 laser etching system. To make electrical connections, the working electrodes were combined with silver screen-printed paper in a sandwich type two-electrode configuration. The devices were characterized using linear sweep voltammetry, and the results are in good agreement with theoretical predictions for electrode size and shape. As a proof-of-concept, cysteine was measured using cobalt phthalocyanine as a redox mediator. The rate constant (k(obs)) for the chemical reaction between cysteine and the redox mediator was obtained by chronoamperometry and found to be on the order of 10(5) s(-1) M(-1). Using a microelectrode array, it was possible to reach a limit of detection of 4.8 μM for cysteine. The results show that carbon paste microelectrodes can be easily integrated with paper-based analytical devices.

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

DNA-Mediated Electrochemistry

PubMed Central

Gorodetsky, Alon A.; Buzzeo, Marisa C.

2009-01-01

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

Fabrication and characterization of electrochemically prepared bioanode (polyaniline/ferritin/glucose oxidase) for biofuel cell application

NASA Astrophysics Data System (ADS)

ul Haque, Sufia; Inamuddin; Nasar, Abu; Asiri, Abdullah M.

2018-01-01

Porous matrix of polyaniline (PANI) has been electrodeposited along with the entrapment of biocompatible redox mediator ferritin (Frt) and glucose oxidase (GOx) on the surface of glassy carbon (GC) electrode. The characterizations have been carried out by X-ray Diffraction (XRD) and Transmission electron microscopy (TEM). The enhanced electrochemical signal transfer rate from enzyme to the electrode surface was due to the intimate contact of the enzyme with the electrochemically polymerized conducting PANI matrix. The PANI/Frt/GOx modified GC bioanode was used to investigate the electrocatalytic activity as a function of the concentration of glucose in the range of 10-60 mM. It was confirmed by the electrochemical impedance spectroscopy (EIS), the thick deposition of PANI layer becomes more compact due to which the charge transfer resistance of PANI matrix becomes higher. All the electrochemical measurements of the electrode were carried out by using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). CV curves were recorded at different scan rates (20-100 mV/s) at 50 mM of glucose in 0.3 M potassium ferrocyanide. A normalized saturation current density of 22.3 ± 2 mA/cm2 was observed for the oxidation of 50 mM glucose at a scan rate of 100 mV/s.

Molecular Machine Powered Surface Programmatic Chain Reaction for Highly Sensitive Electrochemical Detection of Protein.

PubMed

Zhu, Jing; Gan, Haiying; Wu, Jie; Ju, Huangxian

2018-04-17

A bipedal molecular machine powered surface programmatic chain reaction was designed for electrochemical signal amplification and highly sensitive electrochemical detection of protein. The bipedal molecular machine was built through aptamer-target specific recognition for the binding of one target protein with two DNA probes, which hybridized with surface-tethered hairpin DNA 1 (H1) via proximity effect to expose the prelocked toehold domain of H1 for the hybridization of ferrocene-labeled hairpin DNA 2 (H2-Fc). The toehold-mediated strand displacement reaction brought the electrochemical signal molecule Fc close to the electrode and meanwhile released the bipedal molecular machine to traverse the sensing surface by the surface programmatic chain reaction. Eventually, a large number of duplex structures of H1-H2 with ferrocene groups facing to the electrode were formed on the sensor surface to generate an amplified electrochemical signal. Using thrombin as a model target, this method showed a linear detection range from 2 pM to 20 nM with a detection limit of 0.76 pM. The proposed detection strategy was enzyme-free and allowed highly sensitive and selective detection of a variety of protein targets by using corresponding DNA-based affinity probes, showing potential application in bioanalysis.

Layer-by-Layer Assembly of Glucose Oxidase on Carbon Nanotube Modified Electrodes.

PubMed

Suroviec, Alice H

2017-01-01

The use of enzymatically modified electrodes for the detection of glucose or other non-electrochemically active analytes is becoming increasingly common. Direct heterogeneous electron transfer to glucose oxidase has been shown to be kinetically difficult, which is why electron transfer mediators or indirect detection is usually used for monitoring glucose with electrochemical sensors. It has been found, however, that electrodes modified with single or multi-walled carbon nanotubes (CNTs) demonstrate fast heterogeneous electron transfer kinetics as compared to that found for traditional electrodes. Incorporating CNTs into the assembly of electrochemical glucose sensors, therefore, affords the possibility of facile electron transfer to glucose oxidase, and a more direct determination of glucose. This chapter describes the methods used to use CNTs in a layer-by-layer structure along with glucose oxidase to produce an enzymatically modified electrode with high turnover rates, increased stability and shelf-life.

Organic reactions mediated by electrochemically generated ArS+.

PubMed

Matsumoto, Kouichi; Suga, Seiji; Yoshida, Jun-ichi

2011-04-21

Low-temperature electrochemical oxidation of ArSSAr was carried out to generate a pool of "ArS(+)". Spectroscopic studies ((1)H NMR and CSI-MS) of the resulting solution revealed the accumulation of ArS(ArSSAr)(+). The resulting "ArS(+)" pool reacted with alkenes and alkynes to give diarylthio-substituted products. The "ArS(+)" pool rapidly reacted with thioacetals to give the corresponding alkoxycarbenium ion pools, which reacted with various carbon nucleophiles (indirect cation pool method). The reaction of the alkoxycarbenium ion pools with stilbene derivatives in the presence of ArSSAr gave thiochroman derivatives. In addition to such stoichiometric reactions, a catalytic amount of "ArS(+)" serves as an initiator and a chain carrier of some cationic chain reactions involving intramolecular carbon-carbon bond formation. In situ generation of "ArS(+)" by electrochemical oxidation of ArSSAr with a catalytic amount of electricity in the presence of a substrate is also effective for such cationic chain reactions.

Harvesting waste thermal energy using a carbon-nanotube-based thermo-electrochemical cell.

PubMed

Hu, Renchong; Cola, Baratunde A; Haram, Nanda; Barisci, Joseph N; Lee, Sergey; Stoughton, Stephanie; Wallace, Gordon; Too, Chee; Thomas, Michael; Gestos, Adrian; Cruz, Marilou E Dela; Ferraris, John P; Zakhidov, Anvar A; Baughman, Ray H

2010-03-10

Low efficiencies and costly electrode materials have limited harvesting of thermal energy as electrical energy using thermo-electrochemical cells (or "thermocells"). We demonstrate thermocells, in practical configurations (from coin cells to cells that can be wrapped around exhaust pipes), that harvest low-grade thermal energy using relatively inexpensive carbon multiwalled nanotube (MWNT) electrodes. These electrodes provide high electrochemically accessible surface areas and fast redox-mediated electron transfer, which significantly enhances thermocell current generation capacity and overall efficiency. Thermocell efficiency is further improved by directly synthesizing MWNTs as vertical forests that reduce electrical and thermal resistance at electrode/substrate junctions. The efficiency of thermocells with MWNT electrodes is shown to be as high as 1.4% of Carnot efficiency, which is 3-fold higher than for previously demonstrated thermocells. With the cost of MWNTs decreasing, MWNT-based thermocells may become commercially viable for harvesting low-grade thermal energy.

Electrochemical detection of uric acid using ruthenium-dioxide-coated carbon nanotube directly grown onto Si wafer

NASA Astrophysics Data System (ADS)

Shih, Yi-Ting; Lee, Kuei-Yi; Lin, Chung-Kuang

2015-12-01

Carbon nanotubes (CNTs) directly grown onto a Si substrate by thermal chemical vapor deposition were used in uric acid (UA) detection. The process is simple and formation is easy without the need for additional chemical treatments. However, CNTs lack selectivity and sensitivity to UA. To enhance the electrochemical analysis, ruthenium oxide was used as a catalytic mediator in the modification of electrodes. The electrochemical results show that RuO2 nanostructures coated onto CNTs can strengthen the UA signal. The peak currents of RuO2 nanostructures coated onto CNTs linearly increase with increasing UA concentration, meaning that they can work as electrodes for UA detection. The lowest detection limit and highest sensitivity were 55 nM and 4.36 µA/µM, respectively. Moreover, the characteristics of RuO2 nanostructures coated onto CNTs were examined by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy.

Purinoceptor modulation of noradrenaline release in rat tail artery: tonic modulation mediated by inhibitory P2Y- and facilitatory A2A-purinoceptors.

PubMed Central

Gonçalves, J.; Queiroz, G.

1996-01-01

1. The effects of analogues of adenosine and ATP on noradrenaline release elicited by electrical stimulation (5 Hz, 2700 pulses) were studied in superfused preparations of rat tail artery. The effects of purinoceptor antagonists, of adenosine deaminase and of adenosine uptake blockade were also examined. Noradrenaline was measured by h.p.l.c. electrochemical detection. 2. The A1-adenosine receptor agonist, N6-cyclopentyladenosine (CPA; 0.1-100 nM) reduced, whereas the A2A-receptor agonist 2-p-(2-carboxyethyl)phenethylamino-5'-N-ethylcarboxamidoadenosine (CGS 21680; 3-30 nM) increased evoked noradrenaline overflow. These effects were antagonized by the A1-adenosine receptor antagonist, 8-cyclopentyl-1,3-dipropylxanthine (DPCPX; 20 nM) and the A2-adenosine receptor antagonist, 3,7-dimethyl-1-propargylxanthine (DMPX; 100 nM), respectively. The P2Y-purinoceptor agonist, 2-methylthio-ATP (1-100 microM) reduced noradrenaline overflow, an effect prevented by the P2-purinoceptor antagonist, cibacron blue 3GA (100 microM) and suramin (100 microM). 3. Adenosine deaminase (2 u ml-1), DMPX (100 nM) and inhibition of adenosine uptake with S-(p-nitrobenzyl)-6-thioinosine (NBTI; 50 nM) decreased evoked noradrenaline overflow. DPCPX alone did not change noradrenaline overflow but prevented the inhibition caused by NBTI. The P2Y-purinoceptor antagonist, cibacron blue 3GA (100 microM) increased evoked noradrenaline overflow as did suramin, a non-selective P2-antagonist. 4. It is concluded that, in rat tail artery, inhibitory (A1 and P2Y) and facilitatory (A2A) purinoceptors are present and modulate noradrenaline release evoked by electrical stimulation. Endogenous purines tonically modulate noradrenaline release through activation of inhibitory P2Y and facilitatory A2A purinoceptors, whereas a tonic activation of inhibitory A1 purinoceptors seems to be prevented by adenosine uptake. PMID:8825357

Redox properties of structural Fe in clay minerals. 2. Electrochemical and spectroscopic characterization of electron transfer irreversibility in ferruginous smectite, SWa-1.

PubMed

Gorski, Christopher A; Klüpfel, Laura; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

2012-09-04

Structural Fe in clay minerals is an important, albeit poorly characterized, redox-active phase found in many natural and engineered environments. This work develops an experimental approach to directly assess the redox properties of a natural Fe-bearing smectite (ferruginous smectite, SWa-1, 12.6 wt % Fe) with mediated electrochemical reduction (MER) and oxidation (MEO). By utilizing a suite of one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in SWa-1 and a working electrode, we show that the Fe2+/Fe3+ couple in SWa-1 is redox-active over a large range of potentials (from E(H) = -0.63 V to +0.61 V vs SHE). Electrochemical and spectroscopic analyses of SWa-1 samples that were subject to reduction and re-oxidation cycling revealed both reversible and irreversible structural Fe rearrangements that altered the observed apparent standard reduction potential (E(H)(ø)) of structural Fe. E(H)(ø)-values vary by as much as 0.56 V between SWa-1 samples with different redox histories. The wide range of E(H)-values over which SWa-1 is redox-active and redox history-dependent E(H)(ø)-values underscore the importance of Fe-bearing clay minerals as redox-active phases in a wide range of redox regimes.

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.

Enhanced bimolecular exchange reaction through programmed coordination of a five-coordinate oxovanadium complex for efficient redox mediation in dye-sensitized solar cells.

PubMed

Oyaizu, Kenichi; Hayo, Noriko; Sasada, Yoshito; Kato, Fumiaki; Nishide, Hiroyuki

2013-12-07

Electrochemical reversibility and fast bimolecular exchange reaction found for VO(salen) gave rise to a highly efficient redox mediation to enhance the photocurrent of a dye-sensitized solar cell, leading to an excellent photovoltaic performance with a conversion efficiency of 5.4%. A heterogeneous electron-transfer rate constant at an electrode (k0) and a second-order rate constant for an electron self-exchange reaction (k(ex)) were proposed as key parameters that dominate the charge transport property, which afforded a novel design concept for the mediators based on their kinetic aspects.

Control of synaptic function by endocannabinoid-mediated retrograde signaling.

PubMed

Kano, Masanobu

2014-01-01

Since the first reports in 2001, great advances have been made towards the understanding of endocannabinoid-mediated synaptic modulation. Electrophysiological studies have revealed that one of the two major endocannabinoids, 2-arachidonoylglycerol (2-AG), is produced from membrane lipids upon postsynaptic Ca(2+) elevation and/or activation of Gq/11-coupled receptors, and released from postsynaptic neurons. The released 2-AG then acts retrogradely onto presynaptic cannabinoid CB1 receptors and induces suppression of neurotransmitter release either transiently or persistently. These forms of 2-AG-mediated retrograde synaptic modulation are functional throughout the brain. The other major endocannabinoid, anandamide, mediates a certain form of endocannabinoid-mediated long-term depression (LTD). Anandamide also functions as an agonist for transient receptor potential vanilloid receptor type 1 (TRPV1) and mediates endocannabinoid-independent and TRPV1-dependent forms of LTD. It has also been demonstrated that the endocannabinoid system itself is plastic, which can be either up- or down-regulated by experimental or environmental conditions. In this review, I will make an overview of the mechanisms underlying endocannabinoid-mediated synaptic modulation.

Control of synaptic function by endocannabinoid-mediated retrograde signaling

PubMed Central

KANO, Masanobu

2014-01-01

Since the first reports in 2001, great advances have been made towards the understanding of endocannabinoid-mediated synaptic modulation. Electrophysiological studies have revealed that one of the two major endocannabinoids, 2-arachidonoylglycerol (2-AG), is produced from membrane lipids upon postsynaptic Ca2+ elevation and/or activation of Gq/11-coupled receptors, and released from postsynaptic neurons. The released 2-AG then acts retrogradely onto presynaptic cannabinoid CB1 receptors and induces suppression of neurotransmitter release either transiently or persistently. These forms of 2-AG-mediated retrograde synaptic modulation are functional throughout the brain. The other major endocannabinoid, anandamide, mediates a certain form of endocannabinoid-mediated long-term depression (LTD). Anandamide also functions as an agonist for transient receptor potential vanilloid receptor type 1 (TRPV1) and mediates endocannabinoid-independent and TRPV1-dependent forms of LTD. It has also been demonstrated that the endocannabinoid system itself is plastic, which can be either up- or down-regulated by experimental or environmental conditions. In this review, I will make an overview of the mechanisms underlying endocannabinoid-mediated synaptic modulation. PMID:25169670

Virtual electrochemical nitric oxide analyzer using copper, zinc superoxide dismutase immobilized on carbon nanotubes in polypyrrole matrix.

PubMed

Madasamy, Thangamuthu; Pandiaraj, Manickam; Balamurugan, Murugesan; Karnewar, Santosh; Benjamin, Alby Robson; Venkatesh, Krishna Arun; Vairamani, Kanagavel; Kotamraju, Srigiridhar; Karunakaran, Chandran

2012-10-15

In this work, we have designed and developed a novel and cost effective virtual electrochemical analyzer for the measurement of NO in exhaled breath and from hydrogen peroxide stimulated endothelial cells using home-made potentiostat. Here, data acquisition system (NI MyDAQ) was used to acquire the data from the electrochemical oxidation of NO mediated by copper, zinc superoxide dismutase (Cu,ZnSOD). The electrochemical control programs (graphical user-interface software) were developed using LabVIEW 10.0 to sweep the potential, acquire the current response and process the acquired current signal. The Cu,ZnSOD (SOD1) immobilized on the carbon nanotubes in polypyrrole modified platinum electrode was used as the NO biosensor. The electrochemical behavior of the SOD1 modified electrode exhibited the characteristic quasi-reversible redox peak at the potential, +0.06 V vs. Ag/AgCl. The biological interferences were eliminated by nafion coated SOD1 electrode and then NO was measured selectively. Further, this biosensor showed a wide linear range of response over the concentration of NO from 0.1 μM to 1 mM with a detection limit of 0.1 μM and high sensitivity of 1.1 μA μM(-1). The electroanalytical results obtained here using the developed virtual electrochemical instrument were also compared with the standard cyclic voltammetry instrument and found in agreement with each other. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Hypothesis: Leukocyte Endogenous Mediator/Endogenous Pyrogen/Lymphocyte-Activating Factor Modulates the Development of Nonspecific and Specific Immunity and Affects Nutritional Status

DTIC Science & Technology

1982-04-01

Hypothesis: leukocyte endogenous mediator/ endogenous pyrogen /lymphocyte-activating factor modulates the development of nonspecific and specific... endogenous pyrogen /lympho- NI cyte-activating factor (LEM/EP/LAF) integrates the host’s nonspecific and specific immune responses to infection by...mediator/ endogenous pyrogen /lymphocyte-activating factor, nonspecific and specific immunity, infection, metabolism, nutrition. Introduction LAF which lead

Co-immobilization of gold nanoparticles with glucose oxidase to improve bioelectrocatalytic glucose oxidation

NASA Astrophysics Data System (ADS)

Aquino Neto, Sidney; Milton, Ross D.; Crepaldi, Laís B.; Hickey, David P.; de Andrade, Adalgisa R.; Minteer, Shelley D.

2015-07-01

Recently, there has been much effort in developing metal nanoparticle catalysts for fuel oxidation, as well as the development of enzymatic bioelectrocatalysts for fuel oxidation. However, there has been little study of the synergy of hybrid electrocatalytic systems. We report the preparation of hybrid bioanodes based on Au nanoparticles supported on multi-walled carbon nanotubes (MWCNTs) co-immobilized with glucose oxidase (GOx). Mediated electron transfer was achieved by two strategies: ferrocene entrapped within polypyrrole and a ferrocene-modified linear poly(ethylenimine) (Fc-LPEI) redox polymer. Electrochemical characterization of the Au nanoparticles supported on MWCNTs indicate that this catalyst exhibits an electrocatalytic response for glucose even in acidic conditions. Using the redox polymer Fc-LPEI as the mediator, voltammetric and amperometric data demonstrated that these bioanodes can efficiently achieve mediated electron transfer and also indicated higher catalytic currents with the hybrid bioelectrode. From the amperometry, the maximum current density (Jmax) achieved with the hybrid bioelectrode was 615 ± 39 μA cm-2, whereas the bioanode employing GOx only achieved a Jmax of 409 ± 26 μA cm-2. Biofuel cell tests are consistent with the electrochemical characterization, thus confirming that the addition of the metallic species into the bioanode structure can improve fuel oxidation and consequently, improve the power generated by the system.

Voltammetric determination of attomolar levels of a sequence derived from the genom of hepatitis B virus by using molecular beacon mediated circular strand displacement and rolling circle amplification.

PubMed

Huang, Shan; Feng, Mengmeng; Li, Jiawen; Liu, Yi; Xiao, Qi

2018-03-03

The authors describe an electrochemical method for the determination of the single-stranded DNA (ssDNA) oligonucleotide with a sequence derived from the genom of hepatitis B virus (HBV). It is making use of circular strand displacement (CSD) and rolling circle amplification (RCA) strategies mediated by a molecular beacon (MB). This ssDNA hybridizes with the loop portion of the MB immobilized on the surface of a gold electrode, while primer DNA also hybridizes with the rest of partial DNA sequences of MB. This triggers the MB-mediated CSD. The RCA is then initiated to produce a long DNA strand with multiple tandem-repeat sequences, and this results in a significant increase of the differential pulse voltammetric response of the electrochemical probe Methylene Blue at a rather low working potential of -0.24 V (vs. Ag/AgCl). Under optimal experimental conditions, the assay displays an ultrahigh sensitivity (with a 2.6 aM detection limit) and excellent selectivity. Response is linear in the 10 to 700 aM DNA concentration range. Graphical abstract Schematic of a voltammetric method for the determination of attomolar levels of target DNA. It is based on molecular beacon mediated circular strand displacement and rolling circle amplification strategies. Under optimal experimental conditions, the assay displays an ultrahigh sensitivity with a 2.6 aM detection limit and excellent selectivity.

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.

Strain- and Substrate-Dependent Redox Mediator and Electricity Production by Pseudomonas aeruginosa.

PubMed

Bosire, Erick M; Blank, Lars M; Rosenbaum, Miriam A

2016-08-15

Pseudomonas aeruginosa is an important, thriving member of microbial communities of microbial bioelectrochemical systems (BES) through the production of versatile phenazine redox mediators. Pure culture experiments with a model strain revealed synergistic interactions of P. aeruginosa with fermenting microorganisms whereby the synergism was mediated through the shared fermentation product 2,3-butanediol. Our work here shows that the behavior and efficiency of P. aeruginosa in mediated current production is strongly dependent on the strain of P. aeruginosa We compared levels of phenazine production by the previously investigated model strain P. aeruginosa PA14, the alternative model strain P. aeruginosa PAO1, and the BES isolate Pseudomonas sp. strain KRP1 with glucose and the fermentation products 2,3-butanediol and ethanol as carbon substrates. We found significant differences in substrate-dependent phenazine production and resulting anodic current generation for the three strains, with the BES isolate KRP1 being overall the best current producer and showing the highest electrochemical activity with glucose as a substrate (19 μA cm(-2) with ∼150 μg ml(-1) phenazine carboxylic acid as a redox mediator). Surprisingly, P. aeruginosa PAO1 showed very low phenazine production and electrochemical activity under all tested conditions. Microbial fuel cells and other microbial bioelectrochemical systems hold great promise for environmental technologies such as wastewater treatment and bioremediation. While there is much emphasis on the development of materials and devices to realize such systems, the investigation and a deeper understanding of the underlying microbiology and ecology are lagging behind. Physiological investigations focus on microorganisms exhibiting direct electron transfer in pure culture systems. Meanwhile, mediated electron transfer with natural redox compounds produced by, for example, Pseudomonas aeruginosa might enable an entire microbial community to access a solid electrode as an alternative electron acceptor. To better understand the ecological relationships between mediator producers and mediator utilizers, we here present a comparison of the phenazine-dependent electroactivities of three Pseudomonas strains. This work forms the foundation for more complex coculture investigations of mediated electron transfer in microbial fuel cells. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Strain- and Substrate-Dependent Redox Mediator and Electricity Production by Pseudomonas aeruginosa

PubMed Central

Bosire, Erick M.; Blank, Lars M.

2016-01-01

ABSTRACT Pseudomonas aeruginosa is an important, thriving member of microbial communities of microbial bioelectrochemical systems (BES) through the production of versatile phenazine redox mediators. Pure culture experiments with a model strain revealed synergistic interactions of P. aeruginosa with fermenting microorganisms whereby the synergism was mediated through the shared fermentation product 2,3-butanediol. Our work here shows that the behavior and efficiency of P. aeruginosa in mediated current production is strongly dependent on the strain of P. aeruginosa. We compared levels of phenazine production by the previously investigated model strain P. aeruginosa PA14, the alternative model strain P. aeruginosa PAO1, and the BES isolate Pseudomonas sp. strain KRP1 with glucose and the fermentation products 2,3-butanediol and ethanol as carbon substrates. We found significant differences in substrate-dependent phenazine production and resulting anodic current generation for the three strains, with the BES isolate KRP1 being overall the best current producer and showing the highest electrochemical activity with glucose as a substrate (19 μA cm−2 with ∼150 μg ml−1 phenazine carboxylic acid as a redox mediator). Surprisingly, P. aeruginosa PAO1 showed very low phenazine production and electrochemical activity under all tested conditions. IMPORTANCE Microbial fuel cells and other microbial bioelectrochemical systems hold great promise for environmental technologies such as wastewater treatment and bioremediation. While there is much emphasis on the development of materials and devices to realize such systems, the investigation and a deeper understanding of the underlying microbiology and ecology are lagging behind. Physiological investigations focus on microorganisms exhibiting direct electron transfer in pure culture systems. Meanwhile, mediated electron transfer with natural redox compounds produced by, for example, Pseudomonas aeruginosa might enable an entire microbial community to access a solid electrode as an alternative electron acceptor. To better understand the ecological relationships between mediator producers and mediator utilizers, we here present a comparison of the phenazine-dependent electroactivities of three Pseudomonas strains. This work forms the foundation for more complex coculture investigations of mediated electron transfer in microbial fuel cells. PMID:27287325

Selectivity and Sensitivity of Ultrathin Monolayer Electrodes

NASA Astrophysics Data System (ADS)

Cheng, Quan

The objective of this work is to build a molecular architecture on the electrode surface with a well-defined morphology and desirable electrochemical characteristics. The goal is accomplished by means of self-assembly of thioctic acid, a sulfur-terminated organic molecule with a short alkyl chain and a hydrophilic carboxylic headgroup, on a gold electrode. Characterization of the monolayer structure and the electrochemical response of the monolayer electrodes is performed by means of capacitance measurements and voltammetry. Investigation of the capacitance of the self-assembled monolayers provides insight into the macroscopic permeability of the films and reveals that penetration of solvent/ions into the thioctic acid monolayer film occurs extensively. Voltammetric results demonstrate that permselectivity of the monolayer electrode can be obtained as a result of the induced electrostatic interactions between the monolayer interface and the electroactive species. Measurement of the voltammetric response of the redox probes at the monolayers as a function of the electrolyte concentration and composition is used to qualitatively analyze the effect of electrolyte on response. A model describing the role of the interfacial charge in the electrochemical response of the monolayers as a function of the solution composition and surface smoothness is proposed. A strategy is developed to further explore the applications of the monolayer electrodes to control the electrochemical response of the biological molecules such as catecholamines. The ability to control the surface hydrophobicity of the monolayer electrodes through coadsorption of thioctic acid and hexanethiol, to display different electrochemical properties towards biological molecules is tested. The optimum conditions for detection of the biological molecules on the monolayer electrodes are discussed. In order to pursue selective analysis in microenvironments, the thioctic acid monolayer formed on the ultramicroelectrodes (UME) is investigated, demonstrating high permselectivity and high sensitivity of the monolayer modified UMEs. Because of the more effective mass transport to the UMEs, effects of electrolyte on the monolayer response can be characterized facilely. Amperometric pH sensing on the thioctic acid UMEs using a redox mediator is discussed. Finally, the thioctic acid monolayer microelectrode is applied to investigate direct electrochemistry of a redox protein, cytochrome c. A sketch for developing a biosensor via mediation effects using the monolayer assembly is proposed.

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.

Detection of eQTL modules mediated by activity levels of transcription factors.

PubMed

Sun, Wei; Yu, Tianwei; Li, Ker-Chau

2007-09-01

Studies of gene expression quantitative trait loci (eQTL) in different organisms have shown the existence of eQTL hot spots: each being a small segment of DNA sequence that harbors the eQTL of a large number of genes. Two questions of great interest about eQTL hot spots arise: (1) which gene within the hot spot is responsible for the linkages, i.e. which gene is the quantitative trait gene (QTG)? (2) How does a QTG affect the expression levels of many genes linked to it? Answers to the first question can be offered by available biological evidence or by statistical methods. The second question is harder to address. One simple situation is that the QTG encodes a transcription factor (TF), which regulates the expression of genes linked to it. However, previous results have shown that TFs are not overrepresented in the eQTL hot spots. In this article, we consider the scenario that the propagation of genetic perturbation from a QTG to other linked genes is mediated by the TF activity. We develop a procedure to detect the eQTL modules (eQTL hot spots together with linked genes) that are compatible with this scenario. We first detect 27 eQTL modules from a yeast eQTL data, and estimate TF activity profiles using the method of Yu and Li (2005). Then likelihood ratio tests (LRTs) are conducted to find 760 relationships supporting the scenario of TF activity mediation: (DNA polymorphism --> cis-linked gene --> TF activity --> downstream linked gene). They are organized into 4 eQTL modules: an amino acid synthesis module featuring a cis-linked gene LEU2 and the mediating TF Leu3; a pheromone response module featuring a cis-linked gene GPA1 and the mediating TF Ste12; an energy-source control module featuring two cis-linked genes, GSY2 and HAP1, and the mediating TF Hap1; a mitotic exit module featuring four cis-linked genes, AMN1, CSH1, DEM1 and TOS1, and the mediating TF complex Ace2/Swi5. Gene Ontology is utilized to reveal interesting functional groups of the downstream genes in each module. Our methods are implemented in an R package: eqtl.TF, which includes source codes and relevant data. It can be freely downloaded at http://www.stat.ucla.edu/~sunwei/software.htm. http://www.stat.ucla.edu/~sunwei/yeast_eQTL_TF/supplementary.pdf.

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.

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.

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.

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

PubMed

Nöll, Tanja; Nöll, Gilbert

2011-07-01

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

Porous platinum nanotubes labeled with hemin/G-quadruplex based electrochemical aptasensor for sensitive thrombin analysis via the cascade signal amplification.

PubMed

Sun, Aili; Qi, Qingan; Wang, Xuannian; Bie, Ping

2014-07-15

For the first time, a sensitive electrochemical aptasensor for thrombin (TB) was developed by using porous platinum nanotubes (PtNTs) labeled with hemin/G-quadruplex and glucose dehydrogenase (GDH) as labels. Porous PtNTs with large surface area exhibited the peroxidase-like activity. Coupling with GDH and hemin/G-quadruplex as NADH oxidase and HRP-mimicking DNAzyme, the cascade signal amplification was achieved by the following ways: in the presence of glucose and NAD(+) in the working buffer, GDH electrocatalyzed the oxidation of glucose with the production of NADH. Then, hemin/G-quadruplex as NADH oxidase catalyzed the oxidation of NADH to in situ generate H2O2. Based on the corporate electrocatalysis of PtNTs and hemin/G-quadruplex toward H2O2, the electrochemical signal was significantly amplified, allowing the detection limit of TB down to 0.15 pM level. Moreover, the proposed strategy was simple because the intercalated hemin offered the readout signal, avoiding the adding of additional redox mediator as signal donator. Such an electrochemical aptasensor is highly promising for sensitive detection of other proteins in clinical diagnostics. Copyright © 2014 Elsevier B.V. All rights reserved.

GaN light-emitting device based on ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Hirai, Tomoaki; Sakanoue, Tomo; Takenobu, Taishi

2018-06-01

Ionic liquids (ILs) are attractive materials for fabricating unique hybrid devices based on electronics and electrochemistry; thus, IL-gated transistors and organic light-emitting devices of light-emitting electrochemical cells (LECs) are investigated for future low-voltage and high-performance devices. In LECs, voltage application induces the formation of electrochemically doped p–n homojunctions owing to ion rearrangements in composites of semiconductors and electrolytes, and achieves electron–hole recombination for light emission at the homojunctions. In this work, we applied this concept of IL-induced electrochemical doping to the fabrication of GaN-based light-emitting devices. We found that voltage application to the layered IL/GaN structure accumulated electrons on the GaN surface owing to ion rearrangements and improved the conductivity of GaN. The ion rearrangement also enabled holes to be injected by the strong electric field of electric double layers on hole injection contacts. This simultaneous injection of holes and electrons into GaN mediated by ions achieves light emission at a low voltage of around 3.4 V. The light emission from the simple IL/GaN structure indicates the usefulness of an electrochemical technique in generating light emission with great ease of fabrication.

An electrochemical microRNAs biosensor with the signal amplification of alkaline phosphatase and electrochemical-chemical-chemical redox cycling.

PubMed

Xia, Ning; Zhang, Youjuan; Wei, Xin; Huang, Yaping; Liu, Lin

2015-06-09

MicroRNAs (MiRNAs) have been regarded as clinically important biomarkers and drug discovery targets. In this work, we reported a simple and ultrasensitive electrochemical method for miRNAs detection based on single enzyme amplification and electrochemical-chemical-chemical (ECC) redox cycling. Specifically, upon contact with the target miRNAs, the hairpin structure of biotinylated DNA immobilized on gold electrode was destroyed and the biotin group in DNA was forced away from the electrode surface, allowing for the coupling of streptavidin-conjugated alkaline phosphatase (SA-ALP). Then, ascorbic acid (AA, the enzymatic product of ALP) triggered the ECC redox cycling with ferrocene methanol (FcM) and tris(2-carboxyethyl)phosphine (TCEP) as the redox mediator and the chemical reducing reagent, respectively. The method was more sensitive than that with horseradish peroxidase (HRP) or glucose oxidase (GOx) triggered recycling since one ALP molecule captured by one target miRNA molecule promoted the production of thousands of AA. Analytical merits (e.g., detection limit, dynamic range, specificity, regeneration and reproducibility) were evaluated. The feasibility of the method for analysis of miRNA-21 in human serum has also been demonstrated. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical Glucose Sensors—Developments Using Electrostatic Assembly and Carbon Nanotubes for Biosensor Construction

PubMed Central

Harper, Alice; Anderson, Mark R.

2010-01-01

In 1962, Clark and Lyons proposed incorporating the enzyme glucose oxidase in the construction of an electrochemical sensor for glucose in blood plasma. In their application, Clark and Lyons describe an electrode in which a membrane permeable to glucose traps a small volume of solution containing the enzyme adjacent to a pH electrode, and the presence of glucose is detected by the change in the electrode potential that occurs when glucose reacts with the enzyme in this volume of solution. Although described nearly 50 years ago, this seminal development provides the general structure for constructing electrochemical glucose sensors that is still used today. Despite the maturity of the field, new developments that explore solutions to the fundamental limitations of electrochemical glucose sensors continue to emerge. Here we discuss two developments of the last 15 years; confining the enzyme and a redox mediator to a very thin molecular films at electrode surfaces by electrostatic assembly, and the use of electrodes modified by carbon nanotubes (CNTs) to leverage the electrocatalytic effect of the CNTs to reduce the oxidation overpotential of the electrode reaction or for the direct electron transport to the enzyme. PMID:22163652

Electrochemical glucose sensors--developments using electrostatic assembly and carbon nanotubes for biosensor construction.

PubMed

Harper, Alice; Anderson, Mark R

2010-01-01

In 1962, Clark and Lyons proposed incorporating the enzyme glucose oxidase in the construction of an electrochemical sensor for glucose in blood plasma. In their application, Clark and Lyons describe an electrode in which a membrane permeable to glucose traps a small volume of solution containing the enzyme adjacent to a pH electrode, and the presence of glucose is detected by the change in the electrode potential that occurs when glucose reacts with the enzyme in this volume of solution. Although described nearly 50 years ago, this seminal development provides the general structure for constructing electrochemical glucose sensors that is still used today. Despite the maturity of the field, new developments that explore solutions to the fundamental limitations of electrochemical glucose sensors continue to emerge. Here we discuss two developments of the last 15 years; confining the enzyme and a redox mediator to a very thin molecular films at electrode surfaces by electrostatic assembly, and the use of electrodes modified by carbon nanotubes (CNTs) to leverage the electrocatalytic effect of the CNTs to reduce the oxidation overpotential of the electrode reaction or for the direct electron transport to the enzyme.

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

PubMed

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

2016-06-21

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

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

Development of a new paper based nano-biosensor using the co-catalytic effect of tyrosinase from banana peel tissue (Musa Cavendish) and functionalized silica nanoparticles for voltammetric determination of l-tyrosine.

PubMed

Rahimi-Mohseni, Mohadeseh; Raoof, Jahan Bakhsh; Ojani, Reza; Aghajanzadeh, Tahereh A; Bagheri Hashkavayi, Ayemeh

2018-07-01

In this paper, a new and facile method for the electrochemical determination of l-tyrosine was designed. First, 3-mercaptopropyl trimethoxysilane-functionalized silica nanoparticles were added to a paper disc. Then, the banana peel tissue and the mediator potassium hexacyanoferrate were dropped onto the paper, respectively. The modified paper disc was placed on the top of the graphite screen printed electrode and electrochemical characterization of this biosensor was studied by cyclic voltammetry and electrochemical impedance spectroscopy methods. The effective parameters like pH, banana peel tissue percentage, and the amount of mediator loading were optimized. l-tyrosine measurements were done by differential pulse voltammetry with a little sample (3 μL) for analysis. The biosensor showed a linear response for l-tyrosine in the wide concentration range of 0.05-600 μM and a low detection limit about 0.02 μM because of the co-catalytic effect of enzyme and nanoparticles. The stability of the biosensor and its selectivity were evaluated. This biosensor was applied for the voltammetric determination of l-tyrosine in the blood plasma sample. The results of the practical application study were comparable with the standard method (HPLC). In conclusion, a simple, inexpensive, rapid, sensitive and selective technique was successfully applied to the l-tyrosine analysis of the little samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Efficient low-temperature transparent electrocatalytic layers based on graphene oxide nanosheets for dye-sensitized solar cells.

PubMed

Seo, Seon Hee; Jeong, Eun Ji; Han, Joong Tark; Kang, Hyon Chol; Cha, Seung I; Lee, Dong Yoon; Lee, Geon-Woong

2015-05-27

Electrocatalytic materials with a porous structure have been fabricated on glass substrates, via high-temperature fabrication, for application as alternatives to platinum in dye-sensitized solar cells (DSCs). Efficient, nonporous, nanometer-thick electrocatalytic layers based on graphene oxide (GO) nanosheets were prepared on plastic substrates using electrochemical control at low temperatures of ≤100 °C. Single-layer, oxygen-rich GO nanosheets prepared on indium tin oxide (ITO) substrates were electrochemically deoxygenated in acidic medium within a narrow scan range in order to obtain marginally reduced GO at minimum expense of the oxygen groups. The resulting electrochemically reduced GO (E-RGO) had a high density of residual alcohol groups with high electrocatalytic activity toward the positively charged cobalt-complex redox mediators used in DSCs. The ultrathin, alcohol-rich E-RGO layer on ITO-coated poly(ethylene terephthalate) was successfully applied as a lightweight, low-temperature counter electrode with an extremely high optical transmittance of ∼97.7% at 550 nm. A cobalt(II/III)-mediated DSC employing the highly transparent, alcohol-rich E-RGO electrode exhibited a photovoltaic power conversion efficiency of 5.07%. This is superior to that obtained with conventionally reduced GO using hydrazine (3.94%) and even similar to that obtained with platinum (5.10%). This is the first report of a highly transparent planar electrocatalytic layer based on carbonaceous materials fabricated on ITO plastics for application in DSCs.

Targeting Cellular Calcium Homeostasis to Prevent Cytokine-Mediated Beta Cell Death.

PubMed

Clark, Amy L; Kanekura, Kohsuke; Lavagnino, Zeno; Spears, Larry D; Abreu, Damien; Mahadevan, Jana; Yagi, Takuya; Semenkovich, Clay F; Piston, David W; Urano, Fumihiko

2017-07-17

Pro-inflammatory cytokines are important mediators of islet inflammation, leading to beta cell death in type 1 diabetes. Although alterations in both endoplasmic reticulum (ER) and cytosolic free calcium levels are known to play a role in cytokine-mediated beta cell death, there are currently no treatments targeting cellular calcium homeostasis to combat type 1 diabetes. Here we show that modulation of cellular calcium homeostasis can mitigate cytokine- and ER stress-mediated beta cell death. The calcium modulating compounds, dantrolene and sitagliptin, both prevent cytokine and ER stress-induced activation of the pro-apoptotic calcium-dependent enzyme, calpain, and partly suppress beta cell death in INS1E cells and human primary islets. These agents are also able to restore cytokine-mediated suppression of functional ER calcium release. In addition, sitagliptin preserves function of the ER calcium pump, sarco-endoplasmic reticulum Ca 2+ -ATPase (SERCA), and decreases levels of the pro-apoptotic protein thioredoxin-interacting protein (TXNIP). Supporting the role of TXNIP in cytokine-mediated cell death, knock down of TXNIP in INS1-E cells prevents cytokine-mediated beta cell death. Our findings demonstrate that modulation of dynamic cellular calcium homeostasis and TXNIP suppression present viable pharmacologic targets to prevent cytokine-mediated beta cell loss in diabetes.

Optically transparent FTO-free cathode for dye-sensitized solar cells.

PubMed

Kavan, Ladislav; Liska, Paul; Zakeeruddin, Shaik M; Grätzel, Michael

2014-12-24

The woven fabric containing electrochemically platinized tungsten wire is an affordable flexible cathode for liquid-junction dye-sensitized solar cells with the I3(-)/I(-) redox mediator and electrolyte solution consisting of ionic liquids and propionitrile. The fabric-based electrode outperforms the thermally platinized FTO in serial ohmic resistance and charge-transfer resistance for triiodide reduction, and it offers comparable or better optical transparency in the visible and particularly in the near-IR spectral region. The electrode exhibits good stability during electrochemical loading and storage at open circuit. The dye-sensitized solar cells with a C101-sensitized titania photoanode and either Pt-W/PEN or Pt-FTO cathodes show a comparable performance.

Sensitive electrochemical immunoassay for 2,4,6-trinitrotoluene based on functionalized silica nanoparticle labels

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

Wang, Jun; Liu, Guodong; Wu, Hong

2008-03-03

We present a poly(guanine)-functionalized silica nanoparticle (NP) label-based electrochemical immunoassay for sensitively detecting 2,4,6-trinitrotoluene (TNT). This immunoassay takes advantage of magnetic bead–based platform for competitive displacement immunoreactions and separation, and use electroactive nanoparticles as labels for signal amplification. For this assay, anti-TNT-coated magnetic beads interacted with TNT analog-conjugated poly(guanine)-silica NPs and formed analog-anti-TNT immunocomplexes on magnetic beads. The immunocomplexes coated magnetic beads were exposed to TNT samples, which resulted in displacing the analog conjugated poly(guanine) silica NPs into solution by TNT. In contrast, there are no guanine residues releasing into the solution in the absence of TNT. The reaction solutionmore » was then separated from the magnetic beads and transferred to the electrode surface for electrochemical measurements of guanine oxidation with Ru(bpy)32+ as mediator. The sensitivity of this TNT assay was greatly enhanced through dual signal amplifications: 1) a large amount of guanine residues on silica nanoparticles is introduced into the test solution by displacement immunoreactions and 2) a Ru(bpy)32+-induced guanine catalytic oxidation further enhances the electrochemical signal. Some experimental parameters for the nanoparticle label-based electrochemical immunoassay were studied and the performance of this assay was evaluated. The method is found to be very sensitive and the detection limit of this assay is ~ 0.1 ng mL-1 TNT. The electrochemical immunoassay based on the poly[guanine]-functionalized silica NP label offers a new approach for sensitive detection of explosives.« less

Catalytic Role Of Palladium And Relative Reactivity Of Substituted Chlorines During Adsorption And Treatment Of PCBs On Reactive Activated Carbon

EPA Science Inventory

The adsorption-mediated dechlorination of polychlorinated biphenyls (PCBs) is a unique feature of reactive activated cabon (RAC). Here, we address the RAC system, containing a tunable amount of Fe as a primary electron donor coupled with Pd as an electrochemical catalyst to pote...

Hydroxynaphthoquinone ultrathin films obtained by diazonium electroreduction: toward design of biosensitive electroactive interfaces.

PubMed

March, Gregory; Reisberg, Steeve; Piro, Benoit; Pham, Minh-Chau; Fave, Claire; Noel, Vincent

2010-05-01

Electroactive 2-(phenylsulfanyl)-8-hydroxy-1,4-naphthoquinone has been electrodeposited via the reduction of the corresponding diazonium salt on Au electrodes. Surface characterizations by X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IRRAS) reveal that the mechanism of film deposition follows an aryl radical formation and its immobilization on the electrode surface. Electrochemical study shows that the surface coverage can be finely tuned (thickness between one and four layers) by adjusting the potential and the deposition time. By managing the potential applied when reducing diazonium in potentiostatic mode, the formed layer could mediate or not charge transfer. This is the first time that the films obtained by diazonium process are demonstrated to act as mediators in the growth process. Hence, with potentials higher than the formal potential of quinone group, very thin and homogeneous layers are obtained, whereas thicker films are formed when more cathodic potentials than that of quinone are applied. The possibility to manage the charge-transfer kinetics, the thickness, and the homogeneity of electroactive deposits is interesting in the scope of designing electrochemical transducers.

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.

Simultaneous exposure to concentrated ambient particles and acrolein causes cardiac effects mediated by parasympathetic modulation in mice

EPA Science Inventory

This study shows that exposure to CAPs and acrolein causes an increase in HRV that is mediated by the parasympathetic nervous system. Numerous studies show that short-term air pollution exposure modulates heart rate variability (HRV), which is an indicator of autonomic influence...

Prostanoids and their receptors that modulate dendritic cell-mediated immunity.

PubMed

Gualde, Norbert; Harizi, Hedi

2004-08-01

Dendritic cells (DC) are essential for the initiation of immune responses by capturing, processing and presenting antigens to T cells. In addition to their important role as professional APC, they are able to produce immunosuppressive and pro-inflammatory prostanoids from arachidonic acid (AA) by the action of cyclooxygenase (COX) enzymes. In an autocrine and paracrine fashion, the secreted lipid mediators subsequently modulate the maturation, cytokine production, Th-cell polarizing ability, chemokine receptor expression, migration, and apoptosis of these extremely versatile APC. The biological actions of prostanoids, including their effects on APC-mediated immunity and acute inflammatory responses, are exerted by G protein-coupled receptors on plasma membrane. Some COX metabolites act as anti-inflammatory lipid mediators by binding to nuclear receptors and modulating DC functions. Although the role of cytokines in DC function has been studied extensively, the effects of prostanoids on DC biology have only recently become the focus of investigation. This review summarizes the current knowledge about the role of prostanoids and their receptors in modulating DC function and the subsequent immune responses.

A multifunctional hemin@metal-organic framework and its application to construct an electrochemical aptasensor for thrombin detection

NASA Astrophysics Data System (ADS)

Xie, Shunbi; Ye, Jiawei; Yuan, Yali; Chai, Yaqin; Yuan, Ruo

2015-10-01

A new type of multifunctional metal-organic framework (MOF) has been synthesized by encapsulating hemin into the nano-sized Fe-MIL-88 MOFs (hemin@MOFs) and first applied in an electrochemical aptasensor to detect thrombin (TB) with the aid of an enzyme for signal amplification. The gold nanoparticle functionalized hemin@MOFs (Au/hemin@MOFs) have not only simultaneously served as redox mediators and solid electrocatalysts, but have also been utilized as an ideal loading platform to immobilize a large number of biomolecules. In this aptasensor, Au/hemin@MOFs conjugated with glucose oxidase (GOD) and thrombin binding aptamer (TBA II) were used as the secondary aptamer bioconjugates (Au/hemin@MOF-TBA II-GOD bioconjugates), and TB was sandwiched between Au/hemin@MOF-TBA II-GOD bioconjugates and the amino-terminated TBA I which was self-assembled on the gold nanoparticle (AuNP) modified electrode. The GOD could oxidize glucose into gluconic acid accompanied by the generation of H2O2. The generated H2O2 on the electrode surface was further electrocatalyzed by hemin@MOFs to amplify the electrochemical signal of hemin contained in hemin@MOFs. Therefore, the synthesized hemin@MOFs represented a new paradigm for multifunctional materials since it combined three different functions including serving as catalysts, redox mediators and loading platforms within a single material. With such an ingenious design, a wide linear range of 0.0001 nM to 30 nM was acquired with a relatively low detection limit of 0.068 pM for TB detection.A new type of multifunctional metal-organic framework (MOF) has been synthesized by encapsulating hemin into the nano-sized Fe-MIL-88 MOFs (hemin@MOFs) and first applied in an electrochemical aptasensor to detect thrombin (TB) with the aid of an enzyme for signal amplification. The gold nanoparticle functionalized hemin@MOFs (Au/hemin@MOFs) have not only simultaneously served as redox mediators and solid electrocatalysts, but have also been utilized as an ideal loading platform to immobilize a large number of biomolecules. In this aptasensor, Au/hemin@MOFs conjugated with glucose oxidase (GOD) and thrombin binding aptamer (TBA II) were used as the secondary aptamer bioconjugates (Au/hemin@MOF-TBA II-GOD bioconjugates), and TB was sandwiched between Au/hemin@MOF-TBA II-GOD bioconjugates and the amino-terminated TBA I which was self-assembled on the gold nanoparticle (AuNP) modified electrode. The GOD could oxidize glucose into gluconic acid accompanied by the generation of H2O2. The generated H2O2 on the electrode surface was further electrocatalyzed by hemin@MOFs to amplify the electrochemical signal of hemin contained in hemin@MOFs. Therefore, the synthesized hemin@MOFs represented a new paradigm for multifunctional materials since it combined three different functions including serving as catalysts, redox mediators and loading platforms within a single material. With such an ingenious design, a wide linear range of 0.0001 nM to 30 nM was acquired with a relatively low detection limit of 0.068 pM for TB detection. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04532k

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.

A lactate electrochemical biosensor with a titanate nanotube as direct electron transfer promoter

NASA Astrophysics Data System (ADS)

Yang, Mingli; Wang, Jin; Li, Huaqing; Zheng, Jian-Guo; Wu, Nianqiang Nick

2008-02-01

Hydrogen titanate (H2Ti3O7) nanotubes (TNTs) have been synthesized by a one-step hydrothermal processing. Lactate oxidase (LOx) enzyme has been immobilized on the three-dimensional porous TNT network to make an electrochemical biosensor for lactate detection. Cyclic voltammetry and amperometry tests reveal that the LOx enzyme, which is supported on TNTs, maintains their substrate-specific catalytic activity. The nanotubes offer the pathway for direct electron transfer between the electrode surface and the active redox centers of LOx, which enables the biosensor to operate at a low working potential and to avoid the influence of the presence of O2 on the amperometric current response. The biosensor exhibits a sensitivity of 0.24 µA cm-2 mM-1, a 90% response time of 5 s, and a linear response in the range from 0.5 to 14 mM and the redox center of enzyme obviates the need of redox mediators for electrochemical enzymatic sensors, which is attractive for the development of reagentless biosensors.

Achieving Simultaneous CO2 and H2 S Conversion via a Coupled Solar-Driven Electrochemical Approach on Non-Precious-Metal Catalysts.

PubMed

Ma, Weiguang; Wang, Hong; Yu, Wei; Wang, Xiaomei; Xu, Zhiqiang; Zong, Xu; Li, Can

2018-03-19

Carbon dioxide (CO 2 ) and hydrogen sulfide (H 2 S) are generally concomitant with methane (CH 4 ) in natural gas and traditionally deemed useless or even harmful. Developing strategies that can simultaneously convert both CO 2 and H 2 S into value-added products is attractive; however it has not received enough attention. A solar-driven electrochemical process is demonstrated using graphene-encapsulated zinc oxide catalyst for CO 2 reduction and graphene catalyst for H 2 S oxidation mediated by EDTA-Fe 2+ /EDTA-Fe 3+ redox couples. The as-prepared solar-driven electrochemical system can realize the simultaneous conversion of CO 2 and H 2 S into carbon monoxide and elemental sulfur at near neutral conditions with high stability and selectivity. This conceptually provides an alternative avenue for the purification of natural gas with added economic and environmental benefits. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of morphology and chemical doping on electrochemical properties of metal hydroxides in pseudocapacitors.

PubMed

Lee, Gyeonghee; Varanasi, Chakrapani V; Liu, Jie

2015-02-21

It is well known that both the structural morphology and chemical doping are important factors that affect the properties of metal hydroxide materials in electrochemical energy storage devices. In this work, an effective method to tailor the morphology and chemical doping of metal hydroxides is developed. It is shown that the morphology and the degree of crystallinity of Ni(OH)2 can be changed by adding glucose in the ethanol-mediated solvothermal synthesis. Ni(OH)2 produced in this manner exhibited an increased specific capacitance, which is partially attributed to its increased surface area. Interestingly, the effect of morphology on cobalt doped-Ni(OH)2 is found to be more effective at low cobalt contents than at high cobalt contents in terms of improving the electrochemical performance. This result reveals the existence of competitive effects between chemical doping and morphology change. These findings will provide important insights to design effective materials for energy storage devices.

Calcium accelerates SNARE-mediated lipid mixing through modulating α-synuclein membrane interaction.

PubMed

Zhang, Zeting; Jiang, Xin; Xu, Danrui; Zheng, Wenwen; Liu, Maili; Li, Conggang

2018-04-04

α-Synuclein is involved in Parkinson's disease, and its interaction with cell membrane is vital to its pathological and physiological functions. We have shown that Ca 2+ can regulate α-synuclein membrane interaction, but the physiological role of Ca 2+ in modulating α-synuclein membrane interaction is still unexplored. Based on the previous findings that α-synuclein inhibits membrane fusion and its inhibitory effect is highly related to its membrane binding, here we employed solution state Nuclear Magnetic Resonance (NMR) spectroscopy and the ensemble fluorescence fusion assay to show that Ca 2+ can modulate the inhibitory effect of α-synuclein on SNARE-mediated membrane fusion through disrupting α-synuclein membrane interaction, resulting in acceleration of SNARE-mediated membrane fusion. These results suggest a modulatory effect of Ca 2+ on membrane mediated normal function of α-synuclein, which of importance for the study of the Parkinson's disease. Copyright © 2018 Elsevier B.V. All rights reserved.

Beta-adrenergic receptor sensitivity, autonomic balance and serotonergic activity in practitioners of Transcendental Meditation

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

Hill, D.A.

1989-01-01

The aim of this thesis was to investigate the acute autonomic effects of the Transcendental Meditation Program (TM) and resolve the conflict arising from discrepant neurochemical and psychophysiological data. Three experimental investigations were performed. The first examined beta{sub 2}-adrenergic receptors (AR's) on peripheral blood lymphocytes, via (I{sup 125})iodocyanopindolol binding, in 10 male mediating and 10 age matched non-meditating control subjects, to test the hypothesis that the long-term practice of TM and the TM Sidhi Program (TMSP) reduces end organ sensitivity to adrenergic agonists. The second investigated respiratory sinus arrhythmia (an indirect measure of cardiac Parasympathetic Nervous System tone), and skinmore » resistance (a measure of Sympathetic Nervous System tone) during periods of spontaneous respiratory apneusis, a phenomenon occurring during TM that is known to mark the subjective experience of transcending. The third was within subject investigation of the acute effects of the TMSP on 5-hydroxytryptamine (5-HT) activity. Platelet 5-HT was assayed by high pressure liquid chromatography with electrochemical detection, plasma prolactin (PL) and lutenizing hormone (LH) by radioimmunoassay, tryptophan by spectrofluorimetry, and alpha-1-acid glycoprotein (AGP, a modulator of 5-HT uptake) by radial immunodiffusion assay.« less

A Stimuli-Responsive Biosensor of Glucose on Layer-by-Layer Films Assembled through Specific Lectin-Glycoenzyme Recognition.

PubMed

Yao, Huiqin; Gan, Qianqian; Peng, Juan; Huang, Shan; Zhu, Meilin; Shi, Keren

2016-04-20

The research on intelligent bioelectrocatalysis based on stimuli-responsive materials or interfaces is of great significance for biosensors and other bioelectronic devices. In the present work, lectin protein concanavalin A (Con A) and glycoenzyme glucose oxidase (GOD) were assembled into {Con A/GOD}n layer-by-layer (LbL) films by taking advantage of the biospecific lectin-glycoenzyme affinity between them. These film electrodes possess stimuli-responsive properties toward electroactive probes such as ferrocenedicarboxylic acid (Fc(COOH)₂) by modulating the surrounding pH. The CV peak currents of Fc(COOH)₂ were quite large at pH 4.0 but significantly suppressed at pH 8.0, demonstrating reversible stimuli-responsive on-off behavior. The mechanism of stimuli-responsive property of the films was explored by comparative experiments and attributed to the different electrostatic interaction between the films and the probes at different pH. This stimuli-responsive films could be used to realize active/inactive electrocatalytic oxidation of glucose by GOD in the films and mediated by Fc(COOH)₂ in solution, which may establish a foundation for fabricating novel stimuli-responsive electrochemical biosensors based on bioelectrocatalysis with immobilized enzymes.

Characterisation of Weibel-Palade body fusion by amperometry in endothelial cells reveals fusion pore dynamics and the effect of cholesterol on exocytosis.

PubMed

Cookson, Emma A; Conte, Ianina L; Dempster, John; Hannah, Matthew J; Carter, Tom

2013-12-01

Regulated secretion from endothelial cells is mediated by Weibel-Palade body (WPB) exocytosis. Plasma membrane cholesterol is implicated in regulating secretory granule exocytosis and fusion pore dynamics; however, its role in modulating WPB exocytosis is not clear. To address this we combined high-resolution electrochemical analysis of WPB fusion pore dynamics, by amperometry, with high-speed optical imaging of WPB exocytosis following cholesterol depletion or supplementation in human umbilical vein endothelial cells. We identified serotonin (5-HT) immunoreactivity in WPBs, and VMAT1 expression allowing detection of secreted 5-HT as discrete current spikes during exocytosis. A high proportion of spikes (∼75%) had pre-spike foot signals, indicating that WPB fusion proceeds via an initial narrow pore. Cholesterol depletion significantly reduced pre-spike foot signal duration and increased the rate of fusion pore expansion, whereas cholesterol supplementation had broadly the reverse effect. Cholesterol depletion slowed the onset of hormone-evoked WPB exocytosis, whereas its supplementation increased the rate of WPB exocytosis and hormone-evoked proregion secretion. Our results provide the first analysis of WPB fusion pore dynamics and highlight an important role for cholesterol in the regulation of WPB exocytosis.

A Stimuli-Responsive Biosensor of Glucose on Layer-by-Layer Films Assembled through Specific Lectin-Glycoenzyme Recognition

PubMed Central

Yao, Huiqin; Gan, Qianqian; Peng, Juan; Huang, Shan; Zhu, Meilin; Shi, Keren

2016-01-01

The research on intelligent bioelectrocatalysis based on stimuli-responsive materials or interfaces is of great significance for biosensors and other bioelectronic devices. In the present work, lectin protein concanavalin A (Con A) and glycoenzyme glucose oxidase (GOD) were assembled into {Con A/GOD}n layer-by-layer (LbL) films by taking advantage of the biospecific lectin-glycoenzyme affinity between them. These film electrodes possess stimuli-responsive properties toward electroactive probes such as ferrocenedicarboxylic acid (Fc(COOH)2) by modulating the surrounding pH. The CV peak currents of Fc(COOH)2 were quite large at pH 4.0 but significantly suppressed at pH 8.0, demonstrating reversible stimuli-responsive on-off behavior. The mechanism of stimuli-responsive property of the films was explored by comparative experiments and attributed to the different electrostatic interaction between the films and the probes at different pH. This stimuli-responsive films could be used to realize active/inactive electrocatalytic oxidation of glucose by GOD in the films and mediated by Fc(COOH)2 in solution, which may establish a foundation for fabricating novel stimuli-responsive electrochemical biosensors based on bioelectrocatalysis with immobilized enzymes. PMID:27104542

Modulation of neonatal microbial recognition: TLR-mediated innate immune responses are specifically and differentially modulated by human milk.

PubMed

LeBouder, Emmanuel; Rey-Nores, Julia E; Raby, Anne-Catherine; Affolter, Michael; Vidal, Karine; Thornton, Catherine A; Labéta, Mario O

2006-03-15

The mechanisms controlling innate microbial recognition in the neonatal gut are still to be fully understood. We have sought specific regulatory mechanisms operating in human breast milk relating to TLR-mediated microbial recognition. In this study, we report a specific and differential modulatory effect of early samples (days 1-5) of breast milk on ligand-induced cell stimulation via TLRs. Although a negative modulation was exerted on TLR2 and TLR3-mediated responses, those via TLR4 and TLR5 were enhanced. This effect was observed in human adult and fetal intestinal epithelial cell lines, monocytes, dendritic cells, and PBMC as well as neonatal blood. In the latter case, milk compensated for the low capacity of neonatal plasma to support responses to LPS. Cell stimulation via the IL-1R or TNFR was not modulated by milk. This, together with the differential effect on TLR activation, suggested that the primary effect of milk is exerted upstream of signaling proximal to TLR ligand recognition. The analysis of TLR4-mediated gene expression, used as a model system, showed that milk modulated TLR-related genes differently, including those coding for signal intermediates and regulators. A proteinaceous milk component of > or =80 kDa was found to be responsible for the effect on TLR4. Notably, infant milk formulations did not reproduce the modulatory activity of breast milk. Together, these findings reveal an unrecognized function of human milk, namely, its capacity to influence neonatal microbial recognition by modulating TLR-mediated responses specifically and differentially. This in turn suggests the existence of novel mechanisms regulating TLR activation.

Amperometric determination of nitrite using natural fibers as template for titanium dioxide nanotubes with immobilized hemin as electron transfer mediator.

PubMed

Ranjani, Balasubramanian; Kalaiyarasi, Jayaprakasham; Pavithra, Loganathan; Devasena, Thiyagarajan; Pandian, Kannaiyan; Gopinath, Subash C B

2018-02-23

A sensing device was constructed for the amperometric determination of nitrite. It is based on the use of titanium dioxide (TiO 2 ) nanotubes template with natural fibers and carrying hemin acting as the electron mediator. A glassy carbon electrode (GCE) was modified with the hemin/TNT nanocomposite. The electrochemical response to nitrite was characterized by impedance spectroscopy and cyclic voltammetry. An amperometric study, performed at a working potential of + 0.75 V (vs. Ag/AgCl), showed the sensor to enable determination of nitrite with a linear response in the 0.6 to 130 μM concentration range and with a 59 nM limit of detection. Corresponding studies by differential study voltammetry (E p  = 0.75 V) exhibited a linear range from 0.6 × 10 -6 to 7.3 × 10 -5  M with a limit of detection of 84 nM. The sensing device was applied to the determination of nitrite in spiked tap and lake water samples. Graphical abstract Natural fibers templated synthesis of TNT immobilized hemin as electron transfer mediator for quantitative detection of nitrite with detection limit of 59 nM and good electrochemical sensitivity and the method can be used for quantitative determination of nitrite in water samples.

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.

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.

Nitric Oxide from IFNγ-Primed Macrophages Modulates the Antimicrobial Activity of β-Lactams against the Intracellular Pathogens Burkholderia pseudomallei and Nontyphoidal Salmonella

PubMed Central

Jones-Carson, Jessica; Zweifel, Adrienne E.; Tapscott, Timothy; Austin, Chad; Brown, Joseph M.; Jones, Kenneth L.; Voskuil, Martin I.; Vázquez-Torres, Andrés

2014-01-01

Our investigations show that nonlethal concentrations of nitric oxide (NO) abrogate the antibiotic activity of β-lactam antibiotics against Burkholderia pseudomallei, Escherichia coli and nontyphoidal Salmonella enterica serovar Typhimurium. NO protects B. pseudomallei already exposed to β-lactams, suggesting that this diatomic radical tolerizes bacteria against the antimicrobial activity of this important class of antibiotics. The concentrations of NO that elicit antibiotic tolerance repress consumption of oxygen (O2), while stimulating hydrogen peroxide (H2O2) synthesis. Transposon insertions in genes encoding cytochrome c oxidase-related functions and molybdenum assimilation confer B. pseudomallei a selective advantage against the antimicrobial activity of the β-lactam antibiotic imipenem. Cumulatively, these data support a model by which NO induces antibiotic tolerance through the inhibition of the electron transport chain, rather than by potentiating antioxidant defenses as previously proposed. Accordingly, pharmacological inhibition of terminal oxidases and nitrate reductases tolerizes aerobic and anaerobic bacteria to β-lactams. The degree of NO-induced β-lactam antibiotic tolerance seems to be inversely proportional to the proton motive force (PMF), and thus the dissipation of ΔH+ and ΔΨ electrochemical gradients of the PMF prevents β-lactam-mediated killing. According to this model, NO generated by IFNγ-primed macrophages protects intracellular Salmonella against imipenem. On the other hand, sublethal concentrations of imipenem potentiate the killing of B. pseudomallei by NO generated enzymatically from IFNγ-primed macrophages. Our investigations indicate that NO modulates the antimicrobial activity of β-lactam antibiotics. PMID:25121731

Monoamines and neuropeptides interact to inhibit aversive behaviour in Caenorhabditis elegans.

PubMed

Mills, Holly; Wragg, Rachel; Hapiak, Vera; Castelletto, Michelle; Zahratka, Jeffrey; Harris, Gareth; Summers, Philip; Korchnak, Amanda; Law, Wenjing; Bamber, Bruce; Komuniecki, Richard

2012-02-01

Pain modulation is complex, but noradrenergic signalling promotes anti-nociception, with α(2)-adrenergic agonists used clinically. To better understand the noradrenergic/peptidergic modulation of nociception, we examined the octopaminergic inhibition of aversive behaviour initiated by the Caenorhabditis elegans nociceptive ASH sensory neurons. Octopamine (OA), the invertebrate counterpart of norepinephrine, modulates sensory-mediated reversal through three α-adrenergic-like OA receptors. OCTR-1 and SER-3 antagonistically modulate ASH signalling directly, with OCTR-1 signalling mediated by Gα(o). In contrast, SER-6 inhibits aversive responses by stimulating the release of an array of 'inhibitory' neuropeptides that activate receptors on sensory neurons mediating attraction or repulsion, suggesting that peptidergic signalling may integrate multiple sensory inputs to modulate locomotory transitions. These studies highlight the complexity of octopaminergic/peptidergic interactions, the role of OA in activating global peptidergic signalling cascades and the similarities of this modulatory network to the noradrenergic inhibition of nociception in mammals, where norepinephrine suppresses chronic pain through inhibitory α(2)-adrenoreceptors on afferent nociceptors and stimulatory α(1)-receptors on inhibitory peptidergic interneurons.

Monoamines and neuropeptides interact to inhibit aversive behaviour in Caenorhabditis elegans

PubMed Central

Mills, Holly; Wragg, Rachel; Hapiak, Vera; Castelletto, Michelle; Zahratka, Jeffrey; Harris, Gareth; Summers, Philip; Korchnak, Amanda; Law, Wenjing; Bamber, Bruce; Komuniecki, Richard

2012-01-01

Pain modulation is complex, but noradrenergic signalling promotes anti-nociception, with α2-adrenergic agonists used clinically. To better understand the noradrenergic/peptidergic modulation of nociception, we examined the octopaminergic inhibition of aversive behaviour initiated by the Caenorhabditis elegans nociceptive ASH sensory neurons. Octopamine (OA), the invertebrate counterpart of norepinephrine, modulates sensory-mediated reversal through three α-adrenergic-like OA receptors. OCTR-1 and SER-3 antagonistically modulate ASH signalling directly, with OCTR-1 signalling mediated by Gαo. In contrast, SER-6 inhibits aversive responses by stimulating the release of an array of ‘inhibitory' neuropeptides that activate receptors on sensory neurons mediating attraction or repulsion, suggesting that peptidergic signalling may integrate multiple sensory inputs to modulate locomotory transitions. These studies highlight the complexity of octopaminergic/peptidergic interactions, the role of OA in activating global peptidergic signalling cascades and the similarities of this modulatory network to the noradrenergic inhibition of nociception in mammals, where norepinephrine suppresses chronic pain through inhibitory α2-adrenoreceptors on afferent nociceptors and stimulatory α1-receptors on inhibitory peptidergic interneurons. PMID:22124329

A protein interaction mechanism for suppressing the mechanosensitive Piezo channels.

PubMed

Zhang, Tingxin; Chi, Shaopeng; Jiang, Fan; Zhao, Qiancheng; Xiao, Bailong

2017-11-27

Piezo proteins are bona fide mammalian mechanotransduction channels for various cell types including endothelial cells. The mouse Piezo1 of 2547 residues forms a three-bladed, propeller-like homo-trimer comprising a central pore-module and three propeller-structures that might serve as mechanotransduction-modules. However, the mechanogating and regulation of Piezo channels remain unclear. Here we identify the sarcoplasmic /endoplasmic-reticulum Ca 2+ ATPase (SERCA), including the widely expressed SERCA2, as Piezo interacting proteins. SERCA2 strategically suppresses Piezo1 via acting on a 14-residue-constituted intracellular linker connecting the pore-module and mechanotransduction-module. Mutating the linker impairs mechanogating and SERCA2-mediated modulation of Piezo1. Furthermore, the synthetic linker-peptide disrupts the modulatory effects of SERCA2, demonstrating the key role of the linker in mechanogating and regulation. Importantly, the SERCA2-mediated regulation affects Piezo1-dependent migration of endothelial cells. Collectively, we identify SERCA-mediated regulation of Piezos and the functional significance of the linker, providing important insights into the mechanogating and regulation mechanisms of Piezo channels.

Label-free electrochemical aptasensor for detection of alpha-fetoprotein based on AFP-aptamer and thionin/reduced graphene oxide/gold nanoparticles.

PubMed

Li, Guiyin; Li, Shanshan; Wang, Zhihong; Xue, Yewei; Dong, Chenyang; Zeng, Junxiang; Huang, Yong; Liang, Jintao; Zhou, Zhide

2018-04-15

Sensitive and accurate detection of tumor markers is critical to early diagnosis, point-of-care and portable medical supervision. Alpha fetoprotein (AFP) is an important clinical tumor marker for hepatocellular carcinoma (HCC), and the concentration of AFP in human serum is related to the stage of HCC. In this paper, a label-free electrochemical aptasensor for AFP detection was fabricated using AFP-aptamer as the recognition molecule and thionin/reduced graphene oxide/gold nanoparticles (TH/RGO/Au NPs) as the sensor platform. With high electrocatalytic property and large specific surface area, RGO and Au NPs were employed on the screen-printed carbon electrode to load TH molecules. The TH not only acted as a bridging molecule to effectively capture and immobilize AFP-aptamer, but as the electron transfer mediator to provide the electrochemical signal. The AFP detection was based on the monitoring of the electrochemical current response change of TH by the differential pulse voltammetry. Under optimal conditions, the electrochemical responses were proportional to the AFP concentration in the range of 0.1-100.0 μg/mL. The limit of detection was 0.050 μg/mL at a signal-to-noise ratio of 3. The proposed method may provide a promising application of aptamer with the properties of facile procedure, low cost, high selectivity in clinic. Copyright © 2018. Published by Elsevier Inc.

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

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.

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.

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.

Structures of transcription pre-initiation complex with TFIIH and Mediator.

PubMed

Schilbach, S; Hantsche, M; Tegunov, D; Dienemann, C; Wigge, C; Urlaub, H; Cramer, P

2017-11-09

For the initiation of transcription, RNA polymerase II (Pol II) assembles with general transcription factors on promoter DNA to form the pre-initiation complex (PIC). Here we report cryo-electron microscopy structures of the Saccharomyces cerevisiae PIC and PIC-core Mediator complex at nominal resolutions of 4.7 Å and 5.8 Å, respectively. The structures reveal transcription factor IIH (TFIIH), and suggest how the core and kinase TFIIH modules function in the opening of promoter DNA and the phosphorylation of Pol II, respectively. The TFIIH core subunit Ssl2 (a homologue of human XPB) is positioned on downstream DNA by the 'E-bridge' helix in TFIIE, consistent with TFIIE-stimulated DNA opening. The TFIIH kinase module subunit Tfb3 (MAT1 in human) anchors the kinase Kin28 (CDK7), which is mobile in the PIC but preferentially located between the Mediator hook and shoulder in the PIC-core Mediator complex. Open spaces between the Mediator head and middle modules may allow access of the kinase to its substrate, the C-terminal domain of Pol II.

Electrochemical sensing of modified ABO3 perovskite: LaFe0.8 R0.2O3(R= Cr, Co, Al)

NASA Astrophysics Data System (ADS)

Vidya Rajan, N.; Alexander, L. K.

2017-06-01

Perovskite LaFeO3 with orthorhombic structure has been synthesized by citric acid mediated solution method. The effectiveness of ionic radii and Oxidation state of the doping material on ionic conductivity of the host matrix was evaluated by B-site (Fe) doping on LaFeO3 with Cr, Co and Al, resulting LaFe0.8 R0.2O3 (R = Cr, Co, Al). XRD with Rietveld refinement and Raman spectroscopic analysis demonstrate successful synthesis. The effect of the 20% B site doping on electrochemical activity is reported. The doped materials exhibit a decrease in sensing activity towards the non enzymatic detection of H2O2.

Additive-mediated electrochemical synthesis of platelike copper crystals for methanol electrooxidation.

PubMed

Venkatasubramanian, Rajesh; He, Jibao; Johnson, Michael W; Stern, Ilan; Kim, Dae Ho; Pesika, Noshir S

2013-10-29

A room-temperature electrochemical approach to synthesizing anisotropic platelike copper microcrystals and nanocrystals in the presence of potassium bromide is presented. Morphological and elemental characterization was performed using SEM, TEM, and XRD to confirm the anisotropic morphology and crystal structure of the synthesized copper particles. A possible mechanism for explaining the anisotropic crystal growth is proposed on the basis of the preferential adsorption of bromide ions to selective crystal faces. The shape-dependent electrocatalytic property of copper particles is demonstrated by its enhanced catalytic activity for methanol oxidation. Further development of such anisotropic copper particles localized on an electrode surface will lead us to find a suitable alternative for noble metal-based electrocatalysts for the methanol oxidation reaction relevant to fuel cells.

Restoring voluntary control of locomotion after paralyzing spinal cord injury.

PubMed

van den Brand, Rubia; Heutschi, Janine; Barraud, Quentin; DiGiovanna, Jack; Bartholdi, Kay; Huerlimann, Michèle; Friedli, Lucia; Vollenweider, Isabel; Moraud, Eduardo Martin; Duis, Simone; Dominici, Nadia; Micera, Silvestro; Musienko, Pavel; Courtine, Grégoire

2012-06-01

Half of human spinal cord injuries lead to chronic paralysis. Here, we introduce an electrochemical neuroprosthesis and a robotic postural interface designed to encourage supraspinally mediated movements in rats with paralyzing lesions. Despite the interruption of direct supraspinal pathways, the cortex regained the capacity to transform contextual information into task-specific commands to execute refined locomotion. This recovery relied on the extensive remodeling of cortical projections, including the formation of brainstem and intraspinal relays that restored qualitative control over electrochemically enabled lumbosacral circuitries. Automated treadmill-restricted training, which did not engage cortical neurons, failed to promote translesional plasticity and recovery. By encouraging active participation under functional states, our training paradigm triggered a cortex-dependent recovery that may improve function after similar injuries in humans.

Electrochemical characterization of the pyranose 2-oxidase variant N593C shows a complete loss of the oxidase function with full preservation of substrate (dehydrogenase) activity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6cp06009a Click here for additional data file.

PubMed Central

Brugger, Dagmar; Sützl, Leander; Zahma, Kawah; Haltrich, Dietmar; Peterbauer, Clemens K.

2016-01-01

This study presents the first electrochemical characterization of the pyranose oxidase (POx) variant N593C (herein called POx-C), which is considered a promising candidate for future glucose-sensing applications. The resulting cyclic voltammograms obtained in the presence of various concentrations of glucose and mediator (1,4-benzoquinone, BQ), as well as the control experiments by addition of catalase, support the conclusion of a complete suppression of the oxidase function and oxygen reactivity at POx-C. Additionally, these electrochemical experiments demonstrate, contrary to previous biochemical studies, that POx-C has a fully retained enzymatic activity towards glucose. POx-C was immobilized on a special screen-printed electrode (SPE) based on carbon ink and grafted with gold-nanoparticles (GNP). Suppression of the oxygen reactivity at N593C-POx variant is a prerequisite for utilizing POx in electrochemical applications for glucose sensing. To our knowledge, this is the first report presented in the literature showing an absolute conversion of an oxidase into a fully active equivalent dehydrogenase via a single residue exchange. PMID:27808302

An ultra-sensitive Au nanoparticles functionalized DNA biosensor for electrochemical sensing of mercury ions.

PubMed

Zhang, Yanyan; Zhang, Cong; Ma, Rui; Du, Xin; Dong, Wenhao; Chen, Yuan; Chen, Qiang

2017-06-01

The present work describes an effective strategy to fabricate a highly sensitive and selective DNA-biosensor for the determination of mercury ions (Hg 2+ ). The DNA 1 was modified onto the surface of Au electrode by the interaction between sulfydryl group and Au electrode. DNA probe is complementary with DNA 1. In the presence of Hg 2+ , the electrochemical signal increases owing to that Hg 2+ -mediated thymine bases induce the conformation of DNA probe to change from line to hairpin and less DNA probes adsorb into DNA 1. Taking advantage of its reduction property, methylene blue is considered as the signal indicating molecule. For improving the sensitivity of the biosensor, Au nanoparticles (Au NPs) modified reporter DNA 3 is used to adsorb DNA 1. Electrochemical behaviors of the biosensor were evaluated by electrochemical impedance spectroscopy and cyclic voltammetry. Several important parameters which could affect the property of the biosensor were studied and optimized. Under the optimal conditions, the biosensor exhibits wide linear range, high sensitivity and low detection limit. Besides, it displays superior selectivity and excellent stability. The biosensor was also applied for water sample detection with satisfactory result. The novel strategy of fabricating biosensor provides a potential platform for fabricating a variety of metal ions biosensors. Copyright © 2017 Elsevier B.V. All rights reserved.

Silencing of OsGRX17 in rice improves drought stress tolerance by modulating ROS accumulation and stomatal closure

USDA-ARS?s Scientific Manuscript database

Glutaredoxins (GRXs) have emerged as key mediators in plant responses to environmental stimuli by modulating redox-dependent signaling pathways. Here, we report that RNAi-mediated suppression of the rice gene OsGRXS17, encoding a monothiol GRX with a CGFS-type active site motif, elevates H2O2 produc...

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.

A multifunctional hemin@metal-organic framework and its application to construct an electrochemical aptasensor for thrombin detection.

PubMed

Xie, Shunbi; Ye, Jiawei; Yuan, Yali; Chai, Yaqin; Yuan, Ruo

2015-11-21

A new type of multifunctional metal-organic framework (MOF) has been synthesized by encapsulating hemin into the nano-sized Fe-MIL-88 MOFs (hemin@MOFs) and first applied in an electrochemical aptasensor to detect thrombin (TB) with the aid of an enzyme for signal amplification. The gold nanoparticle functionalized hemin@MOFs (Au/hemin@MOFs) have not only simultaneously served as redox mediators and solid electrocatalysts, but have also been utilized as an ideal loading platform to immobilize a large number of biomolecules. In this aptasensor, Au/hemin@MOFs conjugated with glucose oxidase (GOD) and thrombin binding aptamer (TBA II) were used as the secondary aptamer bioconjugates (Au/hemin@MOF-TBA II-GOD bioconjugates), and TB was sandwiched between Au/hemin@MOF-TBA II-GOD bioconjugates and the amino-terminated TBA I which was self-assembled on the gold nanoparticle (AuNP) modified electrode. The GOD could oxidize glucose into gluconic acid accompanied by the generation of H2O2. The generated H2O2 on the electrode surface was further electrocatalyzed by hemin@MOFs to amplify the electrochemical signal of hemin contained in hemin@MOFs. Therefore, the synthesized hemin@MOFs represented a new paradigm for multifunctional materials since it combined three different functions including serving as catalysts, redox mediators and loading platforms within a single material. With such an ingenious design, a wide linear range of 0.0001 nM to 30 nM was acquired with a relatively low detection limit of 0.068 pM for TB detection.

Early detection of Candida albicans biofilms at porous electrodes.

PubMed

Congdon, Robert B; Feldberg, Alexander S; Ben-Yakar, Natalie; McGee, Dennis; Ober, Christopher; Sammakia, Bahgat; Sadik, Omowunmi A

2013-02-15

We describe the development of an electrochemical sensor for early detection of biofilm using Candida albicans. The electrochemical sensor used the ability of biofilms to accept electrons from redox mediators relative to the number of metabolically active cells present. Cyclic voltammetry and differential pulse voltammetry techniques were used to monitor the redox reaction of K(3)Fe(CN)(6) at porous reticulated vitreous carbon (RVC) (238.7 cm(2)) working electrodes versus Ag/AgCl reference. A shift in the peak potential occurred after 12 h of film growth, which is attributed to the presence of C. albicans. Moreover, the intensity of the ferricyanide reduction peak first increased as C. albicans deposited onto the porous electrodes at various growth times. The peak current subsequently decreased at extended periods of growth of 48 h. The reduction in peak current was attributed to the biofilm reaching its maximum growth thickness, which correlated with the maximum number of metabolically active cells. The observed diffusion coefficients for the bare RVC and biofilm-coated electrodes were 2.2 × 10(-3) and 7.0 × 10(-6) cm(2)/s, respectively. The increase in diffusivity from the bare electrode to the biofilm-coated electrode indicated some enhancement of electron transfer mediated by the biofilm to the porous electrode. Verification of the growth of biofilm was achieved using scanning electron microcopy and laser scanning confocal imaging microscopy. Validation with conventional plating techniques confirmed that the correlation (R(2) = 0.9392) could be achieved between the electrochemical sensors data and colony-forming units. Copyright © 2012 Elsevier Inc. All rights reserved.

The Mediator Kinase Module Restrains Epidermal Growth Factor Receptor Signaling and Represses Vulval Cell Fate Specification in Caenorhabditis elegans.

PubMed

Grants, Jennifer M; Ying, Lisa T L; Yoda, Akinori; You, Charlotte C; Okano, Hideyuki; Sawa, Hitoshi; Taubert, Stefan

2016-02-01

Cell signaling pathways that control proliferation and determine cell fates are tightly regulated to prevent developmental anomalies and cancer. Transcription factors and coregulators are important effectors of signaling pathway output, as they regulate downstream gene programs. In Caenorhabditis elegans, several subunits of the Mediator transcriptional coregulator complex promote or inhibit vulva development, but pertinent mechanisms are poorly defined. Here, we show that Mediator's dissociable cyclin dependent kinase 8 (CDK8) module (CKM), consisting of cdk-8, cic-1/Cyclin C, mdt-12/dpy-22, and mdt-13/let-19, is required to inhibit ectopic vulval cell fates downstream of the epidermal growth factor receptor (EGFR)-Ras-extracellular signal-regulated kinase (ERK) pathway. cdk-8 inhibits ectopic vulva formation by acting downstream of mpk-1/ERK, cell autonomously in vulval cells, and in a kinase-dependent manner. We also provide evidence that the CKM acts as a corepressor for the Ets-family transcription factor LIN-1, as cdk-8 promotes transcriptional repression by LIN-1. In addition, we find that CKM mutation alters Mediator subunit requirements in vulva development: the mdt-23/sur-2 subunit, which is required for vulva development in wild-type worms, is dispensable for ectopic vulva formation in CKM mutants, which instead display hallmarks of unrestrained Mediator tail module activity. We propose a model whereby the CKM controls EGFR-Ras-ERK transcriptional output by corepressing LIN-1 and by fine tuning Mediator specificity, thus balancing transcriptional repression vs. activation in a critical developmental signaling pathway. Collectively, these data offer an explanation for CKM repression of EGFR signaling output and ectopic vulva formation and provide the first evidence of Mediator CKM-tail module subunit crosstalk in animals. Copyright © 2016 by the Genetics Society of America.

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

Cell Adhesions: Actin-Based Modules that Mediate Cell-Extracellular Matrix and Cell-Cell Interactions

PubMed Central

Bachir, Alexia; Horwitz, Alan Rick; Nelson, W. James; Bianchini, Julie M.

2018-01-01

Cell adhesions link cells to the extracellular matrix (ECM) and to each other, and depend on interactions with the actin cytoskeleton. Both cell-ECM and cell-cell adhesion sites contain discrete, yet overlapping functional modules. These modules establish physical association with the actin cytoskeleton, locally modulate actin organization and dynamics, and trigger intracellular signaling pathways. Interplay between these modules generates distinct actin architectures that underlie different stages, types, and functions of cell-ECM and cell-cell adhesions. Actomyosin contractility is required to generate mature, stable adhesions, as well as sense and translate the mechanical properties of the cellular environment to changes in cell organization and behavior. In this chapter we discuss the organization and function of different adhesion modules and how they interact with the actin cytoskeleton. We highlight the molecular mechanisms of mechanotransduction in adhesions, and how adhesion molecules mediate crosstalk between cell-ECM and cell-cell adhesion sites. PMID:28679638

Strong G-Protein-Mediated Inhibition of Sodium Channels.

PubMed

Mattheisen, Glynis B; Tsintsadze, Timur; Smith, Stephen M

2018-05-29

Voltage-gated sodium channels (VGSCs) are strategically positioned to mediate neuronal plasticity because of their influence on action potential waveform. VGSC function may be strongly inhibited by local anesthetic and antiepileptic drugs and modestly modulated via second messenger pathways. Here, we report that the allosteric modulators of the calcium-sensing receptor (CaSR) cinacalcet, calindol, calhex, and NPS 2143 completely inhibit VGSC current in the vast majority of cultured mouse neocortical neurons. This form of VGSC current block persisted in CaSR-deficient neurons, indicating a CaSR-independent mechanism. Cinacalcet-mediated blockade of VGSCs was prevented by the guanosine diphosphate (GDP) analog GDPβs, indicating that G-proteins mediated this effect. Cinacalcet inhibited VGSCs by increasing channel inactivation, and block was reversed by prolonged hyperpolarization. Strong cinacalcet inhibition of VGSC currents was also present in acutely isolated mouse cortical neurons. These data identify a dynamic signaling pathway by which G-proteins regulate VGSC current to indirectly modulate central neuronal excitability. Published by Elsevier Inc.

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.

Glutamate Receptor GluA1 Subunit Is Implicated in Capsaicin Induced Modulation of Amygdala LTP but Not LTD

ERIC Educational Resources Information Center

Gebhardt, Christine; Albrecht, Doris

2018-01-01

Capsaicin has been shown to modulate synaptic plasticity in various brain regions including the amygdala. Whereas in the lateral amygdala the modulatory effect of capsaicin on long-term potentiation (LA-LTP) is mediated by TRPV1 channels, we have recently shown that capsaicin-induced enhancement of long term depression (LA-LTD) is mediated by…

Effective connectivity during processing of facial affect: evidence for multiple parallel pathways.

PubMed

Dima, Danai; Stephan, Klaas E; Roiser, Jonathan P; Friston, Karl J; Frangou, Sophia

2011-10-05

The perception of facial affect engages a distributed cortical network. We used functional magnetic resonance imaging and dynamic causal modeling to characterize effective connectivity during explicit (conscious) categorization of affective stimuli in the human brain. Specifically, we examined the modulation of connectivity from posterior regions of the face-processing network to the lateral ventral prefrontal cortex (VPFC) during affective categorization and we tested for a potential role of the amygdala (AMG) in mediating this modulation. We found that explicit processing of facial affect led to prominent modulation (increase) in the effective connectivity from the inferior occipital gyrus (IOG) to the VPFC, while there was less evidence for modulation of the afferent connections from fusiform gyrus and AMG to VPFC. More specifically, the forward connection from IOG to the VPFC exhibited a selective increase under anger (as opposed to fear or sadness). Furthermore, Bayesian model comparison suggested that the modulation of afferent connections to the VPFC was mediated directly by facial affect, as opposed to an indirect modulation mediated by the AMG. Our results thus suggest that affective information is conveyed to the VPFC along multiple parallel pathways and that AMG activity is not sufficient to account for the gating of information transfer to the VPFC during explicit emotional processing.

Nanobioprobe mediated DNA aptamers for explosive detection.

PubMed

Priyanka; Shorie, Munish; Bhalla, Vijayender; Pathania, Preeti; Suri, C Raman

2014-02-04

Specific nucleic acid aptamers using the microtiter plate based modified SELEX method against explosive trinitrotoluene are reported. Efficient partitioning of dsDNA was carried out using streptavidin labeled gold nanoprobes for the selection of specific aptamers. The selected binders having an affinity of ~10(-7) M were used in the newly developed electrochemical aptasensor, exhibiting a detection limit of around 1 ppb for trinitrotoluene.

Biomass production from electricity using ammonia as an electron carrier in a reverse microbial fuel cell.

PubMed

Khunjar, Wendell O; Sahin, Asli; West, Alan C; Chandran, Kartik; Banta, Scott

2012-01-01

The storage of renewable electrical energy within chemical bonds of biofuels and other chemicals is a route to decreasing petroleum usage. A critical challenge is the efficient transfer of electrons into a biological host that can covert this energy into high energy organic compounds. In this paper, we describe an approach whereby biomass is grown using energy obtained from a soluble mediator that is regenerated electrochemically. The net result is a separate-stage reverse microbial fuel cell (rMFC) that fixes CO₂ into biomass using electrical energy. We selected ammonia as a low cost, abundant, safe, and soluble redox mediator that facilitated energy transfer to biomass. Nitrosomonas europaea, a chemolithoautotroph, was used as the biocatalyst due to its inherent capability to utilize ammonia as its sole energy source for growth. An electrochemical reactor was designed for the regeneration of ammonia from nitrite, and current efficiencies of 100% were achieved. Calculations indicated that overall bioproduction efficiency could approach 2.7±0.2% under optimal electrolysis conditions. The application of chemolithoautotrophy for industrial bioproduction has been largely unexplored, and results suggest that this and related rMFC platforms may enable biofuel and related biochemical production.

The electrochemical behavior of a FAD dependent glucose dehydrogenase with direct electron transfer subunit by immobilization on self-assembled monolayers.

PubMed

Lee, Inyoung; Loew, Noya; Tsugawa, Wakako; Lin, Chi-En; Probst, David; La Belle, Jeffrey T; Sode, Koji

2018-06-01

Continuous glucose monitoring (CGM) is a vital technology for diabetes patients by providing tight glycemic control. Currently, many commercially available CGM sensors use glucose oxidase (GOD) as sensor element, but this enzyme is not able to transfer electrons directly to the electrode without oxygen or an electronic mediator. We previously reported a mutated FAD dependent glucose dehydrogenase complex (FADGDH) capable of direct electron transfer (DET) via an electron transfer subunit without involving oxygen or a mediator. In this study, we investigated the electrochemical response of DET by controlling the immobilization of DET-FADGDH using 3 types of self-assembled monolayers (SAMs) with varying lengths. With the employment of DET-FADGDH and SAM, high current densities were achieved without being affected by interfering substances such as acetaminophen and ascorbic acid. Additionally, the current generated from DET-FADGDH electrodes decreased with increasing length of SAM, suggesting that the DET ability can be affected by the distance between the enzyme and the electrode. These results indicate the feasibility of controlling the immobilization state of the enzymes on the electrode surface. Copyright © 2017. Published by Elsevier B.V.

Impedimetric biosensor based on cell-mediated bioimprinted films for bacterial detection.

PubMed

Qi, Peng; Wan, Yi; Zhang, Dun

2013-01-15

This work presents the synthesis of bacteria-mediated bioimprinted films for selective bacterial detection. Marine pathogen sulfate-reducing bacteria (SRB) were chosen as the template bacteria. Chitosan (CS) doped with reduced graphene sheets (RGSs) was electrodeposited on an indium tin oxide electrode, and the resulting RGSs-CS hybrid film served as a platform for bacterial attachment. The electrodeposition conditions were optimized to obtain RGSs-CS hybrid films with excellent electrochemical performance. A layer of nonconductive CS film was deposited to embed the pathogen, and acetone was used to wash away the bacterial templates. Electrochemical impedance spectroscopy was performed to characterize the stepwise modification process and monitor the SRB population. Faradic impedance measurements revealed that the charge transfer resistance (R(ct)) increased with increased SRB concentration. A linear relationship between ΔR(ct) and the logarithm of SRB concentration was obtained within the concentration range of 1.0×10(4)cfum L(-1) to 1.0×10(8)cfum L(-1). The impedimetric sensor showed good selectivity towards SRB based on size and shape. Hence, selectivity for bacterial detection can be improved if the bioimprinting technique is combined with other bio-recognition elements. Copyright © 2012 Elsevier B.V. All rights reserved.

A Highly Active Low Voltage Redox Mediator for Enhanced Rechargeability of Lithium-Oxygen Batteries.

PubMed

Kundu, Dipan; Black, Robert; Adams, Brian; Nazar, Linda F

2015-12-23

Owing to its high theoretical specific energy, the Li-oxygen battery is one of the fundamentally most promising energy storage systems, but also one of the most challenging. Poor rechargeability, involving the oxidation of insoluble and insulating lithium peroxide (Li2O2), has remained the "Achilles' heel" of this electrochemical energy storage system. We report here on a new redox mediator tris[4-(diethylamino)phenyl]amine (TDPA), that-at 3.1 V-exhibits the lowest and closest potential redox couple compared to the equilibrium voltage of the Li-oxygen cell of those reported to date, with a second couple also at a low potential of 3.5 V. We show it is a soluble "catalyst" capable of lowering the Li2O2 charging potential by >0.8 V without requiring direct electrical contact of the peroxide and that it also facilitates high discharge capacities. Its chemical and electrochemical stability, fast diffusion kinetics, and two dynamic redox potentials represent a significant advance in oxygen-evolution catalysis. It enables Li-O2 cells that can be recharged more than 100 cycles with average round-trip efficiencies >80%, opening a new avenue for practical Li-oxygen batteries.

Biomass Production from Electricity Using Ammonia as an Electron Carrier in a Reverse Microbial Fuel Cell

PubMed Central

West, Alan C.; Chandran, Kartik; Banta, Scott

2012-01-01

The storage of renewable electrical energy within chemical bonds of biofuels and other chemicals is a route to decreasing petroleum usage. A critical challenge is the efficient transfer of electrons into a biological host that can covert this energy into high energy organic compounds. In this paper, we describe an approach whereby biomass is grown using energy obtained from a soluble mediator that is regenerated electrochemically. The net result is a separate-stage reverse microbial fuel cell (rMFC) that fixes CO2 into biomass using electrical energy. We selected ammonia as a low cost, abundant, safe, and soluble redox mediator that facilitated energy transfer to biomass. Nitrosomonas europaea, a chemolithoautotroph, was used as the biocatalyst due to its inherent capability to utilize ammonia as its sole energy source for growth. An electrochemical reactor was designed for the regeneration of ammonia from nitrite, and current efficiencies of 100% were achieved. Calculations indicated that overall bioproduction efficiency could approach 2.7±0.2% under optimal electrolysis conditions. The application of chemolithoautotrophy for industrial bioproduction has been largely unexplored, and results suggest that this and related rMFC platforms may enable biofuel and related biochemical production. PMID:23028643

Intensive Study on the Catalytical Behavior of N-Methylphenothiazine as a Soluble Mediator to Oxidize the Li2O2 Cathode of the Li-O2 Battery.

PubMed

Feng, Ningning; Mu, Xiaowei; Zhang, Xueping; He, Ping; Zhou, Haoshen

2017-02-01

Aprotic Li-O 2 batteries have attracted worldwide interest owing to their ultrahigh theoretical energy density. However, the practical Li-O 2 batteries still suffer from high charge overpotential and low energy efficiency resulting from the sluggish kinetics in electrochemically oxidizing the insulating lithium peroxide (Li 2 O 2 ). Recently, dissolved redox mediators in the electrolyte have enabled the effective catalytic oxidation of Li 2 O 2 at the liquid-solid interface. Here, we report that the incorporation of N-methylphenothiazine (MPT), as a redox shuttle in Li-O 2 batteries, provides a dramatic reduction in charge overpotential to 0.67 V and an improved round-trip efficiency close to 76%. Moreover, the efficacy of MPT in Li-O 2 cells was further investigated by various characterizations. On charging, MPT + cations are first generated electrochemically at the cathode surface and subsequently oxidize the solid discharge products Li 2 O 2 through a chemical reaction. Furthermore, the presence of MPT has been demonstrated to improve the cycling stability of the cells and suppress side reactions arising from carbon and electrolytes at high potentials.

Immobilization of a mediator onto carbon cloth electrode and employment of the modified electrode to an electroenzymatic bioreactor.

PubMed

Jeong, Eun-Seon; Sathishkumar, Muthuswamy; Jayabalan, Rasu; Jeong, Su-Hyeon; Park, Song-Yie; Mun, Sung-Phil; Yun, Sei-Eok

2012-10-01

5,5'-Dithiobis(2-nitrobenzoic acid) (DTNB) was selected as an electron transfer mediator and was covalently immobilized onto high porosity carbon cloth to employ as a working electrode in an electrochemical NAD(+)-regeneration process, which was coupled to an enzymatic reaction. The voltammetric behavior of DTNB attached to carbon cloth resembled that of DTNB in buffered aqueous solution, and the electrocatalytic anodic current grew continuously upon addition of NADH at different concentrations, indicating that DTNB is immobilized to carbon cloth effectively and the immobilized DTNB is active as a soluble one. The bioelectrocatalytic NAD+ regeneration was coupled to the conversion of L-glutamate into alpha-ketoglutarate by L-glutamate dehydrogenase within the same microreactor. The conversion at 3 mM monosodium glutamate was very rapid, up to 12 h, to result in 90%, and then slow up to 24 h, showing 94%, followed by slight decrease. Low conversion was shown when substrate concentration exceeding 4 mM was tested, suggesting that L-glutamate dehydrogenase is inhibited by alpha-ketoglutarate. However, our electrochemical NAD+ regeneration procedure looks advantageous over the enzymatic procedure using NADH oxidase, from the viewpoint of reaction time to completion.

Advances in studying phasic dopamine signaling in brain reward mechanisms

PubMed Central

Wickham, Robert J.; Solecki, Wojciech; Rathbun, Liza R.; Neugebauer, Nichole M.; Wightman, R. Mark; Addy, Nii A.

2013-01-01

The last sixty years of research have provided extraordinary advances of our knowledge of the reward system. Since its initial discovery as a neurotransmitter by Carlsson and colleagues (Carlsson et al., 1957), dopamine (DA) has emerged as an important mediator of reward processing. As a result, a number of electrochemical techniques have been developed to directly measure DA levels in the brain using various preparations. Many of these techniques and preparations differ in the types of questions that they can address. Together, these techniques have begun to elucidate the complex roles of tonic and phasic DA signaling in reward processing and in addiction. In this review, we will first provide a guide for the most commonly used electrochemical methods for DA detection and describe their utility in furthering our knowledge about DA's role in reward and addiction. Second, we will review the value of common in vitro and in vivo preparations and describe their ability to address different types of questions. Last, we will review recent data that has provided new insight of the mechanisms of in vivo phasic DA signaling and its role in reward processing and reward-mediated behavior. PMID:23747914

Resonance-mode electrochemical impedance measurements of silicon dioxide supported lipid bilayer formation and ion channel mediated charge transport.

PubMed

Lundgren, Anders; Hedlund, Julia; Andersson, Olof; Brändén, Magnus; Kunze, Angelika; Elwing, Hans; Höök, Fredrik

2011-10-15

A single-chip electrochemical method based on impedance measurements in resonance mode has been employed to study lipid monolayer and bilayer formation on hydrophobic alkanethiolate and SiO(2) substrates, respectively. The processes were monitored by temporally resolving changes in interfacial capacitance and resistance, revealing information about the rate of formation, coverage, and defect density (quality) of the layers at saturation. The resonance-based impedance measurements were shown to reveal significant differences in the layer formation process of bilayers made from (i) positively charged lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-ethylphosphocholine (POEPC), (ii) neutral lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) on SiO(2), and (iii) monolayers made from POEPC on hydrophobic alkanethiolate substrates. The observed responses were represented with an equivalent circuit, suggesting that the differences primarily originate from the presence of a conductive aqueous layer between the lipid bilayers and the SiO(2). In addition, by adding the ion channel gramicidin D to bilayers supported on SiO(2), channel-mediated charge transport could be measured with high sensitivity (resolution around 1 pA). © 2011 American Chemical Society

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.

Building an open academic environment - a new approach to empowering students in their learning of anatomy through 'Shadow Modules'.

PubMed

Scott, Jonathan L; Moxham, Bernard J; Rutherford, Stephen M

2014-03-01

Teaching and learning in anatomy is undertaken by a variety of methodologies, yet all of these pedagogies benefit from students discussing and reflecting upon their learning activities. An approach of particular potency is peer-mediated learning, through either peer-teaching or collaborative peer-learning. Collaborative, peer-mediated, learning activities help promote deep learning approaches and foster communities of practice in learning. Students generally flourish in collaborative learning settings but there are limitations to the benefits of collaborative learning undertaken solely within the confines of modular curricula. We describe the development of peer-mediated learning through student-focused and student-led study groups we have termed 'Shadow Modules'. The 'Shadow Module' takes place parallel to the formal academically taught module and facilitates collaboration between students to support their learning for that module. In 'Shadow Module' activities, students collaborate towards curating existing online open resources as well as developing learning resources of their own to support their study. Through the use of communication technologies and Web 2.0 tools these resources are able to be shared with their peers, thus enhancing the learning experience of all students following the module. The Shadow Module activities have the potential to lead to participants feeling a greater sense of engagement with the subject material, as well as improving their study and group-working skills and developing digital literacy. The outputs from Shadow Module collaborative work are open-source and may be utilised by subsequent student cohorts, thus building up a repository of learning resources designed by and for students. Shadow Module activities would benefit all pedagogies in the study of anatomy, and support students moving from being passive consumers to active participants in learning. © 2013 Anatomical Society.

Amplified electrochemical detection of nucleic acid hybridization via selective preconcentration of unmodified gold nanoparticles.

PubMed

Li, Yuan; Tian, Rui; Zheng, Xingwang; Huang, Rongfu

2016-08-31

The common drawback of optical methods for rapid detection of nucleic acid by exploiting the differential affinity of single-/double-stranded nucleic acids for unmodified gold nanoparticles (AuNPs) is its relatively low sensitivity. In this article, on the basis of selective preconcentration of AuNPs unprotected by single-stranded DNA (ssDNA) binding, a novel electrochemical strategy for nucleic acid sequence identification assay has been developed. Through detecting the redox signal mediated by AuNPs on 1, 6-hexanedithiol blocked gold electrode, the proposed method is able to ensure substantial signal amplification and a low background current. This strategy is demonstrated for quantitative analysis of the target microRNA (let-7a) in human breast adenocarcinoma cells, and a detection limit of 16 fM is readily achieved with desirable specificity and sensitivity. These results indicate that the selective preconcentration of AuNPs for electrochemical signal readout can offer a promising platform for the detection of specific nucleic acid sequence. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydrogel-based electrochemical sensor for non-invasive and continuous glucose monitoring

NASA Astrophysics Data System (ADS)

Park, Habeen; Lee, Ji-Young; Kim, Dong-Chul; Koh, Younggook; Cha, Junhoe

2017-07-01

Monitoring blood glucose level of diabetic patients is crucial in diabetes care from life threating complications. Selfmonitoring blood glucose (SMBG) that involves finger prick to draw blood samples into the measurement system is a widely-used method of routine measurement of blood glucose levels to date. SMBG includes, however, unavoidable pain problems resulting from the repetitive measurements. We hereby present a hydrogel-based electrochemical (H-EC) sensor to monitor the glucose level, non-invasively. Glucose oxidase (GOx) was immobilized in the disc-type hydroxyethyl methacrylate (HEMA) based hydrogel and kept intact in the hydrogel. Fast electron transfer mediated by Prussian blue (PB, hexacyanoferrate) generated efficient signal amplifications to facilitate the detection of the extracted glucose from the interstitial fluid. The linear response and the selectivity against glucose of the H-EC sensor were validated by chronoamperometry. For the practical use, the outcomes from the correlation of the extracted glucose concentration and the blood glucose value by on-body extraction, as well as the validation of the hydrogel-based electrochemical (H-EC) device, were applied to the on-body glucose monitoring.

Electrochemical processing of solid waste

NASA Technical Reports Server (NTRS)

Bockris, J. OM.; Hitchens, G. D.; Kaba, L.

1988-01-01

The investigation into electrolysis as a means of waste treatment and recycling on manned space missions is described. The electrochemical reactions of an artificial fecal waste mixture was examined. Waste electrolysis experiments were performed in a single compartment reactor, on platinum electrodes, to determine conditions likely to maximize the efficiency of oxidation of fecal waste material to CO2. The maximum current efficiencies for artificial fecal waste electrolysis to CO2 was found to be around 50 percent in the test apparatus. Experiments involving fecal waste oxidation on platinum indicates that electrodes with a higher overvoltage for oxygen evolution such as lead dioxide will give a larger effective potential range for organic oxidation reactions. An electrochemical packed column reactor was constructed with lead dioxide as electrode material. Preliminary experiments were performed using a packed-bed reactor and continuous flow techniques showing this system may be effective in complete oxidation of fecal material. The addition of redox mediator Ce(3+)/Ce(4+) enhances the oxidation process of biomass components. Scientific literature relevant to biomass and fecal waste electrolysis were reviewed.

Carbonization-dependent nitrogen-doped hollow porous carbon nanospheres synthesis and electrochemical study for supercapacitors

NASA Astrophysics Data System (ADS)

Zhou, Lingyun; Xie, Guohong; Chen, Xiling

2018-05-01

In this paper, a nitrogen-doped hollow microporous carbon nanospheres was synthesized via the combination of hyper-crosslinking mediated self-assembly and further pyrolysis using polylactide-b-polystyrene (PLA-b-PS) copolymers and aniline monomers as precursor. The pore structure and the correlative electrochemical performance of nitrogen-doped hollow microporous carbon nanospheres were affected by the molar mass ratio of aniline and PS in block copolymers and the carbonization conditions. The electrochemical measurements results showed that the obtained PLA150-PS250-N4-900-10H sample with nitrogen content of 3.57% and the BET surface area of 945 m2 g-1 displays the best capacitance performance. At a current density of 1.0 Ag-1, the resultant specific capacitance is 250 Fg-1. In addition, it also exhibits high capacitance retention of 98% after charging-discharging 1500 times at 25 Ag-1. The results demonstrate the nitrogen-doped hollow microporous carbon nanospheres can be used as promising supercapacitor electrode materials for high performance energy storage devices.

Oxidation-Mediated Fingering in Liquid Metals

NASA Astrophysics Data System (ADS)

Eaker, Collin B.; Hight, David C.; O'Regan, John D.; Dickey, Michael D.; Daniels, Karen E.

2017-10-01

We identify and characterize a new class of fingering instabilities in liquid metals; these instabilities are unexpected due to the large interfacial tension of metals. Electrochemical oxidation lowers the effective interfacial tension of a gallium-based liquid metal alloy to values approaching zero, thereby inducing drastic shape changes, including the formation of fractals. The measured fractal dimension (D =1.3 ±0.05 ) places the instability in a different universality class than other fingering instabilities. By characterizing changes in morphology and dynamics as a function of droplet volume and applied electric potential, we identify the three main forces involved in this process: interfacial tension, gravity, and oxidative stress. Importantly, we find that electrochemical oxidation can generate compressive interfacial forces that oppose the tensile forces at a liquid interface. The surface oxide layer ultimately provides a physical and electrochemical barrier that halts the instabilities at larger positive potentials. Controlling the competition between interfacial tension and oxidative (compressive) stresses at the interface is important for the development of reconfigurable electronic, electromagnetic, and optical devices that take advantage of the metallic properties of liquid metals.

Copper recovery and gold enrichment from waste printed circuit boards by mediated electrochemical oxidation.

PubMed

Fogarasi, Szabolcs; Imre-Lucaci, Florica; Imre-Lucaci, Arpád; Ilea, Petru

2014-05-30

The present study aims to develop an eco-friendly chemical-electrochemical process for the simultaneous recovery of copper and separation of a gold rich residue from waste printed circuit boards (WPCBs). The process was carried out by employing two different types of reactors coupled in series: a leaching reactor with a perforated rotating drum, for the dissolution of base metals and a divided electrochemical reactor for the regeneration of the leaching solution with the parallel electrowinning of copper. The process performances were evaluated on the basis of the dissolution efficiency, current efficiency and specific energy consumptions. Finally a process scale up was realized taking into consideration the optimal values of the operating parameters. The laboratory scale leaching plant allowed the recovery of a high purity copper deposit (99.04wt.%) at a current efficiency of 63.84% and specific energy consumption of 1.75kWh/kg cooper. The gold concentration in the remained solid residue was 25 times higher than the gold concentration in the initial WPCB samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Low heart rate variability in unemployed men: The possible mediating effects of life satisfaction.

PubMed

Jandackova, V K; Jackowska, M

2015-01-01

Unemployment has consistently been associated with increased risk of cardiovascular disease and premature mortality, and impaired autonomic modulation of the heart might be one mechanism partly explaining this. This study examined whether the possible effect of unemployment on cardiac autonomic modulation is in part mediated by lower psychological well-being. The sample comprised of 15 job-seeking men aged 30-49 years matched with 15 employed men on age, type of job, smoking habits, alcohol intake, frequency of physical activity, and body mass index. Heart rate variability (HRV) during a modified orthostatic test was the measure of cardiac autonomic modulation, and life satisfaction was the measure of psychological well-being. Unemployed men had significantly lower overall HRV (p = .040) than controls. This association was partially mediated through lower general life satisfaction, and in particular, by low financial satisfaction, independently of demographic and/or behavioral factors that influence HRV. These findings suggest that seeking a job is a potential stressor that may reduce overall HRV and contribute towards disturbance of cardiac autonomic modulation in men. Financial difficulties could be one mechanism through which the effects of unemployment are translated into impaired autonomic modulation.

Development of mediated BOD biosensor system of flow injection mode for shochu distillery wastewater.

PubMed

Oota, Shinichi; Hatae, Yuta; Amada, Kei; Koya, Hidekazu; Kawakami, Mitsuyasu

2010-09-15

Although microbial biochemical oxygen demand (BOD) sensors utilizing redox mediators have attracted much attention as a rapid BOD measurement method, little attempts have been made to apply the mediated BOD biosensors to the flow injection analysis system. In this work, a mediated BOD sensor system of flow injection mode, constructed by combining an immobilized microbial reactor with an electrochemical flow cell of three electrodes configuration, has been developed to estimate BOD of shochu distillery wastewater (SDW). It was demonstrated consequently that the mediated sensing was realized by employing phosphate buffer containing potassium hexacyanoferrate as the carrier. The output current was found to yield a peak with a sample injection, and to result from reoxidation of reduced mediator at the electrode. By employing the peak area as the sensor response, the effects of flow rate and pH of the carrier on the sensitivity were investigated. The sensor system using a microorganism of high SDW-assimilation capacity showed good performance and proved to be available for estimation of BOD of SDW. Copyright 2010 Elsevier B.V. All rights reserved.

Signal-on electrochemical assay for label-free detection of TdT and BamHI activity based on grown DNA nanowire-templated copper nanoclusters.

PubMed

Hu, Yufang; Zhang, Qingqing; Xu, Lihua; Wang, Jiao; Rao, Jiajia; Guo, Zhiyong; Wang, Sui

2017-11-01

Electrochemical methods allow fast and inexpensive analysis of enzymatic activity. Here, a simple and yet efficient "signal-on" electrochemical assay for sensitive, label-free detection of DNA-related enzyme activity was established on the basis of terminal deoxynucleotidyl transferase (TdT)-mediated extension strategy. TdT, which is a template-independent DNA polymerase, can catalyze the sequential addition of deoxythymidine triphosphate (dTTP) at the 3'-OH terminus of single-stranded DNA (ssDNA); then, the TdT-yield T-rich DNA nanowires can be employed as the synthetic template of copper nanoclusters (CuNCs). Grown DNA nanowires-templated CuNCs (noted as DNA-CuNCs) were attached onto graphene oxide (GO) surface and exhibited unique electrocatalytic activity to H 2 O 2 reduction. Under optimal conditions, the proposed biosensor was utilized for quantitatively monitoring TdT activity, with the observed LOD of 0.1 U/mL. It also displayed high selectivity to TdT with excellent stability, and offered a facile, convenient electrochemical method for TdT-relevant inhibitors screening. Moreover, the proposed sensor was successfully used for BamHI activity detection, in which a new 3'-OH terminal was exposed by the digestion of a phosphate group. Ultimately, it has good prospects in DNA-related enzyme-based biochemical studies, disease diagnosis, and drug discovery. Graphical Abstract Extraordinary TdT-generated DNA-CuNCs are synthesized and act as a novel electrochemical sensing platform for sensitive detection of TdT and BamHI activity in biological environments.

ARM-microcontroller based portable nitrite electrochemical analyzer using cytochrome c reductase biofunctionalized onto screen printed carbon electrode.

PubMed

Santharaman, Paulraj; Venkatesh, Krishna Arun; Vairamani, Kanagavel; Benjamin, Alby Robson; Sethy, Niroj K; Bhargava, Kalpana; Karunakaran, Chandran

2017-04-15

Nitrite (NO 2 - ) supplementation limits hypoxia-induced oxidative stress and activates the alternate NO pathway which may partially account for the nitrite-mediated cardioprotection. So, sensitive and selective biosensors with point-of-care devices need to be explored to detect the physiological nitrite level due to its important role in human pathophysiology. In this work, cytochrome c reductase (CcR) biofunctionalized self assembled monolayer (SAM) functionalized on gold nanoparticles (GNPs) in polypyrrole (PPy) nanocomposite onto the screen printed carbon electrode (SPCE) was investigated as a biosensor for the detection of nitrite based on its electrochemical and catalytic properties. CcR was covalently coupled with SAM layers on GNPs by using EDC and NHS. Direct electrochemical response of CcR biofunctionalized electrodes showed a couple of well-defined and nearly reversible cyclic voltammetric peaks at -0.34 and -0.45 vs. Ag/AgCl. Under optimal conditions, the biosensor could be used for the determination of NO 2 - with a linear range from 0.1-1600µm and a detection limit of 60nM with a sensitivity of 0.172µAµM -1 cm -2 . Further, we have designed and developed a novel and cost effective portable electrochemical analyzer for the measurement of NO 2 - in hypoxia induced H9c2 cardiac cells using ARM microcontroller. The results obtained here using the developed portable electrochemical nitrite analyzer were also compared with the standard cyclic voltammetry instrument and found in agreement with each other. Copyright © 2016 Elsevier B.V. All rights reserved.

The Efficacy of IRIS "STAR Legacy" Modules under Different Instructional Conditions

ERIC Educational Resources Information Center

Sayeski, Kristin L.; Hamilton-Jones, Bethany; Oh, Susan

2015-01-01

The vast majority of special education teacher preparation programs in the United States incorporate the IRIS Center's "STAR Legacy" modules into their coursework. Given the diversity of module content and ways in which the modules are employed, the purpose of this study was to explore the potential mediating effects of instructional…

Peptide-based biosensors: From self-assembled interfaces to molecular probes in electrochemical assays.

PubMed

Puiu, Mihaela; Bala, Camelia

2018-04-01

Redox-tagged peptides have emerged as functional materials with multiple applications in the area of sensing and biosensing applications due to their high stability, excellent redox properties and versatility of biomolecular interactions. They allow direct observation of molecular interactions in a wide range of affinity and enzymatic assays and act as electron mediators. Short helical peptides possess the ability to self-assemble in specific configurations with the possibility to develop in highly-ordered, stable 1D, 2D and 3D architectures in a hierarchical controlled manner. We provide here a brief overview of the electrochemical techniques available to study the electron transfer in peptide films with particular interest in developing biosensors with immobilized peptide motifs, for biological and clinical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

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

The on/off switches of the mitochondrial uncoupling proteins

PubMed Central

Azzu, Vian; Brand, Martin D.

2013-01-01

Mitochondrial uncoupling proteins disengage substrate oxidation from ADP phosphorylation by dissipating the proton electrochemical gradient that is required for ATP synthesis. In doing this, the archetypal uncoupling protein, UCP1, mediates adaptive thermogenesis. By contrast, its paralogues UCP2 and UCP3 are not thought to mediate whole body thermogenesis in mammals. Instead, they have been implicated in a variety of physiological and pathological processes, including protection from oxidative stress, negative regulation of glucose sensing systems and the adaptation of fatty acid oxidation capacity to starving. Although much work has been devoted to how these proteins are activated, little is known of the mechanisms that reverse this activation. PMID:20006514

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.

Pathway and network-based analysis of genome-wide association studies and RT-PCR validation in polycystic ovary syndrome

PubMed Central

Shen, Haoran; Liang, Zhou; Zheng, Saihua; Li, Xuelian

2017-01-01

The purpose of this study was to identify promising candidate genes and pathways in polycystic ovary syndrome (PCOS). Microarray dataset GSE345269 obtained from the Gene Expression Omnibus database includes 7 granulosa cell samples from PCOS patients, and 3 normal granulosa cell samples. Differentially expressed genes (DEGs) were screened between PCOS and normal samples. Pathway enrichment analysis was conducted for DEGs using ClueGO and CluePedia plugin of Cytoscape. A Reactome functional interaction (FI) network of the DEGs was built using ReactomeFIViz, and then network modules were extracted, followed by pathway enrichment analysis for the modules. Expression of DEGs in granulosa cell samples was measured using quantitative RT-PCR. A total of 674 DEGs were retained, which were significantly enriched with inflammation and immune-related pathways. Eight modules were extracted from the Reactome FI network. Pathway enrichment analysis revealed significant pathways of each module: module 0, Regulation of RhoA activity and Signaling by Rho GTPases pathways shared ARHGAP4 and ARHGAP9; module 2, GlycoProtein VI-mediated activation cascade pathway was enriched with RHOG; module 3, Thromboxane A2 receptor signaling, Chemokine signaling pathway, CXCR4-mediated signaling events pathways were enriched with LYN, the hub gene of module 3. Results of RT-PCR confirmed the finding of the bioinformatic analysis that ARHGAP4, ARHGAP9, RHOG and LYN were significantly upregulated in PCOS. RhoA-related pathways, GlycoProtein VI-mediated activation cascade pathway, ARHGAP4, ARHGAP9, RHOG and LYN may be involved in the pathogenesis of PCOS. PMID:28949383

Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

NASA Astrophysics Data System (ADS)

Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

2015-12-01

Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction.

PubMed

Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

2015-12-18

Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

Bioglass incorporation improves mechanical properties and enhances cell-mediated mineralization on electrochemically aligned collagen threads.

PubMed

Nijsure, Madhura P; Pastakia, Meet; Spano, Joseph; Fenn, Michael B; Kishore, Vipuil

2017-09-01

Bone tissue engineering mandates the development of a functional scaffold that mimics the physicochemical properties of native bone. Bioglass 45S5 (BG) is a highly bioactive material known to augment bone formation and restoration. Hybrid scaffolds fabricated using collagen type I and BG resemble the organic and inorganic composition of the bone extracellular matrix and hence have been extensively investigated for bone tissue engineering applications. However, collagen-BG scaffolds developed thus far do not recapitulate the aligned structure of collagen found in native bone. In this study, an electrochemical fabrication method was employed to synthesize BG-incorporated electrochemically aligned collagen (BG-ELAC) threads that are compositionally similar to native bone. Further, aligned collagen fibrils within BG-ELAC threads mimic the anisotropic arrangement of collagen fibrils in native bone. The effect of BG incorporation on the mechanical properties and cell-mediated mineralization on ELAC threads was investigated. The results indicated that BG can be successfully incorporated within ELAC threads, without disturbing collagen fibril alignment. Further, BG incorporation significantly increased the ultimate tensile stress (UTS) and modulus of ELAC threads (p < 0.05). SBF conditioning showed extensive mineralization on BG-ELAC threads that increased over time demonstrating the bone bioactivity of BG-ELAC threads. Additionally, BG incorporation into ELAC threads resulted in increased cell proliferation (p < 0.05) and deposition of a highly dense and continuous mineralized matrix. In conclusion, incorporation of BG into ELAC threads is a viable strategy for the development of an osteoconductive material for bone tissue engineering applications. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 2429-2440, 2017. © 2017 Wiley Periodicals, Inc.

Electrochemical Characterization of a Novel Exoelectrogenic Bacterium Strain SCS5, Isolated from a Mediator-Less Microbial Fuel Cell and Phylogenetically Related to Aeromonas jandaei.

PubMed

Sharma, Subed Chandra Dev; Feng, Cuijie; Li, Jiangwei; Hu, Anyi; Wang, Han; Qin, Dan; Yu, Chang-Ping

2016-09-29

A facultative anaerobic bacterium, designated as strain SCS5, was isolated from the anodic biofilm of a mediator-less microbial fuel cell using acetate as the electron donor and α-FeOOH as the electron acceptor. The isolate was Gram-negative, motile, and shaped as short rods (0.9-1.3 μm in length and 0.4-0.5 μm in width). A phylogenetic analysis of the 16S rRNA, gyrB, and rpoD genes suggested that strain SCS5 belonged to the Aeromonas genus in the Aeromonadaceae family and exhibited the highest 16S rRNA gene sequence similarity (99.45%) with Aeromonas jandaei ATCC 49568. However, phenotypic, cellular fatty acid profile, and DNA G+C content analyses revealed that there were some distinctions between strain SCS5 and the type strain A. jandaei ATCC 49568. The optimum growth temperature, pH, and NaCl (%) for strain SCS5 were 35°C, 7.0, and 0.5% respectively. The DNA G+C content of strain SCS5 was 59.18%. The isolate SCS5 was capable of reducing insoluble iron oxide (α-FeOOH) and transferring electrons to extracellular material (the carbon electrode). The electrochemical activity of strain SCS5 was corroborated by cyclic voltammetry and a Raman spectroscopic analysis. The cyclic voltammogram of strain SCS5 revealed two pairs of oxidation-reduction peaks under anaerobic and aerobic conditions. In contrast, no redox pair was observed for A. jandaei ATCC 49568. Thus, isolated strain SCS5 is a novel exoelectrogenic bacterium phylogenetically related to A. jandaei, but shows distinct electrochemical activity from its close relative A. jandaei ATCC 49568.

Electron transfer from a solid-state electrode assisted by methyl viologen sustains efficient microbial reductive dechlorination of TCE.

PubMed

Aulenta, Federico; Catervi, Alessandro; Majone, Mauro; Panero, Stefania; Reale, Priscilla; Rossetti, Simona

2007-04-01

The ability to transfer electrons, via an extracellular path, to solid surfaces is typically exploited by microorganisms which use insoluble electron acceptors, such as iron-or manganese-oxides or inert electrodes in microbial fuel cells. The reverse process, i.e., the use of solid surfaces or electrodes as electron donors in microbial respirations, although largely unexplored, could potentially have important environmental applications, particularly for the removal of oxidized pollutants from contaminated groundwater or waste streams. Here we show, for the first time, that an electrochemical cell with a solid-state electrode polarized at -500 mV (vs standard hydrogen electrode), in combination with a low-potential redox mediator (methyl viologen), can efficiently transfer electrochemical reducing equivalents to microorganisms which respire using chlorinated solvents. By this approach, the reductive transformation of trichloroethene, a toxic yet common groundwater contaminant, to harmless end-products such as ethene and ethane could be performed. Furthermore, using a methyl-viologen-modified electrode we could even demonstrate that dechlorinating bacteria were able to accept reducing equivalents directly from the modified electrode surface. The innovative concept, based on the stimulation of dechlorination reactions through the use of solid-state electrodes (we propose for this process the acronym BEARD: Bio-Electrochemically Assisted Reductive Dechlorination), holds promise for in situ bioremediation of chlorinated-solvent-contaminated groundwater, and has several potential advantages over traditional approaches based on the subsurface injection of organic compounds. The results of this study raise the possibility that immobilization of selected redox mediators may be a general strategy for stimulating and controlling a range of microbial reactions using insoluble electrodes as electron donors.

Modulation of NMDA and AMPA-Mediated Synaptic Transmission by CB1 Receptors in Frontal Cortical Pyramidal Cells

PubMed Central

Li, Qiang; Yan, Haidun; Wilson, Wilkie A.; Swartzwelder, H. Scott

2010-01-01

Although the endogenous cannabinoid system modulates a variety of physiological and pharmacological processes, the specific role of cannabinoid CB1 receptors in the modulation of glutamatergic neurotransmission and neural plasticity is not well understood. Using whole-cell patch clamp recording techniques, evoked or spontaneous excitatory postsynaptic currents (eEPSCs or sEPSCs) were recorded from visualized, layer II/III pyramidal cells in frontal cortical slices from rat brain. Bath application of the CB1 receptor agonist, WIN 55212-2 (WIN), reduced the amplitude of NMDA receptor-mediated EPSCs in a concentration-dependent manner. When co-applied with the specific CB1 antagonists, AM251 or AM281, WIN did not suppress NMDA receptor mediated EPSCs. WIN also reduced the amplitude of evoked AMPA receptor-mediated EPSCs, an effect that was also reversed by AM251. Both the frequency and amplitude of spontaneous AMPA receptor-mediated EPSCs were significantly reduced by WIN. In contrast, WIN reduced the frequency, but not the amplitude of miniature EPSCs, suggesting that the suppression of glutmatergic activity by CB1 receptors in the frontal neocortex is mediated by a pre-synaptic mechanism. Taken together, these data indicate a critical role for endocannabinoid signaling in the regulation of excitatory synaptic transmission in frontal neocortex, and suggest a possible neuronal mechanism whereby THC regulates cortical function. PMID:20420813

Long non-coding RNA UCA1/miR-182/PFKFB2 axis modulates glioblastoma-associated stromal cells-mediated glycolysis and invasion of glioma cells.

PubMed

He, Zongze; You, Chao; Zhao, Dongdong

2018-06-07

Glioblastoma (GB) is the most common and deadliest malignant primary brain tumor with a high recurrence. In this study, lncRNA UCA1/miR-182 axis has been regarded as a nodal driver of glioma invasion mediated by GB-associated stromal cells (GASCs) and GASC-secreted chemokine CXCL14. In clinical specimens, CXCL14 upregulation in GASCs also correlated with poor prognosis. Notably, CXCL14-high GASCs mediated lncRNA UCA1 upregulation and miR-182 downregulation in glioma cells. Moreover, miR-182 directly bound to the fructose-2,6-biphosphatase PFKFB2; UCA1/miR-182 axis thereby modulated GASC-induced glycolysis in glioma cells. Overall, UCA1/miR-182/PFKFB2 axis modulates chemokine CXCL14 secretion, glycolysis and invasion of glioma cells in GASCs. Copyright © 2018 Elsevier Inc. All rights reserved.

Actin-Based Adhesion Modules Mediate Cell Interactions with the Extracellular Matrix and Neighboring Cells.

PubMed

Bachir, Alexia I; Horwitz, Alan Rick; Nelson, W James; Bianchini, Julie M

2017-07-05

Cell adhesions link cells to the extracellular matrix (ECM) and to each other and depend on interactions with the actin cytoskeleton. Both cell-ECM and cell-cell adhesion sites contain discrete, yet overlapping, functional modules. These modules establish physical associations with the actin cytoskeleton, locally modulate actin organization and dynamics, and trigger intracellular signaling pathways. Interplay between these modules generates distinct actin architectures that underlie different stages, types, and functions of cell-ECM and cell-cell adhesions. Actomyosin contractility is required to generate mature, stable adhesions, as well as to sense and translate the mechanical properties of the cellular environment into changes in cell organization and behavior. Here, we review the organization and function of different adhesion modules and how they interact with the actin cytoskeleton. We highlight the molecular mechanisms of mechanotransduction in adhesions and how adhesion molecules mediate cross talk between cell-ECM and cell-cell adhesion sites. Copyright © 2017 Cold Spring Harbor Laboratory Press; all rights reserved.

Song Competition Affects Monoamine Levels in Sensory and Motor Forebrain Regions of Male Lincoln's Sparrows (Melospiza lincolnii)

PubMed Central

Sewall, Kendra B.; Caro, Samuel P.; Sockman, Keith W.

2013-01-01

Male animals often change their behavior in response to the level of competition for mates. Male Lincoln's sparrows (Melospiza lincolnii) modulate their competitive singing over the period of a week as a function of the level of challenge associated with competitors' songs. Differences in song challenge and associated shifts in competitive state should be accompanied by neural changes, potentially in regions that regulate perception and song production. The monoamines mediate neural plasticity in response to environmental cues to achieve shifts in behavioral state. Therefore, using high pressure liquid chromatography with electrochemical detection, we compared levels of monoamines and their metabolites from male Lincoln's sparrows exposed to songs categorized as more or less challenging. We compared levels of norepinephrine and its principal metabolite in two perceptual regions of the auditory telencephalon, the caudomedial nidopallium and the caudomedial mesopallium (CMM), because this chemical is implicated in modulating auditory sensitivity to song. We also measured the levels of dopamine and its principal metabolite in two song control nuclei, area X and the robust nucleus of the arcopallium (RA), because dopamine is implicated in regulating song output. We measured the levels of serotonin and its principal metabolite in all four brain regions because this monoamine is implicated in perception and behavioral output and is found throughout the avian forebrain. After controlling for recent singing, we found that males exposed to more challenging song had higher levels of norepinephrine metabolite in the CMM and lower levels of serotonin in the RA. Collectively, these findings are consistent with norepinephrine in perceptual brain regions and serotonin in song control regions contributing to neuroplasticity that underlies socially-induced changes in behavioral state. PMID:23555809

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.

Energy conservation by oxidation of formate to carbon dioxide and hydrogen via a sodium ion current in a hyperthermophilic archaeon

PubMed Central

Lim, Jae Kyu; Mayer, Florian; Kang, Sung Gyun; Müller, Volker

2014-01-01

Thermococcus onnurineus NA1 is known to grow by the anaerobic oxidation of formate to CO2 and H2, a reaction that operates near thermodynamic equilibrium. Here we demonstrate that this reaction is coupled to ATP synthesis by a transmembrane ion current. Formate oxidation leads to H+ translocation across the cytoplasmic membrane that then drives Na+ translocation. The ion-translocating electron transfer system is rather simple, consisting of only a formate dehydrogenase module, a membrane-bound hydrogenase module, and a multisubunit Na+/H+ antiporter module. The electrochemical Na+ gradient established then drives ATP synthesis. These data give a mechanistic explanation for chemiosmotic energy conservation coupled to formate oxidation to CO2 and H2. Because it is discussed that the membrane-bound hydrogenase with the Na+/H+ antiporter module are ancestors of complex I of mitochondrial and bacterial electron transport these data also shed light on the evolution of ion transport in complex I-like electron transport chains. PMID:25049407

Energy conservation by oxidation of formate to carbon dioxide and hydrogen via a sodium ion current in a hyperthermophilic archaeon.

PubMed

Lim, Jae Kyu; Mayer, Florian; Kang, Sung Gyun; Müller, Volker

2014-08-05

Thermococcus onnurineus NA1 is known to grow by the anaerobic oxidation of formate to CO2 and H2, a reaction that operates near thermodynamic equilibrium. Here we demonstrate that this reaction is coupled to ATP synthesis by a transmembrane ion current. Formate oxidation leads to H(+) translocation across the cytoplasmic membrane that then drives Na(+) translocation. The ion-translocating electron transfer system is rather simple, consisting of only a formate dehydrogenase module, a membrane-bound hydrogenase module, and a multisubunit Na(+)/H(+) antiporter module. The electrochemical Na(+) gradient established then drives ATP synthesis. These data give a mechanistic explanation for chemiosmotic energy conservation coupled to formate oxidation to CO2 and H2. Because it is discussed that the membrane-bound hydrogenase with the Na(+)/H(+) antiporter module are ancestors of complex I of mitochondrial and bacterial electron transport these data also shed light on the evolution of ion transport in complex I-like electron transport chains.

Implications of Mediated Instruction to Remote Learning in Mathematics.

ERIC Educational Resources Information Center

Matthews-Lopez, Joy L.; Lopez-Permouth, Sergio R.; Keck, David

Mediated learning utilizes multimedia-based instructional modules to provide students with individualized access to information in alignment with their individual learning styles (Kinser, Morris, & Hewitt). In contrast with traditional pedagogy, the mission of the instructor in a mediated learning environment is to facilitate learning rather than…

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.

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.

Proresolving lipid mediators resolvin D1, resolvin D2, and maresin 1 are critical in modulating T cell responses.

PubMed

Chiurchiù, Valerio; Leuti, Alessandro; Dalli, Jesmond; Jacobsson, Anders; Battistini, Luca; Maccarrone, Mauro; Serhan, Charles N

2016-08-24

Resolution of inflammation is a finely regulated process mediated by specialized proresolving lipid mediators (SPMs), including docosahexaenoic acid (DHA)-derived resolvins and maresins. The immunomodulatory role of SPMs in adaptive immune cells is of interest. We report that D-series resolvins (resolvin D1 and resolvin D2) and maresin 1 modulate adaptive immune responses in human peripheral blood lymphocytes. These lipid mediators reduce cytokine production by activated CD8(+) T cells and CD4(+) T helper 1 (TH1) and TH17 cells but do not modulate T cell inhibitory receptors or abrogate their capacity to proliferate. Moreover, these SPMs prevented naïve CD4(+) T cell differentiation into TH1 and TH17 by down-regulating their signature transcription factors, T-bet and Rorc, in a mechanism mediated by the GPR32 and ALX/FPR2 receptors; they concomitantly enhanced de novo generation and function of Foxp3(+) regulatory T (Treg) cells via the GPR32 receptor. These results were also supported in vivo in a mouse deficient for DHA synthesis (Elovl2(-/-)) that showed an increase in TH1/TH17 cells and a decrease in Treg cells compared to wild-type mice. Additionally, either DHA supplementation in Elovl2(-/-) mice or in vivo administration of resolvin D1 significantly reduced cytokine production upon specific stimulation of T cells. These findings demonstrate actions of specific SPMs on adaptive immunity and provide a new avenue for SPM-based approaches to modulate chronic inflammation. Copyright © 2016, American Association for the Advancement of Science.

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

Beta receptor-mediated modulation of the late positive potential in humans.

PubMed

de Rover, Mischa; Brown, Stephen B R E; Boot, Nathalie; Hajcak, Greg; van Noorden, Martijn S; van der Wee, Nic J A; Nieuwenhuis, Sander

2012-02-01

Electrophysiological studies have identified a scalp potential, the late positive potential (LPP), which is modulated by the emotional intensity of observed stimuli. Previous work has shown that the LPP reflects the modulation of activity in extrastriate visual cortical structures, but little is known about the source of that modulation. The present study investigated whether beta-adrenergic receptors are involved in the generation of the LPP. We used a genetic individual differences approach (experiment 1) and a pharmacological manipulation (experiment 2) to test the hypothesis that the LPP is modulated by the activation of β-adrenergic receptors. In experiment 1, we found that LPP amplitude depends on allelic variation in the β1-receptor gene polymorphism. In experiment 2, we found that LPP amplitude was modulated by the β-blocker propranolol in a direction dependent on subjects' level of trait anxiety: In participants with lower trait anxiety, propranolol led to a (nonsignificant) decrease in the LPP modulation; in participants with higher trait anxiety, propranolol increased the emotion-related LPP modulation. These results provide initial support for the hypothesis that the LPP reflects the downstream effects, in visual cortical areas, of β-receptor-mediated activation of the amygdala.

Renal intercalated cells and blood pressure regulation.

PubMed

Wall, Susan M

2017-12-01

Type B and non-A, non-B intercalated cells are found within the connecting tubule and the cortical collecting duct. Of these cell types, type B intercalated cells are known to mediate Cl - absorption and HCO 3 - secretion largely through pendrin-dependent Cl - /HCO 3 - exchange. This exchange is stimulated by angiotensin II administration and is also stimulated in models of metabolic alkalosis, for instance after aldosterone or NaHCO 3 administration. In some rodent models, pendrin-mediated HCO 3 - secretion modulates acid-base balance. However, the role of pendrin in blood pressure regulation is likely of more physiological or clinical significance. Pendrin regulates blood pressure not only by mediating aldosterone-sensitive Cl - absorption, but also by modulating the aldosterone response for epithelial Na + channel (ENaC)-mediated Na + absorption. Pendrin regulates ENaC through changes in open channel of probability, channel surface density, and channels subunit total protein abundance. Thus, aldosterone stimulates ENaC activity through both direct and indirect effects, the latter occurring through its stimulation of pendrin expression and function. Therefore, pendrin contributes to the aldosterone pressor response. Pendrin may also modulate blood pressure in part through its action in the adrenal medulla, where it modulates the release of catecholamines, or through an indirect effect on vascular contractile force. This review describes how aldosterone and angiotensin II-induced signaling regulate pendrin and the contributory role of pendrin in distal nephron function and blood pressure.

Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

PubMed

Seber, Gonca; Rudnev, Alexander V; Droghetti, Andrea; Rungger, Ivan; Veciana, Jaume; Mas-Torrent, Marta; Rovira, Concepció; Crivillers, Núria

2017-01-26

A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing the sensitivity of needle-implantable electrochemical glucose sensors via surface rebuilding.

PubMed

Vaddiraju, Santhisagar; Legassey, Allen; Qiang, Liangliang; Wang, Yan; Burgess, Diane J; Papadimitrakopoulos, Fotios

2013-03-01

Needle-implantable sensors have shown to provide reliable continuous glucose monitoring for diabetes management. In order to reduce tissue injury during sensor implantation, there is a constant need for device size reduction, which imposes challenges in terms of sensitivity and reliability, as part of decreasing signal-to-noise and increasing layer complexity. Herein, we report sensitivity enhancement via electrochemical surface rebuilding of the working electrode (WE), which creates a three-dimensional nanoporous configuration with increased surface area. The gold WE was electrochemically rebuilt to render its surface nanoporous followed by decoration with platinum nanoparticles. The efficacy of such process was studied using sensor sensitivity against hydrogen peroxide (H2O2). For glucose detection, the WE was further coated with five layers, namely, (1) polyphenol, (2) glucose oxidase, (3) polyurethane, (4) catalase, and (5) dexamethasone-releasing poly(vinyl alcohol)/poly(lactic-co-glycolic acid) composite. The amperometric response of the glucose sensor was noted in vitro and in vivo. Scanning electron microscopy revealed that electrochemical rebuilding of the WE produced a nanoporous morphology that resulted in a 20-fold enhancement in H2O2 sensitivity, while retaining >98% selectivity. This afforded a 4-5-fold increase in overall glucose response of the glucose sensor when compared with a control sensor with no surface rebuilding and fittable only within an 18 G needle. The sensor was able to reproducibly track in vivo glycemic events, despite the large background currents typically encountered during animal testing. Enhanced sensor performance in terms of sensitivity and large signal-to-noise ratio has been attained via electrochemical rebuilding of the WE. This approach also bypasses the need for conventional and nanostructured mediators currently employed to enhance sensor performance. © 2013 Diabetes Technology Society.

Pathway and network-based analysis of genome-wide association studies and RT-PCR validation in polycystic ovary syndrome.

PubMed

Shen, Haoran; Liang, Zhou; Zheng, Saihua; Li, Xuelian

2017-11-01

The purpose of this study was to identify promising candidate genes and pathways in polycystic ovary syndrome (PCOS). Microarray dataset GSE345269 obtained from the Gene Expression Omnibus database includes 7 granulosa cell samples from PCOS patients, and 3 normal granulosa cell samples. Differentially expressed genes (DEGs) were screened between PCOS and normal samples. Pathway enrichment analysis was conducted for DEGs using ClueGO and CluePedia plugin of Cytoscape. A Reactome functional interaction (FI) network of the DEGs was built using ReactomeFIViz, and then network modules were extracted, followed by pathway enrichment analysis for the modules. Expression of DEGs in granulosa cell samples was measured using quantitative RT-PCR. A total of 674 DEGs were retained, which were significantly enriched with inflammation and immune-related pathways. Eight modules were extracted from the Reactome FI network. Pathway enrichment analysis revealed significant pathways of each module: module 0, Regulation of RhoA activity and Signaling by Rho GTPases pathways shared ARHGAP4 and ARHGAP9; module 2, GlycoProtein VI-mediated activation cascade pathway was enriched with RHOG; module 3, Thromboxane A2 receptor signaling, Chemokine signaling pathway, CXCR4-mediated signaling events pathways were enriched with LYN, the hub gene of module 3. Results of RT-PCR confirmed the finding of the bioinformatic analysis that ARHGAP4, ARHGAP9, RHOG and LYN were significantly upregulated in PCOS. RhoA-related pathways, GlycoProtein VI-mediated activation cascade pathway, ARHGAP4, ARHGAP9, RHOG and LYN may be involved in the pathogenesis of PCOS.

Coulometric determination of NAD+ and NADH in normal and cancer cells using LDH, RVC and a polymer mediator.

PubMed

Torabi, F; Ramanathan, K; Larsson, P O; Gorton, L; Svanberg, K; Okamoto, Y; Danielsson, B; Khayyami, M

1999-11-15

An electrochemical method for the measurement of NAD(+) and NADH in normal and cancer tissues using flow injection analysis (FIA) is reported. Reticulated vitreous carbon (RVC) electrodes with entrapped l-lactate dehydrogenase (LDH) and a new redox polymer containing covalently bound toluidine blue O (TBO) were employed for this purpose. Both NAD(+) and NADH were estimated coulometrically based on their reaction with LDH. The latter was immobilized on controlled pore glass (CPG) by cross-linking with glutaraldehyde and packed within the RVC. The concentrations of NAD(+) and NADH in the tissues, estimated using different electron mediators such as ferricyanide (FCN), meldola blue (MB) and TBO have also been compared. The effects of flow rate, pH, applied potential (versus Ag/AgCl reference) and adsorption of the mediators have also been investigated. Based on the measurements of NAD(+) and NADH in normal and cancer tissues it has been concluded that the NADH concentration is lower, while the NAD(+) concentration is higher in cancer tissues. Amongst the electron mediators TBO was found to be a more stable mediator for such measurements.

Importance of Extracellular Polymeric Substances from Thiobacillus ferrooxidans for Bioleaching

PubMed Central

Gehrke, Tilman; Telegdi, Judit; Thierry, Dominique; Sand, Wolfgang

1998-01-01

Leaching bacteria such as Thiobacillus ferrooxidans attach to pyrite or sulfur by means of extracellular polymeric substances (EPS) (lipopolysaccharides). The primary attachment to pyrite at pH 2 is mediated by exopolymer-complexed iron(III) ions in an electrochemical interaction with the negatively charged pyrite surface. EPS from sulfur cells possess increased hydrophobic properties and do not attach to pyrite, indicating adaptability to the substrate or substratum. PMID:9647862

The creation of a biomimetic interface between boron-doped diamond and immobilized proteins.

PubMed

Hoffmann, René; Kriele, Armin; Obloh, Harald; Tokuda, Norio; Smirnov, Waldemar; Yang, Nianjun; Nebel, Christoph E

2011-10-01

Immobilization of proteins on a solid electrode is to date done by chemical cross-linking or by addition of an adjustable intermediate. In this paper we introduce a concept where a solid with variable surface properties is optimized to mediate binding of the electron-transfer protein Cytochrome c (Cyt c) by mimicking the natural binding environment. It is shown that, as a carbon-based material, boron-doped diamond can be adjusted by simple electrochemical surface treatments to the specific biochemical requirements of Cyt c. The structure and functionality of passively adsorbed Cyt c on variously terminated diamond surfaces were characterized in detail using a combination of electrochemical techniques and atomic force microscopy with single-molecule resolution. Partially oxidized diamond allowed stable immobilization of Cyt c together with high electron transfer activity, driven by a combination of electrostatic and hydrophobic interactions. This surface mimics the natural binding partner, where coarse orientation is governed by electrostatic interaction of the protein's dipole and hydrophobic interactions assist in formation of the electron transfer complex. The optimized surface mediated electron transfer kinetics around 100 times faster than those reported for other solids and even faster kinetics than on self-assembled monolayers of alkanethiols. Copyright © 2011 Elsevier Ltd. All rights reserved.

An enzyme-free homogenous electrochemical assay for sensitive detection of the plasmid-mediated colistin resistance gene mcr-1.

PubMed

Li, Bo; Chai, Zhixin; Yan, Xiaohui; Liu, Chunchen; Situ, Bo; Zhang, Ye; Pan, Weilun; Luo, Shihua; Liu, Jianhua; Zheng, Lei

2018-05-22

Antibiotic resistance associated with the mcr-1 gene of Gram-negative bacteria, which confers resistance to drugs of last resort and has the potential to spread via plasmids, is one of the most pressing issues facing global health today. Point-of-care testing for the mcr-1 gene is needed to aid in the identification of colistin resistance in the field and to control its horizontal transmission. Here, we report the successful development of an enzyme-free homogenous electrochemical strategy for sensitive detection of the antibiotic resistance gene mcr-1 using the hybridization chain reaction and mcr-1-specific toehold probe. The long double-stranded DNA polymer produced using this strategy could be detected by assessing the diffusion of methylene blue towards the surface of a screen-printed gold electrode. Under optimized conditions, a linear relationship was observed between the variation of peak current and the natural logarithm of the mcr-1 gene concentration in the range of 1 nM to 1 μM with a detection limit of 0.78 nM (S/N = 3). This enzyme-free, isothermal platform is a rapid, portable, disposable, and sensitive method for detection of plasmid-mediated colistin resistance.

A repeatedly refuelable mediated biofuel cell based on a hierarchical porous carbon electrode

NASA Astrophysics Data System (ADS)

Fujita, Shuji; Yamanoi, Shun; Murata, Kenichi; Mita, Hiroki; Samukawa, Tsunetoshi; Nakagawa, Takaaki; Sakai, Hideki; Tokita, Yuichi

2014-05-01

Biofuel cells that generate electricity from renewable fuels, such as carbohydrates, must be reusable through repeated refuelling, should these devices be used in consumer electronics. We demonstrate the stable generation of electricity from a glucose-powered mediated biofuel cell through multiple refuelling cycles. This refuelability is achieved by immobilizing nicotinamide adenine dinucleotide (NAD), an electron-transfer mediator, and redox enzymes in high concentrations on porous carbon particles constituting an anode while maintaining their electrochemical and enzymatic activities after the immobilization. This bioanode can be refuelled continuously for more than 60 cycles at 1.5 mA cm-2 without significant potential drop. Cells assembled with these bioanodes and bilirubin-oxidase-based biocathodes can be repeatedly used to power a portable music player at 1 mW cm-3 through 10 refuelling cycles. This study suggests that the refuelability within consumer electronics should facilitate the development of long and repeated use of the mediated biofuel cells as well as of NAD-based biosensors, bioreactors, and clinical applications.

A repeatedly refuelable mediated biofuel cell based on a hierarchical porous carbon electrode.

PubMed

Fujita, Shuji; Yamanoi, Shun; Murata, Kenichi; Mita, Hiroki; Samukawa, Tsunetoshi; Nakagawa, Takaaki; Sakai, Hideki; Tokita, Yuichi

2014-05-13

Biofuel cells that generate electricity from renewable fuels, such as carbohydrates, must be reusable through repeated refuelling, should these devices be used in consumer electronics. We demonstrate the stable generation of electricity from a glucose-powered mediated biofuel cell through multiple refuelling cycles. This refuelability is achieved by immobilizing nicotinamide adenine dinucleotide (NAD), an electron-transfer mediator, and redox enzymes in high concentrations on porous carbon particles constituting an anode while maintaining their electrochemical and enzymatic activities after the immobilization. This bioanode can be refuelled continuously for more than 60 cycles at 1.5 mA cm(-2) without significant potential drop. Cells assembled with these bioanodes and bilirubin-oxidase-based biocathodes can be repeatedly used to power a portable music player at 1 mW cm(-3) through 10 refuelling cycles. This study suggests that the refuelability within consumer electronics should facilitate the development of long and repeated use of the mediated biofuel cells as well as of NAD-based biosensors, bioreactors, and clinical applications.

A repeatedly refuelable mediated biofuel cell based on a hierarchical porous carbon electrode

PubMed Central

Fujita, Shuji; Yamanoi, Shun; Murata, Kenichi; Mita, Hiroki; Samukawa, Tsunetoshi; Nakagawa, Takaaki; Sakai, Hideki; Tokita, Yuichi

2014-01-01

Biofuel cells that generate electricity from renewable fuels, such as carbohydrates, must be reusable through repeated refuelling, should these devices be used in consumer electronics. We demonstrate the stable generation of electricity from a glucose-powered mediated biofuel cell through multiple refuelling cycles. This refuelability is achieved by immobilizing nicotinamide adenine dinucleotide (NAD), an electron-transfer mediator, and redox enzymes in high concentrations on porous carbon particles constituting an anode while maintaining their electrochemical and enzymatic activities after the immobilization. This bioanode can be refuelled continuously for more than 60 cycles at 1.5 mA cm−2 without significant potential drop. Cells assembled with these bioanodes and bilirubin-oxidase-based biocathodes can be repeatedly used to power a portable music player at 1 mW cm−3 through 10 refuelling cycles. This study suggests that the refuelability within consumer electronics should facilitate the development of long and repeated use of the mediated biofuel cells as well as of NAD-based biosensors, bioreactors, and clinical applications. PMID:24820210

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.

New insights into the electrochemical desorption of alkanethiol SAMs on gold

PubMed Central

Pensa, Evangelina; Vericat, Carolina; Grumelli, Doris; Salvarezza, Roberto C.; Park, Sung Hyun; Longo, Gabriel S.; Szleifer, Igal

2012-01-01

A combination of Polarization Modulation Infrared Reflection Absorption Spectroscopy (PMIRRAS) under electrochemical control, Electrochemical Scanning Tunneling Microscopy (ECSTM) and Molecular Dynamics (MD) simulations has been used to shed light on the reductive desorption process of dodecanethiol (C12) and octadecanethiol (C18) SAMs on gold in aqueous electrolytes. Experimental PMIRRAS, ECSTM and MD simulations data for C12 desorption are consistent with formation of randomly distributed micellar aggregates stabilized by Na+ ions, coexisting with a lying-down phase of molecules. The analysis of pit and Au island coverage before and after desorption is consistent with the thiolate-Au adatoms models. On the other hand, PMIRRAS and MD data for C18 indicate that the desorbed alkanethiolates adopt a Na+ ion-stabilized bilayer of interdigitated alkanethiolates, with no evidence of lying down molecules. MD simulations also show that both the degree of order and tilt angle of the desorbed alkanethiolates change with the surface charge on the metal, going from bilayers to micelles. These results demonstrate the complexity of the alkanethiol desorption in the presence of water and the fact that chain length and counterions play a key role in a complex structure. PMID:22870508

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

Increases in reactive oxygen species enhance vascular endothelial cell migration through a mechanism dependent on the transient receptor potential melastatin 4 ion channel.

PubMed

Sarmiento, Daniela; Montorfano, Ignacio; Cerda, Oscar; Cáceres, Mónica; Becerra, Alvaro; Cabello-Verrugio, Claudio; Elorza, Alvaro A; Riedel, Claudia; Tapia, Pablo; Velásquez, Luis A; Varela, Diego; Simon, Felipe

2015-03-01

A hallmark of severe inflammation is reactive oxygen species (ROS) overproduction induced by increased inflammatory mediators secretion. During systemic inflammation, inflammation mediators circulating in the bloodstream interact with endothelial cells (ECs) raising intracellular oxidative stress at the endothelial monolayer. Oxidative stress mediates several pathological functions, including an exacerbated EC migration. Because cell migration critically depends on calcium channel-mediated Ca(2+) influx, the molecular identification of the calcium channel involved in oxidative stress-modulated EC migration has been the subject of intense investigation. The transient receptor potential melastatin 4 (TRPM4) protein is a ROS-modulated non-selective cationic channel that performs several cell functions, including regulating intracellular Ca(2+) overload and Ca(2+) oscillation. This channel is expressed in multiple tissues, including ECs, and contributes to the migration of certain immune cells. However, whether the TRPM4 ion channel participates in oxidative stress-mediated EC migration is not known. Herein, we investigate whether oxidative stress initiates or enhances EC migration and study the role played by the ROS-modulated TRPM4 ion channel in oxidative stress-mediated EC migration. We demonstrate that oxidative stress enhances, but does not initiate, EC migration in a dose-dependent manner. Notably, we demonstrate that the TRPM4 ion channel is critical in promoting H2O2-enhanced EC migration. These results show that TRPM4 is a novel pharmacological target for the possible treatment of severe inflammation and other oxidative stress-mediated inflammatory diseases. Copyright © 2014 Elsevier Inc. All rights reserved.

Eradication of Pseudomonas aeruginosa cells by cathodic electrochemical currents delivered with graphite electrodes.

PubMed

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

2017-03-01

Antibiotic resistance is a major challenge to the treatment of bacterial infections associated with medical devices and biomaterials. One important intrinsic mechanism of such resistance is the formation of persister cells that are phenotypic variants of microorganisms and highly tolerant to antibiotics. Recently, we reported a new approach to eradicating persister cells of Pseudomonas aeruginosa using low-level direct electrochemical current (DC) and synergy with the antibiotic tobramycin. To further understand the underlying mechanism and develop this technology toward possible medical applications, we investigated the electricidal activities of non-metallic biomaterial on persister and biofilm cells of P. aeruginosa using graphite-based TGON™ 805 electrodes. We employed both single and dual chamber systems to compare electrochemical factors of TGON and stainless steel 304 electrodes. The results revealed that TGON-based treatments were highly effective against P. aeruginosa persister cells. In the single chamber system, complete eradication of planktonic persister cells (corresponding to a 7-log killing) was achieved with 70μA/cm 2 DC using TGON electrodes within 40min of treatment, while the cell viability in biofilms was reduced by 2 logs within 1h. The killing effects were dose and time dependent with higher current densities requiring less time. Moreover, reduction reactions were found more effective than oxidation reactions, confirming that metal cations are not indispensable, although they may facilitate cell killing. The findings of this study can help develop electrochemical technologies to eradicate persister and biofilm cells for more effective treatment of medical device and biomaterial associated infections. Infections associated with medical devices and biomaterials present a major challenge due to high-level tolerance of microbes to conventional antibiotics. It is well established that such tolerance is due to the formation of dormant persister cells and multicellular structures known as biofilms. Recent studies have demonstrated electrochemical treatment as a promising alternative to eradicate bacterial infections, since the killing mechanism is independent of the growth phase of bacterial cells, but relies on various electrochemical species interplaying during the treatment. The current study investigated major bactericidal properties of the electrochemical currents mediated via TGON, a carbon-based electrode material. Up to total eradication of Pseudomonas aeruginosa persister cells was achieved. The new knowledge of electrochemical properties and the bioactivity of TGON may help develop new methods/devices to eradicate bacterial infections by delivering safe levels of electrochemical currents. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Real-time mapping of salt glands on the leaf surface of Cynodon dactylon L. using scanning electrochemical microscopy.

PubMed

Parthasarathy, Meera; Pemaiah, Brindha; Natesan, Ravichandran; Padmavathy, Saralla R; Pachiappan, Jayaraman

2015-02-01

Salt glands are specialized organelles present in the leaf tissues of halophytes, which impart salt-tolerance capability to the plant species. These glands are usually identified only by their morphology using conventional staining procedures coupled with optical microscopy. In this work, we have employed scanning electrochemical microscopy to identify the salt glands not only by their morphology but also by their salt excretion behavior. Bermuda grass (Cynodon dactylon L.) species was chosen for the study as they are known to be salt-tolerant and contain salt glands on leaf surfaces. Scanning electrochemical microscopy performed in sodium chloride medium in the presence and absence of potassium ferrocyanide as redox mediator, reveals the identity of salt glands. More insight into the ion expulsion behavior of these glands was obtained by mapping lateral and vertical variations in ion concentrations using surface impedance measurements which indicated five times higher resistance over the salt glands compared to the surrounding tissues and bulk solution. The protocol could be used to understand the developmental processes in plants grown in different soil/water conditions in order to improve salt tolerance of food crops by genetic engineering and hence improve their agricultural productivity.

Nanoparticle-Mediated Physical Exfoliation of Aqueous-Phase Graphene for Fabrication of Three-Dimensionally Structured Hybrid Electrodes.

PubMed

Lee, Younghee; Choi, Hojin; Kim, Min-Sik; Noh, Seonmyeong; Ahn, Ki-Jin; Im, Kyungun; Kwon, Oh Seok; Yoon, Hyeonseok

2016-01-27

Monodispersed polypyrrole (PPy) nanospheres were physically incorporated as guest species into stacked graphene layers without significant property degradation, thereby facilitating the formation of unique three-dimensional hybrid nanoarchitecture. The electrochemical properties of the graphene/particulate PPy (GPPy) nanohybrids were dependent on the sizes and contents of the PPy nanospheres. The nanohybrids exhibited optimum electrochemical performance in terms of redox activity, charge-transfer resistance, and specific capacitance at an 8:1 PPy/graphite (graphene precursor) weight ratio. The packing density of the alternately stacked nanohybrid structure varied with the nanosphere content, indicating the potential for high volumetric capacitance. The nanohybrids also exhibited good long-term cycling stability because of a structural synergy effect. Finally, fabricated nanohybrid-based flexible all-solid state capacitor cells exhibited good electrochemical performance in an acidic electrolyte with a maximum energy density of 8.4 Wh kg(-1) or 1.9 Wh L(-1) at a maximum power density of 3.2 kW kg(-1) or 0.7 kW L(-1); these performances were based on the mass or packing density of the electrode materials.

Geometrical isomerization of carotenoids mediated by cation radical/dication formation

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

Gao, G.; Wei, C.C.; Jeevarajan, A.S.

1996-03-28

Electrochemical oxidation of all-trans-canthaxanthin and {beta}-carotene in dichloromethane leads to significant trans-to-cis isomerization, with cis isomers accounting for about 40% of the products formed. The electrochemically generated isomers were separated by reverse-phase high-performance liquid chromatography and identified as 9-cis, 13-cis, 15-cis, and 9,13-di-cis isomers of the carotenoids by {sup 1}H-NMR spectroscopy and optical spectroscopy (Q ratio). The results of simultaneous bulk electrolysis and optical absorption spectroscopy indicate the following isomerization mechanism: the all-trans cation radicals and/or dications formed by electrochemical oxidation of all-trans-carotenoids can easily undergo geometrical isomerization to form cis cation radicals and/or dications. The latter are converted bymore » the comproportionation equilibrium to cation radicals which are then transformed to neutral cis-carotenoids by exchanging one electron with neutral carotenoids. AM1 molecular orbital calculations, which show that the energy barriers of configurational transformation from trans to cis are much lower in the cation radical and dication species than in the neutral molecule, strongly support the first step of this mechanism. 36 refs., 5 figs., 2 tabs.« less

Nanoparticle-Mediated Physical Exfoliation of Aqueous-Phase Graphene for Fabrication of Three-Dimensionally Structured Hybrid Electrodes

PubMed Central

Lee, Younghee; Choi, Hojin; Kim, Min-Sik; Noh, Seonmyeong; Ahn, Ki-Jin; Im, Kyungun; Kwon, Oh Seok; Yoon, Hyeonseok

2016-01-01

Monodispersed polypyrrole (PPy) nanospheres were physically incorporated as guest species into stacked graphene layers without significant property degradation, thereby facilitating the formation of unique three-dimensional hybrid nanoarchitecture. The electrochemical properties of the graphene/particulate PPy (GPPy) nanohybrids were dependent on the sizes and contents of the PPy nanospheres. The nanohybrids exhibited optimum electrochemical performance in terms of redox activity, charge-transfer resistance, and specific capacitance at an 8:1 PPy/graphite (graphene precursor) weight ratio. The packing density of the alternately stacked nanohybrid structure varied with the nanosphere content, indicating the potential for high volumetric capacitance. The nanohybrids also exhibited good long-term cycling stability because of a structural synergy effect. Finally, fabricated nanohybrid-based flexible all–solid state capacitor cells exhibited good electrochemical performance in an acidic electrolyte with a maximum energy density of 8.4 Wh kg−1 or 1.9 Wh L−1 at a maximum power density of 3.2 kW kg−1 or 0.7 kW L−1; these performances were based on the mass or packing density of the electrode materials. PMID:26813878

Mechanistic Study of the Validity of Using Hydroxyl Radical Probes To Characterize Electrochemical Advanced Oxidation Processes.

PubMed

Jing, Yin; Chaplin, Brian P

2017-02-21

The detection of hydroxyl radicals (OH • ) is typically accomplished by using reactive probe molecules, but prior studies have not thoroughly investigated the suitability of these probes for use in electrochemical advanced oxidation processes (EAOPs), due to the neglect of alternative reaction mechanisms. In this study, we investigated the suitability of four OH • probes (coumarin, p-chlorobenzoic acid, terephthalic acid, and p-benzoquinone) for use in EAOPs. Experimental results indicated that both coumarin and p-chlorobenzoic acid are oxidized via direct electron transfer reactions, while p-benzoquinone and terephthalic acid are not. Coumarin oxidation to form the OH • adduct product 7-hydroxycoumarin was found at anodic potentials lower than that necessary for OH • formation. Density functional theory (DFT) simulations found a thermodynamically favorable and non-OH • mediated pathway for 7-hydroxycoumarin formation, which is activationless at anodic potentials > 2.10 V/SHE. DFT simulations also provided estimates of E° values for a series of OH • probe compounds, which agreed with voltammetry results. Results from this study indicated that terephthalic acid is the most appropriate OH • probe compound for the characterization of electrochemical and catalytic systems.

Novel synthesis and characterization of pristine Cu nanoparticles for the non-enzymatic glucose biosensor.

PubMed

Dayakar, T; Rao, K Venkateswara; Bikshalu, K; Rajendar, V; Park, Si-Hyun

2017-07-01

Non enzymatic electrochemical glucose sensing was developed based on pristine Cu Nanopartilces (NPs)/Glassy Carbon Electrode (GCE) which can be accomplished by simple green method via ocimum tenuiflorum leaf extract. Then, the affect of leaf extract addition on improving Structural, Optical and electrochemical properties of pristine cu NPs was investigated. The synthesized Cu NPs were characterized with X-ray diffraction (X-ray), Uv-Visible spectroscopy (Uv-Vis), Fourier transformation infrared spectroscopy (FTIR), Particle size distribution (PSA), Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDS), Transmission electron microscopy (TEM) for structural optical and morphological studies respectively. The synthesized Cu NPs were coated over glassy carbon electrode (GCE) to study the electrochemical response of glucose by cyclic voltammetry and ampherometer. The results indicates that the modified biosensor shows a remarkable sensitivity (1065.21 μA mM -1  cm -2 ), rapid response time (<3s), wide linear range (1 to 7.2 mM), low detection limit (0.038 μM at S/N = 3). Therefore, the prepared Cu NPs by the Novel Bio-mediated route were exploited to construct a non-enzymatic glucose biosensor for sustainable clinical field applications.

Basolateral choline transport in isolated rabbit renal proximal tubules.

PubMed

Dantzler, W H; Evans, K K; Wright, S H

1998-11-01

Choline can undergo both net secretion and net reabsorption by renal proximal tubules, but at physiological plasma levels net reabsorption occurs. During this process, choline enters the cells at the luminal side down an electrochemical gradient via a specific transporter with a high affinity for choline. It appeared likely that choline was then transported out of the cells against an electrochemical gradient at the basolateral membrane by countertransport for another organic cation. This possibility was examined by studying net transepithelial reabsorption and basolateral uptake and efflux of [14C]choline in isolated S2 segments of rabbit renal proximal tubules. Basolateral uptake, which was inhibited by other organic cations such as tetraethylammonium (TEA), appeared to occur by the standard organic cation transport pathway. However, the addition of TEA to the bathing medium not only failed to trans-stimulate net transepithelial reabsorption and basolateral efflux of [14C]choline but it actually inhibited transepithelial reabsorption by @60%. The results do not support the presence of a countertransport step for choline against an electrochemical gradient at the basolateral membrane. Instead, they suggest that choline crosses this membrane by some form of carrier-mediated diffusion even during the reabsorptive process.

Disposable and reliable electrochemical magnetoimmunosensor for Fumonisins simplified determination in maize-based foodstuffs.

PubMed

Jodra, Adrián; López, Miguel Ángel; Escarpa, Alberto

2015-02-15

An electrochemical magnetoimmunosensor involving magnetic beads and disposable carbon screen-printed electrode (CSPE) for Fumonosins (FB1, FB2 and FB3) has been developed and evaluated through a certified reference material (CRM) and beer samples. Once the immunochemical reactions took place on the magnetic beads solution, they were confined on the surface of CSPE, where electrochemical detection is achieved through the addition of suitable substrate and mediator for enzymatic tracer (Horseradish peroxidase--HRP). A remarkable detection limit of 0.33 μg L(-1), outstanding repeatability and reproducibility (RSD(intraday) of 5.6% and 2.9%; RSD(interday) of 6.9% and 6.0%; both for 0 and 5 μg L(-1) FB1 respectively), and excellent accuracy with recovery rate of 85-96% showed the suggested approach to be a very suitable screening tool for the analysis of Fumonisin B1 and B2 in food samples. A simultaneous simplified calibration and analysis protocol allows a fast and reliable determination of Fumonisin in beer samples with recovery rate of 87-105%. This strategy enhanced the analytical merits of immunosensor approach towards truly disposable tools for food-safety monitoring. Copyright © 2014 Elsevier B.V. All rights reserved.

Production of bioelectricity, bio-hydrogen, high value chemicals and bioinspired nanomaterials by electrochemically active biofilms.

PubMed

Kalathil, Shafeer; Khan, Mohammad Mansoob; Lee, Jintae; Cho, Moo Hwan

2013-11-01

Microorganisms naturally form biofilms on solid surfaces for their mutual benefits including protection from environmental stresses caused by contaminants, nutritional depletion or imbalances. The biofilms are normally dangerous to human health due to their inherited robustness. On the other hand, a recent study suggested that electrochemically active biofilms (EABs) generated by electrically active microorganisms have properties that can be used to catalyze or control the electrochemical reactions in a range of fields, such as bioenergy production, bioremediation, chemical/biological synthesis, bio-corrosion mitigation and biosensor development. EABs have attracted considerable attraction in bioelectrochemical systems (BESs), such as microbial fuel cells and microbial electrolysis cells, where they act as living bioanode or biocathode catalysts. Recently, it was reported that EABs can be used to synthesize metal nanoparticles and metal nanocomposites. The EAB-mediated synthesis of metal and metal-semiconductor nanocomposites is expected to provide a new avenue for the greener synthesis of nanomaterials with high efficiency and speed than other synthetic methods. This review covers the general introduction of EABs, as well as the applications of EABs in BESs, and the production of bio-hydrogen, high value chemicals and bio-inspired nanomaterials. Copyright © 2013 Elsevier Inc. All rights reserved.

Redox-Active Star Molecules Incorporating the 4-Benzoylpyridinium Cation - Implications for the Charge Transfer Along Branches vs. Across the Perimeter in Dendrimer

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Yang, Jinua; Fabrizio,Even F.; Rawashdeh, Abdel-Monem M.; Oh, Woon Su; Sotiriou-Leventis, Chariklia

2004-01-01

Dendrimers are self-repeating globular branched star molecules, whose fractal structure continues to fascinate, challenge, and inspire. Functional dendrimers may incorporate redox centers, and potential applications include antennae molecules for light harvesting, sensors, mediators, and artificial biomolecules. We report the synthesis and redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that on1y two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV/s and as fast as 10 V/s. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers.

Amplified and in situ detection of redox-active metabolite using a biobased redox capacitor.

PubMed

Kim, Eunkyoung; Gordonov, Tanya; Bentley, William E; Payne, Gregory F

2013-02-19

Redox cycling provides a mechanism to amplify electrochemical signals for analyte detection. Previous studies have shown that diverse mediators/shuttles can engage in redox-cycling reactions with a biobased redox capacitor that is fabricated by grafting redox-active catechols onto a chitosan film. Here, we report that redox cycling with this catechol-chitosan redox capacitor can amplify electrochemical signals for detecting a redox-active bacterial metabolite. Specifically, we studied the redox-active bacterial metabolite pyocyanin that is reported to be a virulence factor and signaling molecule for the opportunistic pathogen P. aeruginosa. We demonstrate that redox cycling can amplify outputs from various electrochemical methods (cyclic voltammetry, chronocoulometry, and differential pulse voltammetry) and can lower the detection limit of pyocyanin to 50 nM. Further, the compatibility of this biobased redox capacitor allows the in situ monitoring of the production of redox-active metabolites (e.g., pyocyanin) during the course of P. aeruginosa cultivation. We anticipate that the amplified output of redox-active virulence factors should permit an earlier detection of life-threatening infections by the opportunistic pathogen P. aeruginosa while the "bio-compatibility" of this measurement approach should facilitate in situ study of the spatiotemporal dynamics of bacterial redox signaling.

Microbial Biofilm Voltammetry: Direct Electrochemical Characterization of Catalytic Electrode-Attached Biofilms▿ †

PubMed Central

Marsili, Enrico; Rollefson, Janet B.; Baron, Daniel B.; Hozalski, Raymond M.; Bond, Daniel R.

2008-01-01

While electrochemical characterization of enzymes immobilized on electrodes has become common, there is still a need for reliable quantitative methods for study of electron transfer between living cells and conductive surfaces. This work describes growth of thin (<20 μm) Geobacter sulfurreducens biofilms on polished glassy carbon electrodes, using stirred three-electrode anaerobic bioreactors controlled by potentiostats and nondestructive voltammetry techniques for characterization of viable biofilms. Routine in vivo analysis of electron transfer between bacterial cells and electrodes was performed, providing insight into the main redox-active species participating in electron transfer to electrodes. At low scan rates, cyclic voltammetry revealed catalytic electron transfer between cells and the electrode, similar to what has been observed for pure enzymes attached to electrodes under continuous turnover conditions. Differential pulse voltammetry and electrochemical impedance spectroscopy also revealed features that were consistent with electron transfer being mediated by an adsorbed catalyst. Multiple redox-active species were detected, revealing complexity at the outer surfaces of this bacterium. These techniques provide the basis for cataloging quantifiable, defined electron transfer phenotypes as a function of potential, electrode material, growth phase, and culture conditions and provide a framework for comparisons with other species or communities. PMID:18849456

Gold nanoparticles-induced enhancement of the analytical response of an electrochemical biosensor based on an organic-inorganic hybrid composite material.

PubMed

Barbadillo, M; Casero, E; Petit-Domínguez, M D; Vázquez, L; Pariente, F; Lorenzo, E

2009-12-15

The design and characterization of a new organic-inorganic hybrid composite material for glucose electrochemical sensing are described. This material is based on the entrapment of both gold nanoparticles (AuNPs) and glucose oxidase, which was chosen as a model, into a sol-gel matrix. The addition of spectroscopic grade graphite to this system, which confers conductivity, leads to the development of a material particularly attractive for electrochemical biosensor fabrication. The characterization of the hybrid composite material was performed using atomic force microscopy and scanning electron microscopy techniques. This composite material was applied to the determination of glucose in presence of hydroxymethylferrocene as a redox mediator. The system exhibits a clear electrocatalytic activity towards glucose, allowing its determination at 250 mV vs Ag/AgCl. The performance of the resulting enzyme biosensor was evaluated in terms of sensitivity, detection limit, linear response range, stability and accuracy. Finally, the enhancement of the analytical response of the resulting biosensor induced by the presence of gold nanoparticles was evaluated by comparison with a similar organic-inorganic hybrid composite material without AuNPs.

GAP-43 is essential for the neurotrophic effects of BDNF and positive AMPA receptor modulator S18986.

PubMed

Gupta, S K; Mishra, R; Kusum, S; Spedding, M; Meiri, K F; Gressens, P; Mani, S

2009-04-01

Positive alpha-amino-3-hydroxy-5-methylisoxazole-4-propionic acid (AMPA) receptor modulators include benzamide compounds that allosterically modulate AMPA glutamate receptors. These small molecules that cross the blood-brain barrier have been shown to act as a neuroprotectant by increasing the levels of endogenous brain-derived neurotrophic factor (BDNF). Positive AMPA receptor modulators have also been shown to increase the levels of growth-associated protein-43 (GAP-43). GAP-43 plays a major role in many aspects of neuronal function in vertebrates. The goal of this study was to determine whether GAP-43 was important in mediating the actions of positive AMPA receptor modulator (S18986) and BDNF. Using cortical cultures from GAP-43 knockout and control mice, we show that (1) GAP-43 is upregulated in response to S18986 and BDNF in control cultures; (2) this upregulation of GAP-43 is essential for mediating the neuroprotective effects of S18986 and BDNF; (3) administration of S18986 and BDNF leads to an increase in the expression of the glutamate transporters GLT-1 and GLAST that are key to limiting excitotoxic cell death and this increase in GLT-1 and GLAST expression is completely blocked in the absence of GAP-43. Taken together this study concludes that GAP-43 is an important mediator of the neurotrophic effects of S18986 and BDNF on neuronal survival and plasticity, and is essential for the success of positive AMPA receptor modulator-BDNF-based neurotrophin therapy.

Myeloid-derived suppressor cells modulate B-cell responses.

PubMed

Lelis, Felipe J N; Jaufmann, Jennifer; Singh, Anurag; Fromm, Katja; Teschner, Annkathrin Chiara; Pöschel, Simone; Schäfer, Iris; Beer-Hammer, Sandra; Rieber, Nikolaus; Hartl, Dominik

2017-08-01

Myeloid-derived suppressor cells (MDSCs) are key regulators of adaptive immunity by suppressing T-cell functions. However, their potential action on or interaction with B cells remained poorly understood. Here we demonstrate that human polymorphonuclear MDSCs differentially modulate B-cell function by suppressing B-cell proliferation and antibody production. We further demonstrate that this MDSC-mediated effect is cell contact dependent and involves established mediators such as arginase-1, nitric oxide (NO), reactive oxygen species (ROS) as well as B-cell death. Collectively, our studies provide novel evidence that human MDSCs modulate B cells, which could have future implications for immunotherapy approaches. Copyright © 2017 European Federation of Immunological Societies. Published by Elsevier B.V. All rights reserved.

Evidence for Multiple Mediator Complexes in Yeast Independently Recruited by Activated Heat Shock Factor

PubMed Central

Anandhakumar, Jayamani; Moustafa, Yara W.; Chowdhary, Surabhi; Kainth, Amoldeep S.

2016-01-01

Mediator is an evolutionarily conserved coactivator complex essential for RNA polymerase II transcription. Although it has been generally assumed that in Saccharomyces cerevisiae, Mediator is a stable trimodular complex, its structural state in vivo remains unclear. Using the “anchor away” (AA) technique to conditionally deplete select subunits within Mediator and its reversibly associated Cdk8 kinase module (CKM), we provide evidence that Mediator's tail module is highly dynamic and that a subcomplex consisting of Med2, Med3, and Med15 can be independently recruited to the regulatory regions of heat shock factor 1 (Hsf1)-activated genes. Fluorescence microscopy of a scaffold subunit (Med14)-anchored strain confirmed parallel cytoplasmic sequestration of core subunits located outside the tail triad. In addition, and contrary to current models, we provide evidence that Hsf1 can recruit the CKM independently of core Mediator and that core Mediator has a role in regulating postinitiation events. Collectively, our results suggest that yeast Mediator is not monolithic but potentially has a dynamic complexity heretofore unappreciated. Multiple species, including CKM-Mediator, the 21-subunit core complex, the Med2-Med3-Med15 tail triad, and the four-subunit CKM, can be independently recruited by activated Hsf1 to its target genes in AA strains. PMID:27185874

Trauma exposure and cigarette smoking: the impact of negative affect and affect-regulatory smoking motives.

PubMed

Farris, Samantha G; Zvolensky, Michael J; Beckham, Jean C; Vujanovic, Anka A; Schmidt, Norman B

2014-01-01

Cognitive-affective mechanisms related to the maintenance of smoking among trauma-exposed individuals are largely unknown. Cross-sectional data from trauma-exposed treatment-seeking smokers (n = 283) were utilized to test a series of multiple mediator models of trauma exposure and smoking, as mediated by the sequential effects of negative affect and affect-modulation smoking motives. The sequential effects of both mediators indirectly predicted the effect of greater trauma exposure types on nicotine dependence, a biochemical index of smoking, perceived barriers to smoking cessation, and greater withdrawal-related problems during past quit attempts. Negative affect and affect-modulation motives for smoking may contribute to the trauma-smoking association.

Trauma Exposure and Cigarette Smoking: The Impact of Negative Affect and Affect-Regulatory Smoking Motives

PubMed Central

Farris, Samantha G.; Zvolensky, Michael J.; Beckham, Jean C.; Vujanovic, Anka A.; Schmidt, Norman B.

2014-01-01

Cognitive-affective mechanisms related to the maintenance of smoking among trauma-exposed individuals are largely unknown. Cross-sectional data from trauma-exposed treatment-seeking smokers (n = 283) were utilized to test a series of multiple mediator models of trauma exposure and smoking, as mediated by the sequential effects of negative affect and affect-modulation smoking motives. The sequential effects of both mediators indirectly predicted the effect of greater trauma exposure types on nicotine dependence, a biochemical index of smoking, perceived barriers to smoking cessation, and greater withdrawal-related problems during past quit attempts. Negative affect and affect-modulation motives for smoking may contribute to the trauma-smoking association. PMID:25299617

Dopamine does double duty in motivating cognitive effort

PubMed Central

Westbrook, Andrew; Braver, Todd S.

2015-01-01

Cognitive control is subjectively costly, suggesting that engagement is modulated in relationship to incentive state. Dopamine appears to play key roles. In particular, dopamine may mediate cognitive effort by two broad classes of functions: 1) modulating the functional parameters of working memory circuits subserving effortful cognition, and 2) mediating value-learning and decision-making about effortful cognitive action. Here we tie together these two lines of research, proposing how dopamine serves “double duty”, translating incentive information into cognitive motivation. PMID:26889810

Direct metabolite detection with an n-type accumulation mode organic electrochemical transistor

PubMed Central

Maria, Iuliana Petruta; Uguz, Ilke

2018-01-01

The inherent specificity and electrochemical reversibility of enzymes poise them as the biorecognition element of choice for a wide range of metabolites. To use enzymes efficiently in biosensors, the redox centers of the protein should have good electrical communication with the transducing electrode, which requires either the use of mediators or tedious biofunctionalization approaches. We report an all-polymer micrometer-scale transistor platform for the detection of lactate, a significant metabolite in cellular metabolic pathways associated with critical health care conditions. The device embodies a new concept in metabolite sensing where we take advantage of the ion-to-electron transducing qualities of an electron-transporting (n-type) organic semiconductor and the inherent amplification properties of an ion-to-electron converting device, the organic electrochemical transistor. The n-type polymer incorporates hydrophilic side chains to enhance ion transport/injection, as well as to facilitate enzyme conjugation. The material is capable of accepting electrons of the enzymatic reaction and acts as a series of redox centers capable of switching between the neutral and reduced state. The result is a fast, selective, and sensitive metabolite sensor. The advantage of this device compared to traditional amperometric sensors is the amplification of the input signal endowed by the electrochemical transistor circuit and the design simplicity obviating the need for a reference electrode. The combination of redox enzymes and electron-transporting polymers will open up an avenue not only for the field of biosensors but also for the development of enzyme-based electrocatalytic energy generation/storage devices.

Direct metabolite detection with an n-type accumulation mode organic electrochemical transistor.

PubMed

Pappa, Anna Maria; Ohayon, David; Giovannitti, Alexander; Maria, Iuliana Petruta; Savva, Achilleas; Uguz, Ilke; Rivnay, Jonathan; McCulloch, Iain; Owens, Róisín M; Inal, Sahika

2018-06-01

The inherent specificity and electrochemical reversibility of enzymes poise them as the biorecognition element of choice for a wide range of metabolites. To use enzymes efficiently in biosensors, the redox centers of the protein should have good electrical communication with the transducing electrode, which requires either the use of mediators or tedious biofunctionalization approaches. We report an all-polymer micrometer-scale transistor platform for the detection of lactate, a significant metabolite in cellular metabolic pathways associated with critical health care conditions. The device embodies a new concept in metabolite sensing where we take advantage of the ion-to-electron transducing qualities of an electron-transporting (n-type) organic semiconductor and the inherent amplification properties of an ion-to-electron converting device, the organic electrochemical transistor. The n-type polymer incorporates hydrophilic side chains to enhance ion transport/injection, as well as to facilitate enzyme conjugation. The material is capable of accepting electrons of the enzymatic reaction and acts as a series of redox centers capable of switching between the neutral and reduced state. The result is a fast, selective, and sensitive metabolite sensor. The advantage of this device compared to traditional amperometric sensors is the amplification of the input signal endowed by the electrochemical transistor circuit and the design simplicity obviating the need for a reference electrode. The combination of redox enzymes and electron-transporting polymers will open up an avenue not only for the field of biosensors but also for the development of enzyme-based electrocatalytic energy generation/storage devices.

A Highly-Sensitive Picric Acid Chemical Sensor Based on ZnO Nanopeanuts.

PubMed

Ibrahim, Ahmed A; Tiwari, Preeti; Al-Assiri, M S; Al-Salami, A E; Umar, Ahmad; Kumar, Rajesh; Kim, S H; Ansari, Z A; Baskoutas, S

2017-07-13

Herein, we report a facile synthesis, characterization, and electrochemical sensing application of ZnO nanopeanuts synthesized by a simple aqueous solution process and characterized by various techniques in order to confirm the compositional, morphological, structural, crystalline phase, and optical properties of the synthesized material. The detailed characterizations revealed that the synthesized material possesses a peanut-shaped morphology, dense growth, and a wurtzite hexagonal phase along with good crystal and optical properties. Further, to ascertain the useful properties of the synthesized ZnO nanopeanut as an excellent electron mediator, electrochemical sensors were fabricated based on the form of a screen printed electrode (SPE). Electrochemical and current-voltage characteristics were studied for the determination of picric acid sensing characteristics. The electrochemical sensor fabricated based on the SPE technique exhibited a reproducible and reliable sensitivity of ~1.2 μA/mM (9.23 μA·mM -1 ·cm -2 ), a lower limit of detection at 7.8 µM, a regression coefficient ( R ²) of 0.94, and good linearity over the 0.0078 mM to 10.0 mM concentration range. In addition, the sensor response was also tested using simple I-V techniques, wherein a sensitivity of 493.64 μA·mM -1 ·cm -2 , an experimental Limit of detection (LOD) of 0.125 mM, and a linear dynamic range (LDR) of 1.0 mM-5.0 mM were observed for the fabricated picric acid sensor.

A Highly-Sensitive Picric Acid Chemical Sensor Based on ZnO Nanopeanuts

PubMed Central

Ibrahim, Ahmed A.; Tiwari, Preeti; Al-Assiri, M. S.; Al-Salami, A. E.; Umar, Ahmad; Kumar, Rajesh; Kim, S. H.; Ansari, Z. A.; Baskoutas, S.

2017-01-01

Herein, we report a facile synthesis, characterization, and electrochemical sensing application of ZnO nanopeanuts synthesized by a simple aqueous solution process and characterized by various techniques in order to confirm the compositional, morphological, structural, crystalline phase, and optical properties of the synthesized material. The detailed characterizations revealed that the synthesized material possesses a peanut-shaped morphology, dense growth, and a wurtzite hexagonal phase along with good crystal and optical properties. Further, to ascertain the useful properties of the synthesized ZnO nanopeanut as an excellent electron mediator, electrochemical sensors were fabricated based on the form of a screen printed electrode (SPE). Electrochemical and current-voltage characteristics were studied for the determination of picric acid sensing characteristics. The electrochemical sensor fabricated based on the SPE technique exhibited a reproducible and reliable sensitivity of ~1.2 μA/mM (9.23 μA·mM−1·cm−2), a lower limit of detection at 7.8 µM, a regression coefficient (R2) of 0.94, and good linearity over the 0.0078 mM to 10.0 mM concentration range. In addition, the sensor response was also tested using simple I-V techniques, wherein a sensitivity of 493.64 μA·mM−1·cm−2, an experimental Limit of detection (LOD) of 0.125 mM, and a linear dynamic range (LDR) of 1.0 mM–5.0 mM were observed for the fabricated picric acid sensor. PMID:28773151

Host defense peptides of thrombin modulate inflammation and coagulation in endotoxin-mediated shock and Pseudomonas aeruginosa sepsis.

PubMed

Kalle, Martina; Papareddy, Praveen; Kasetty, Gopinath; Mörgelin, Matthias; van der Plas, Mariena J A; Rydengård, Victoria; Malmsten, Martin; Albiger, Barbara; Schmidtchen, Artur

2012-01-01

Gram-negative sepsis is accompanied by a disproportionate innate immune response and excessive coagulation mainly induced by endotoxins released from bacteria. Due to rising antibiotic resistance and current lack of other effective treatments there is an urgent need for new therapies. We here present a new treatment concept for sepsis and endotoxin-mediated shock, based on host defense peptides from the C-terminal part of human thrombin, found to have a broad and inhibitory effect on multiple sepsis pathologies. Thus, the peptides abrogate pro-inflammatory cytokine responses to endotoxin in vitro and in vivo. Furthermore, they interfere with coagulation by modulating contact activation and tissue factor-mediated clotting in vitro, leading to normalization of coagulation responses in vivo, a previously unknown function of host defense peptides. In a mouse model of Pseudomonas aeruginosa sepsis, the peptide GKY25, while mediating a modest antimicrobial effect, significantly inhibited the pro-inflammatory response, decreased fibrin deposition and leakage in the lungs, as well as reduced mortality. Taken together, the capacity of such thrombin-derived peptides to simultaneously modulate bacterial levels, pro-inflammatory responses, and coagulation, renders them attractive therapeutic candidates for the treatment of invasive infections and sepsis.

Assessment of Computer-Mediated Module Intervention in a Pharmacy Calculations Course

ERIC Educational Resources Information Center

Bell, Edward C.; Fike, David S.; Liang, Dong; Lockman, Paul R.; McCall, Kenneth L.

2017-01-01

Computer module intervention is the process of exposing students to a series of discrete exercises for the purpose of strengthening students' familiarity with conceptual material. The method has been suggested as a remedy to student under-preparedness. This study was conducted to determine the effectiveness of module intervention in improving and…

Regulating the ethylene response of a plant by modulation of F-box proteins

DOEpatents

Guo, Hongwei [Beijing, CN; Ecker, Joseph R [Carlsbad, CA

2014-01-07

The relationship between F-box proteins and proteins invovled in the ethylene response in plants is described. In particular, F-box proteins may bind to proteins involved in the ethylene response and target them for degradation by the ubiquitin/proteasome pathway. The transcription factor EIN3 is a key transcription factor mediating ethylne-regulated gene expression and morphological responses. EIN3 is degraded through a ubiquitin/proteasome pathway mediated by F-box proteins EBF1 and EBF2. The link between F-box proteins and the ethylene response is a key step in modulating or regulating the response of a plant to ethylene. Described herein are transgenic plants having an altered sensitivity to ethylene, and methods for making transgenic plant haing an althered sensitivity to ethylene by modulating the level of activity of F-box proteins. Methods of altering the ethylene response in a plant by modulating the activity or expression of an F-box protein are described. Also described are methods of identifying compounds that modulate the ethylene response in plants by modulating the level of F-box protein expression or activity.

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.

The Role of the Brain's Endocannabinoid System in Pain and Its Modulation by Stress.

PubMed

Corcoran, Louise; Roche, Michelle; Finn, David P

2015-01-01

Stress has a complex, bidirectional modulatory influence on pain. Stress may either reduce (stress-induced analgesia) or exacerbate (stress-induced hyperalgesia) pain depending on the nature, duration, and intensity of the stressor. The endogenous cannabinoid (endocannabinoid) system is present throughout the neuroanatomical pathways that mediate and modulate responses to painful stimuli. The specific role of the endocannabinoid system in the brain in pain and the modulation of pain by stress is reviewed herein. We first provide a brief overview of the endocannabinoid system, followed by a review of the evidence that the brain's endocannabinoid system modulates pain. We provide a comprehensive evaluation of the role of the endocannabinoid system supraspinally, and particularly in the rostral ventromedial medulla, periaqueductal gray, amygdala, and prefrontal cortex, in pain, stress-induced analgesia, and stress-induced hyperalgesia. Increased understanding of endocannabinoid-mediated regulation of pain and its modulation by stress will inform the development of novel therapeutic approaches for pain and its comorbidity with stress-related disorders. © 2015 Elsevier Inc. All rights reserved.

Caveolae: a regulatory platform for nutritional modulation of inflammatory diseases

PubMed Central

Layne, Joseph; Majkova, Zuzana; Smart, Eric J.; Toborek, Michal; Hennig, Bernhard

2010-01-01

Dietary intervention strategies have proven to be an effective means of decreasing several risk factors associated with the development of atherosclerosis. Endothelial cell dysfunction influences vascular inflammation and is involved in promoting the earliest stages of lesion formation. Caveolae are lipid raft microdomains abundant within the plasma membrane of endothelial cells and are responsible for mediating receptor-mediated signal transduction. Caveolae have been implicated in the regulation of enzymes associated with several key signaling pathways capable of determining intracellular redox status. Diet and plasma-derived nutrients may modulate an inflammatory outcome by interacting with and altering caveolae-associated cellular signaling. For example, omega-3 fatty acids and several polyphenolics have been shown to improve endothelial cell function by decreasing the formation of ROS and increasing NO bioavailability, events associated with altered caveolae composition. Thus, nutritional modulation of caveolae-mediated signaling events may provide an opportunity to ameliorate inflammatory signaling pathways capable of promoting the formation of vascular diseases, including atherosclerosis. PMID:21292468

Optimization by Molecular Fine Tuning of Dihydro-β-agarofuran Sesquiterpenoids as Reversers of P-Glycoprotein-Mediated Multidrug Resistance.

PubMed

Callies, Oliver; Sánchez-Cañete, María P; Gamarro, Francisco; Jiménez, Ignacio A; Castanys, Santiago; Bazzocchi, Isabel L

2016-03-10

P-glycoprotein (P-gp) plays a crucial role in the development of multidrug resistance (MDR), a major obstacle for successful chemotherapy in cancer. Herein, we report on the development of a natural-product-based library of 81 dihydro-β-agarofuran sesquiterpenes (2-82) by optimization of the lead compound 1. The compound library was evaluated for its ability to inhibit P-gp-mediated daunomycin efflux in MDR cells. Selected analogues were further analyzed for their P-gp inhibition constant, intrinsic toxicity, and potency to reverse daunomycin and vinblastine resistances. Analogues 6, 24, 28, 59, and 66 were identified as having higher potency than compound 1 and verapamil, a first-generation P-gp modulator. SAR analysis revealed the size of the aliphatic chains and presence of nitrogen atoms are important structural characteristics to modulate reversal activity. The present study highlights the potential of these analogues as modulators of P-gp mediated MDR in cancer cells.

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.

Calpain cleavage within dysferlin exon 40a releases a synaptotagmin-like module for membrane repair

PubMed Central

Redpath, G. M. I.; Woolger, N.; Piper, A. K.; Lemckert, F. A.; Lek, A.; Greer, P. A.; North, K. N.; Cooper, S. T.

2014-01-01

Dysferlin and calpain are important mediators of the emergency response to repair plasma membrane injury. Our previous research revealed that membrane injury induces cleavage of dysferlin to release a synaptotagmin-like C-terminal module we termed mini-dysferlinC72. Here we show that injury-activated cleavage of dysferlin is mediated by the ubiquitous calpains via a cleavage motif encoded by alternately spliced exon 40a. An exon 40a–specific antibody recognizing cleaved mini-dysferlinC72 intensely labels the circumference of injury sites, supporting a key role for dysferlinExon40a isoforms in membrane repair and consistent with our evidence suggesting that the calpain-cleaved C-terminal module is the form specifically recruited to injury sites. Calpain cleavage of dysferlin is a ubiquitous response to membrane injury in multiple cell lineages and occurs independently of the membrane repair protein MG53. Our study links calpain and dysferlin in the calcium-activated vesicle fusion of membrane repair, placing calpains as upstream mediators of a membrane repair cascade that elicits cleaved dysferlin as an effector. Of importance, we reveal that myoferlin and otoferlin are also cleaved enzymatically to release similar C-terminal modules, bearing two C2 domains and a transmembrane domain. Evolutionary preservation of this feature highlights its functional importance and suggests that this highly conserved C-terminal region of ferlins represents a functionally specialized vesicle fusion module. PMID:25143396

Functional metabolomics as a tool to analyze Mediator function and structure in plants.

PubMed

Davoine, Celine; Abreu, Ilka N; Khajeh, Khalil; Blomberg, Jeanette; Kidd, Brendan N; Kazan, Kemal; Schenk, Peer M; Gerber, Lorenz; Nilsson, Ove; Moritz, Thomas; Björklund, Stefan

2017-01-01

Mediator is a multiprotein transcriptional co-regulator complex composed of four modules; Head, Middle, Tail, and Kinase. It conveys signals from promoter-bound transcriptional regulators to RNA polymerase II and thus plays an essential role in eukaryotic gene regulation. We describe subunit localization and activities of Mediator in Arabidopsis through metabolome and transcriptome analyses from a set of Mediator mutants. Functional metabolomic analysis based on the metabolite profiles of Mediator mutants using multivariate statistical analysis and heat-map visualization shows that different subunit mutants display distinct metabolite profiles, which cluster according to the reported localization of the corresponding subunits in yeast. Based on these results, we suggest localization of previously unassigned plant Mediator subunits to specific modules. We also describe novel roles for individual subunits in development, and demonstrate changes in gene expression patterns and specific metabolite levels in med18 and med25, which can explain their phenotypes. We find that med18 displays levels of phytoalexins normally found in wild type plants only after exposure to pathogens. Our results indicate that different Mediator subunits are involved in specific signaling pathways that control developmental processes and tolerance to pathogen infections.

Houttuynia cordata modulates oral innate immune mediators: potential role of herbal plant on oral health.

PubMed

Satthakarn, S; Chung, W O; Promsong, A; Nittayananta, W

2015-05-01

Epithelial cells play an active role in oral innate immunity by producing various immune mediators. Houttuynia cordata Thunb (H. cordata), a herbal plant found in Asia, possesses many activities. However, its impacts on oral innate immunity have never been reported. The aim of this study was to determine the effects of H. cordata extract on the expression of innate immune mediators produced by oral epithelial cells. Primary gingival epithelial cells (GECs) were treated with various concentrations of the extract for 18 h. The gene expression of hBD2, SLPI, cytokines, and chemokines was measured using quantitative real-time RT-PCR. The secreted proteins in the culture supernatants were detected by ELISA or Luminex assay. Cytotoxicity of the extract was assessed using CellTiter-Blue Assay. H. cordata significantly induced the expression of hBD2, SLPI, IL-8, and CCL20 in a dose-dependent manner without cytotoxicity. The secreted hBD2 and SLPI proteins were modulated, and the levels of IL-2, IL-6, IL-8, and IFN-γ were significantly induced by the extract. Our data indicated that H. cordata can modulate oral innate immune mediators. These findings may lead to the development of new topical agents from H. cordata for the prevention and treatment of immune-mediated oral diseases. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

Renal intercalated cells and blood pressure regulation

PubMed Central

Wall, Susan M.

2017-01-01

Type B and non-A, non-B intercalated cells are found within the connecting tubule and the cortical collecting duct. Of these cell types, type B intercalated cells are known to mediate Cl− absorption and HCO3− secretion largely through pendrin-dependent Cl−/HCO3− exchange. This exchange is stimulated by angiotensin II administration and is also stimulated in models of metabolic alkalosis, for instance after aldosterone or NaHCO3 administration. In some rodent models, pendrin-mediated HCO3− secretion modulates acid-base balance. However, the role of pendrin in blood pressure regulation is likely of more physiological or clinical significance. Pendrin regulates blood pressure not only by mediating aldosterone-sensitive Cl− absorption, but also by modulating the aldosterone response for epithelial Na+ channel (ENaC)-mediated Na+ absorption. Pendrin regulates ENaC through changes in open channel of probability, channel surface density, and channels subunit total protein abundance. Thus, aldosterone stimulates ENaC activity through both direct and indirect effects, the latter occurring through its stimulation of pendrin expression and function. Therefore, pendrin contributes to the aldosterone pressor response. Pendrin may also modulate blood pressure in part through its action in the adrenal medulla, where it modulates the release of catecholamines, or through an indirect effect on vascular contractile force. This review describes how aldosterone and angiotensin II-induced signaling regulate pendrin and the contributory role of pendrin in distal nephron function and blood pressure. PMID:29285423

An Allosteric Coagonist Model for Propofol Effects on α1β2γ2L γ-Aminobutyric Acid Type A Receptors

PubMed Central

Ruesch, Dirk; Neumann, Elena; Wulf, Hinnerk; Forman, Stuart A.

2011-01-01

Background Propofol produces its major actions via γ-aminobutyric acid type A (GABAA) receptors. At low concentrations, propofol enhances agonist-stimulated GABAA receptor activity, and high propofol concentrations directly activate receptors. Etomidate produces similar effects, and there is convincing evidence that a single class of etomidate sites mediate both agonist modulation and direct GABAA receptor activation. It is unknown if the propofol binding site(s) on GABAA receptors that modulate agonist-induced activity also mediate direct activation. Methods GABAA α1β2γ2L receptors were heterologously expressed in Xenopus oocytes and activity was quantified using voltage clamp electrophysiology. We tested whether propofol and etomidate display the same linkage between agonist modulation and direct activation of GABAA receptors by identifying equi-efficacious drug solutions for direct activation. We then determined whether these drug solutions produce equal modulation of GABA-induced receptor activity. We also measured propofol-dependent direct activation and modulation of low GABA responses. Allosteric coagonist models similar to that established for etomidate, but with variable numbers of propofol sites, were fitted to combined data. Results Solutions of 19 μM propofol and 10 μM etomidate were found to equally activate GABAA receptors. These two drug solutions also produced indistinguishable modulation of GABA-induced receptor activity. Combined electrophysiological data behaved in a manner consistent with allosteric co-agonist models with more than one propofol site. The best fit was observed when the model assumed three equivalent propofol sites. Conclusions Our results support the hypothesis that propofol, like etomidate, acts at GABAA receptor sites mediating both GABA modulation and direct activation. PMID:22104494

Metabotropic glutamate receptor modulation of dopamine release in the nucleus accumbens shell is unaffected by phencyclidine pretreatment: In vitro assessment using fast-scan cyclic voltammetry rat brain slices.

PubMed

Gupta, Ishan; Young, Andrew M J

2018-05-15

The non-competitive glutamate antagonist, phencyclidine is used in rodents to model behavioural deficits see in schizophrenia. Importantly, these deficits endure long after the cessation of short-term chronic treatment (sub-chronic), indicating that the drug treatment causes long-term changes in the physiology and/or chemistry of the brain. There is evidence that this may occur through glutamatergic modulation of mesolimbic dopamine release, perhaps involving metabotropic glutamate receptors (mGluR). This study sought to investigate the effect of sub-chronic phencyclidine pretreatment on modulation of dopamine neurotransmission by metabotropic glutamate receptors 2 and 5 (mGluR2 and mGluR5) in the nucleus accumbens shell in vitro, with the hypothesis that phencyclidine pretreatment would disrupt the mGluR-mediated modulation of dopamine release. We showed that the orthosteric mGluR2 agonist LY379268 (0.1 µM, 1 µM and 10 µM) and mGluR5 positive allosteric modulator CDPPB (1 µM and 10 µM) both attenuated potassium-evoked dopamine release, underscoring their role in modulating dopamine neurotransmission in the nucleus accumbens. Sub-chronic PCP treatment, which caused cognitive deficits measured by performance in the novel object recognition task, modelling aspects of behavioral deficits seen in schizophrenia, induced neurobiological changes that enhanced dopamine release in the nucleus accumbens, but had no effect on mGluR2 or mGluR5 mediated changes in dopamine release. Therefore it is unlikely that schizophrenia-related behavioural changes seen after sub-chronic phencyclidine pre-treatment are mediated through mGluR modulation of dopamine release. Copyright © 2018 Elsevier B.V. All rights reserved.

Ferrocene-functionalized 4-(2,5-Di(thiophen-2-yl)-1H-pyrrol-1-yl)aniline: a novel design in conducting polymer-based electrochemical biosensors.

PubMed

Ayranci, Rukiye; Demirkol, Dilek Odaci; Ak, Metin; Timur, Suna

2015-01-13

Herein, we report a novel ferrocenyldithiophosphonate functional conducting polymer and its use as an immobilization matrix in amperometric biosensor applications. Initially, 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)amidoferrocenyldithiophosphonate was synthesized and copolymerized with 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)benzenamine at graphite electrodes. The amino groups on the polymer were utilized for covalent attachment of the enzyme glucose oxidase. Besides, ferrocene on the backbone was used as a redox mediator during the electrochemical measurements. Prior to the analytical characterization, optimization studies were carried out. The changes in current signals at +0.45 V were proportional to glucose concentration from 0.5 to 5.0 mM. Finally, the resulting biosensor was applied for glucose analysis in real samples and the data were compared with the spectrophotometric Trinder method.

Copper Salts Mediated Morphological Transformation of Cu2O from Cubes to Hierarchical Flower-like or Microspheres and Their Supercapacitors Performances

PubMed Central

Chen, Liang; Zhang, Yu; Zhu, Pengli; Zhou, Fengrui; Zeng, Wenjin; Lu, Daoqiang Daniel; Sun, Rong; Wong, Chingping

2015-01-01

Monodisperse Cu2O of different microstructures, such as cubes, flower-like, and microspheres, have been extensively synthesized by a simple polyol reduction method using different copper salts, i.e. (Cu(acac)2, Cu(OH)2, and Cu(Ac)2·H2O). The effects of copper salts on the morphology of Cu2O were investigated in details through various characterization methods, including X-ray diffraction, transmission electron microscopy, scanning electron microscopy and UV-Vis absorption spectra. The effects of morphology on the electrochemical properties were further studied. Among the different structures, Cu2O with the microspheric morphology shows the highest specific capacitance and the best cycling stability compared with those of the other two structures, thus bear larger volume charge during the electrochemical reaction due to the microspheres of small nanoparticles. PMID:25857362

Laser-Induced Molybdenum Carbide-Graphene Composites for 3D Foldable Paper Electronics.

PubMed

Zang, Xining; Shen, Caiwei; Chu, Yao; Li, Buxuan; Wei, Minsong; Zhong, Junwen; Sanghadasa, Mohan; Lin, Liwei

2018-05-15

Versatile and low-cost manufacturing processes/materials are essential for the development of paper electronics. Here, a direct-write laser patterning process is developed to make conductive molybdenum carbide-graphene (MCG) composites directly on paper substrates. The hierarchically porous MCG structures are converted from fibrous paper soaked with the gelatin-mediated inks containing molybdenum ions. The resulting Mo 3 C 2 and graphene composites are mechanically stable and electrochemically active for various potential applications, such as electrochemical ion detectors and gas sensors, energy harvesters, and supercapacitors. Experimentally, the electrical conductivity of the composite is resilient to mechanical deformation with less than 5% degradation after 750 cycles of 180° repeated folding tests. As such, the direct laser conversion of MCGs on papers can be applicable for paper-based electronics, including the 3D origami folding structures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recurrent potential pulse technique for improvement of glucose sensing ability of 3D polypyrrole

NASA Astrophysics Data System (ADS)

Cysewska, Karolina; Karczewski, Jakub; Jasiński, Piotr

2017-07-01

In this work, a new approach for using a 3D polypyrrole (PPy) conducting polymer as a sensing material for glucose detection is proposed. Polypyrrole is electrochemically polymerized on a platinum screen-printed electrode in an aqueous solution of lithium perchlorate and pyrrole. PPy exhibits a high electroactive surface area and high electrochemical stability, which results in it having excellent electrocatalytic properties. The studies show that using the recurrent potential pulse technique results in an increase in PPy sensing stability, compared to the amperometric approach. This is due to the fact that the technique, under certain parameters, allows the PPy redox properties to be fully utilized, whilst preventing its anodic degradation. Because of this, the 3D PPy presented here has become a very good candidate as a sensing material for glucose detection, and can work without any additional dopants, mediators or enzymes.

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

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

Wang, Hao; Sa, Niya; He, Meinan

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE PAGES

Wang, Hao; Sa, Niya; He, Meinan; ...

2017-03-03

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

Generalized platform for antibody detection using the antibody catalyzed water oxidation pathway.

PubMed

Welch, M Elizabeth; Ritzert, Nicole L; Chen, Hongjun; Smith, Norah L; Tague, Michele E; Xu, Youyong; Baird, Barbara A; Abruña, Héctor D; Ober, Christopher K

2014-02-05

Infectious diseases, such as influenza, present a prominent global problem including the constant threat of pandemics that initiate in avian or other species and then pass to humans. We report a new sensor that can be specifically functionalized to detect antibodies associated with a wide range of infectious diseases in multiple species. This biosensor is based on electrochemical detection of hydrogen peroxide generated through the intrinsic catalytic activity of all antibodies: the antibody catalyzed water oxidation pathway (ACWOP). Our platform includes a polymer brush-modified surface where specific antibodies bind to conjugated haptens with high affinity and specificity. Hydrogen peroxide provides an electrochemical signal that is mediated by Resorufin/Amplex Red. We characterize the biosensor platform, using model anti-DNP antibodies, with the ultimate goal of designing a versatile device that is inexpensive, portable, reliable, and fast. We demonstrate detection of antibodies at concentrations that fall well within clinically relevant levels.

Ferrocene-Functionalized 4-(2,5-Di(thiophen-2-yl)-1H-pyrrol-1-yl)aniline: A Novel Design in Conducting Polymer-Based Electrochemical Biosensors

PubMed Central

Ayranci, Rukiye; Demirkol, Dilek Odaci; Ak, Metin; Timur, Suna

2015-01-01

Herein, we report a novel ferrocenyldithiophosphonate functional conducting polymer and its use as an immobilization matrix in amperometric biosensor applications. Initially, 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)amidoferrocenyldithiophosphonate was synthesized and copolymerized with 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)benzenamine at graphite electrodes. The amino groups on the polymer were utilized for covalent attachment of the enzyme glucose oxidase. Besides, ferrocene on the backbone was used as a redox mediator during the electrochemical measurements. Prior to the analytical characterization, optimization studies were carried out. The changes in current signals at +0.45 V were proportional to glucose concentration from 0.5 to 5.0 mM. Finally, the resulting biosensor was applied for glucose analysis in real samples and the data were compared with the spectrophotometric Trinder method. PMID:25591169

Contrasting contribution of 5-hydroxytryptamine 1A receptor activation to neurochemical profile of novel antipsychotics: frontocortical dopamine and hippocampal serotonin release in rat brain.

PubMed

Assié, Marie-Bernadette; Ravailhe, Véronique; Faucillon, Valérie; Newman-Tancredi, Adrian

2005-10-01

Several novel antipsychotics, such as aripiprazole, bifeprunox, SSR181507 [(3-exo)-8-benzoyl-N-(((2S)7-chloro-2,3-dihydro-1,4-benzodioxin-1-yl)methyl)-8-azabicyclo(3.2.1)octane-3-methanamine], and SLV313 [1-(2,3-dihydro-benzo[1,4]dioxin-5-yl)-4-[5-(4-fluorophenyl)-pyridin-3-ylmethyl]-piperazine], activate serotonin 5-hydroxytryptamine (5-HT)1A receptors. Such activity is associated with enhanced treatment of negative symptoms and cognitive deficits, which may be mediated by modulation of cerebral dopamine and serotonin levels. We employed microdialysis coupled to high pressure liquid chromatography with electrochemical detection to examine 5-HT1A receptor activation in the modulation of extracellular dopamine in medial prefrontal cortex and serotonin in hippocampus of freely moving rats. The above compounds were compared with drugs that have less interaction with 5-HT1A receptors (clozapine, nemonapride, ziprasidone, olanzapine, risperidone, and haloperidol). Hippocampal 5-HT was decreased by bifeprunox, SSR181507, SLV313, sarizotan, and nemonapride, effects similar to those seen with the 5-HT1A agonist, (+)-8-hydroxy-2-(di-n-propylamino)tetralin [(+)8-OH-DPAT], consistent with activation of 5-HT1A autoreceptors. These decreases were reversed by the selective 5-HT1A antagonist, WAY100635 [N-[2-[4-(2-methoxyphenyl)-1-piperazinyl]ethyl]-N-(2-pyridinyl)cyclohexanecarboxamide]. In contrast, haloperidol, risperidone, clozapine, olanzapine, ziprasidone, and aripiprazole did not significantly modify hippocampal serotonin levels. In medial prefrontal cortex, dopamine levels were increased by SSR181507, SLV313, sarizotan, and (+)8-OH-DPAT. These effects were reversed by WAY100635, indicating mediation by 5-HT1A receptors. In contrast, the increases in dopamine levels induced by clozapine, risperidone, olanzapine, and ziprasidone were not blocked by WAY100635, consistent with predominant influence of other mechanisms in the actions of these drugs. Haloperidol, nemonapride, and the D2 partial agonists, aripiprazole and bifeprunox, did not significantly alter dopamine release. Taken together, these data demonstrate the diverse contribution of 5-HT1A receptor activation to the profile of antipsychotics and suggest that novel drugs selectively targeting D2 and 5-HT1A receptors may present distinctive therapeutic properties.

Trial-to-Trial Modulations of the Simon Effect in Conditions of Attentional Limitations : Evidence from Dual Tasks

ERIC Educational Resources Information Center

Fischer, Rico; Plessow, Franziska; Kunde, Wilfried; Kiesel, Andrea

2010-01-01

Interference effects are reduced after trials including response conflict. This sequential modulation has often been attributed to a top-down mediated adaptive control mechanism and/or to feature repetition mechanisms. In the present study we tested whether mechanisms responsible for such sequential modulations are subject to attentional…

Hormetic Response to Low-Dose Radiation: Focus on the Immune System and Its Clinical Implications

PubMed Central

Cui, Jiuwei; Yang, Guozi; Pan, Zhenyu; Zhao, Yuguang; Liang, Xinyue; Li, Wei; Cai, Lu

2017-01-01

The interrelationship between ionizing radiation and the immune system is complex, multifactorial, and dependent on radiation dose/quality and immune cell type. High-dose radiation usually results in immune suppression. On the contrary, low-dose radiation (LDR) modulates a variety of immune responses that have exhibited the properties of immune hormesis. Although the underlying molecular mechanism is not fully understood yet, LDR has been used clinically for the treatment of autoimmune diseases and malignant tumors. These advancements in preclinical and clinical studies suggest that LDR-mediated immune modulation is a well-orchestrated phenomenon with clinical potential. We summarize recent developments in the understanding of LDR-mediated immune modulation, with an emphasis on its potential clinical applications. PMID:28134809

Populational equilibrium through exosome-mediated Wnt signaling in tumor progression of diffuse large B-cell lymphoma.

PubMed

Koch, Raphael; Demant, Martin; Aung, Thiha; Diering, Nina; Cicholas, Anna; Chapuy, Bjoern; Wenzel, Dirk; Lahmann, Marlen; Güntsch, Annemarie; Kiecke, Christina; Becker, Sabrina; Hupfeld, Timo; Venkataramani, Vivek; Ziepert, Marita; Opitz, Lennart; Klapper, Wolfram; Trümper, Lorenz; Wulf, Gerald G

2014-04-03

Tumors are composed of phenotypically heterogeneous cell populations. The nongenomic mechanisms underlying transitions and interactions between cell populations are largely unknown. Here, we show that diffuse large B-cell lymphomas possess a self-organized infrastructure comprising side population (SP) and non-SP cells, where transitions between clonogenic states are modulated by exosome-mediated Wnt signaling. DNA methylation modulated SP-non-SP transitions and was correlated with the reciprocal expressions of Wnt signaling pathway agonist Wnt3a in SP cells and the antagonist secreted frizzled-related protein 4 in non-SP cells. Lymphoma SP cells exhibited autonomous clonogenicity and exported Wnt3a via exosomes to neighboring cells, thus modulating population equilibrium in the tumor.

The mediator complex in genomic and non-genomic signaling in cancer.

PubMed

Weber, Hannah; Garabedian, Michael J

2018-05-01

Mediator is a conserved, multi-subunit macromolecular machine divided structurally into head, middle, and tail modules, along with a transiently associating kinase module. Mediator functions as an integrator of transcriptional regulatory activity by interacting with DNA-bound transcription factors and with RNA polymerase II (Pol II) to both activate and repress gene expression. Mediator has been shown to affect multiple steps in transcription, including chromatin looping between enhancers and promoters, pre-initiation complex formation, transcriptional elongation, and mRNA splicing. Individual Mediator subunits participate in regulation of gene expression by the estrogen and androgen receptors and are altered in a number of endocrine cancers, including breast and prostate cancer. In addition to its role in genomic signaling, MED12 has been implicated in non-genomic signaling by interacting with and activating TGF-beta receptor 2 in the cytoplasm. Recent structural studies have revealed extensive inter-domain interactions and complex architecture of the Mediator-Pol II complex, suggesting that Mediator is capable of reorganizing its conformation and composition to fit cellular needs. We propose that alterations in Mediator subunit expression that occur in various cancers could impact the organization and function of Mediator, resulting in changes in gene expression that promote malignancy. A better understanding of the role of Mediator in cancer could reveal new approaches to the diagnosis and treatment of Mediator-dependent endocrine cancers, especially in settings of therapy resistance. Copyright © 2017 Elsevier Inc. All rights reserved.

The major brain cholesterol metabolite 24(S)-hydroxycholesterol is a potent allosteric modulator of N-methyl-D-aspartate receptors.

PubMed

Paul, Steven M; Doherty, James J; Robichaud, Albert J; Belfort, Gabriel M; Chow, Brian Y; Hammond, Rebecca S; Crawford, Devon C; Linsenbardt, Andrew J; Shu, Hong-Jin; Izumi, Yukitoshi; Mennerick, Steven J; Zorumski, Charles F

2013-10-30

N-methyl-D-aspartate receptors (NMDARs) are glutamate-gated ion channels that are critical to the regulation of excitatory synaptic function in the CNS. NMDARs govern experience-dependent synaptic plasticity and have been implicated in the pathophysiology of various neuropsychiatric disorders including the cognitive deficits of schizophrenia and certain forms of autism. Certain neurosteroids modulate NMDARs experimentally but their low potency, poor selectivity, and very low brain concentrations make them poor candidates as endogenous ligands or therapeutic agents. Here we show that the major brain-derived cholesterol metabolite 24(S)-hydroxycholesterol (24(S)-HC) is a very potent, direct, and selective positive allosteric modulator of NMDARs with a mechanism that does not overlap that of other allosteric modulators. At submicromolar concentrations 24(S)-HC potentiates NMDAR-mediated EPSCs in rat hippocampal neurons but fails to affect AMPAR or GABAA receptors (GABA(A)Rs)-mediated responses. Cholesterol itself and other naturally occurring oxysterols present in brain do not modulate NMDARs at concentrations ≤10 μM. In hippocampal slices, 24(S)-HC enhances the ability of subthreshold stimuli to induce long-term potentiation (LTP). 24(S)-HC also reverses hippocampal LTP deficits induced by the NMDAR channel blocker ketamine. Finally, we show that synthetic drug-like derivatives of 24(S)-HC, which potently enhance NMDAR-mediated EPSCs and LTP, restore behavioral and cognitive deficits in rodents treated with NMDAR channel blockers. Thus, 24(S)-HC may function as an endogenous modulator of NMDARs acting at a novel oxysterol modulatory site that also represents a target for therapeutic drug development.

Evidence for Multiple Mediator Complexes in Yeast Independently Recruited by Activated Heat Shock Factor.

PubMed

Anandhakumar, Jayamani; Moustafa, Yara W; Chowdhary, Surabhi; Kainth, Amoldeep S; Gross, David S

2016-07-15

Mediator is an evolutionarily conserved coactivator complex essential for RNA polymerase II transcription. Although it has been generally assumed that in Saccharomyces cerevisiae, Mediator is a stable trimodular complex, its structural state in vivo remains unclear. Using the "anchor away" (AA) technique to conditionally deplete select subunits within Mediator and its reversibly associated Cdk8 kinase module (CKM), we provide evidence that Mediator's tail module is highly dynamic and that a subcomplex consisting of Med2, Med3, and Med15 can be independently recruited to the regulatory regions of heat shock factor 1 (Hsf1)-activated genes. Fluorescence microscopy of a scaffold subunit (Med14)-anchored strain confirmed parallel cytoplasmic sequestration of core subunits located outside the tail triad. In addition, and contrary to current models, we provide evidence that Hsf1 can recruit the CKM independently of core Mediator and that core Mediator has a role in regulating postinitiation events. Collectively, our results suggest that yeast Mediator is not monolithic but potentially has a dynamic complexity heretofore unappreciated. Multiple species, including CKM-Mediator, the 21-subunit core complex, the Med2-Med3-Med15 tail triad, and the four-subunit CKM, can be independently recruited by activated Hsf1 to its target genes in AA strains. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Extreme electronic modulation of the cofacial porphyrin structural motif.

PubMed

Fletcher, James T; Therien, Michael J

2002-04-24

The synthesis, electrochemistry, and optical spectroscopy of an extensive series of cofacial bis[(porphinato)zinc(II)] compounds are reported. These species were synthesized using sequential palladium-catalyzed cross-coupling and cobalt-mediated [2+2+2] cycloaddition reactions. This modular methodology enables facile control of the nature of macrocycle-to-macrocycle connectivity and allows unprecedented modulation of the redox properties of face-to-face porphyrin species. We report the synthesis of 5,6-bis[(5',5''-10',20'-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (1), 5,6-bis[(2'-5',10',15',20'-tetraphenylporphinato)zinc(II)]indane (2), 5-([2'-5',10',15',20'-tetraphenylporphinato]zinc(II))-6-[(5"-10'',20''-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (3), 5-([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(5' '-10' ',20' '-bis[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (4), 5-(2'-5',10',15',20'-[tetrakis(trifluoromethyl)porphinato]zinc(II))-6-[(2''-5'',10'',15'',20''-tetraphenylporphinato)zinc(II)]indane (5), 5,6-bis([2'-5',15'-diphenyl-10',20'-(trifluoromethyl)porphinato]zinc(II))indane (6), and 5,6-bis([2'-5',10',15',20'-tetrakis(trifluoromethyl)porphinato]zinc(II))indane (7); 4-7 define the first examples of cofacial bis[(porphinato)metal] compounds in which sigma-electron-withdrawing perfluoroalkyl groups serve as macrocycle substituents, while 2, 6, and 7 constitute the first such structures that possess a beta-to-beta linkage topology. Cyclic voltammetric studies show that the electrochemically determined HOMO and LUMO energy levels of these cofacial bis(porphinato) complexes can be lowered by 780 and 945 mV, respectively, relative to the archetypal members of this class of compounds; importantly, these orbital energy levels can be modulated over well-defined increments throughout these wide potentiometric domains. Analyses of these cofacial bis[(porphinato)metal] potentiometric data, in terms of the absolute and relative frontier orbital energies of their constituent [porphinato]zinc(II) building blocks, as well as the nature of macrocycle-to-macrocycle connectivity, provide predictive electronic structural models that rationalize the redox behavior of these species.

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.

Electrochemical ion transfer mediated by a lipophilic Os(ii)/Os(iii) dinonyl bipyridyl probe incorporated in thin film membranes.

PubMed

Jansod, Sutida; Wang, Lu; Cuartero, Maria; Bakker, Eric

2017-09-28

A new lipophilic dinonyl bipyridyl Os(ii)/Os(iii) complex successfully mediates ion transfer processes across voltammetric thin membranes. An added lipophilic cation-exchanger may impose voltammetric anion or cation transfer waves of Gaussian shape that are reversible and repeatable. The peak potential is found to shift with the ion concentration in agreement with the Nernst equation. The addition of tridodecylmethylammonium nitrate to the polymeric film dramatically reduces the peak separation from 240 mV to 65 mV, and the peak width to a near-theoretical value of 85 mV, which agrees with a surface confined process. It is suggested that the cationic additive serves as a phase transfer catalyst.

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.

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.

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.

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

Studies of Aqueous and Non-Aqueous Electrochemical Interface for Applications in Microelectronic and Energy Storage Systems

NASA Astrophysics Data System (ADS)

Zheng, Jianping

Various electrochemical techniques were utilized to study a wide range of electrochemical systems in this dissertation. Mainly they are grouped in three sections: 1) the conventional metal-aqueous systems for new applications in modern microelectronic devices, 2) unconventional ceramic-organic systems for applications in Li-ion batteries and 3) novel systems composed of ionic liquids and carbon series electrodes. The objects are to probe the electrochemical/chemical reactions and interfacial structures, which are the common features of the aforementioned systems. This dissertation mainly focuses on experimental aspects, however, some theories and new models used to elucidate the experiment data have also been developed and presented. Some new experimental techniques have been explored and their limitations and validity have also been discussed. Oxalic acid (OA)-based nonalkaline solutions with H2O 2 are found to support chemically mediated removal of Ta-oxide surface films on Ta. The associated surface reactions are critical for chemical mechanical planarization (CMP) of Ta barrier. In chapter 4, a Ta coupon electrode is used as a model system in abrasive-free solutions of OA and H2O 2, where the chemical component of CMP is selectively examined. In chapter 5, electrochemical impedance spectroscopy (EIS) is employed to study the competitive reactions of surface corrosion and passivating film formation on a Cu-rotating disc electrode (RDE) in pH-adjusted solutions of H2O2, acetic acid (HAc) and ammonium dodecyl sulfate (ADS). Micrometric LiMn2O4 particles are mechano-chemically modified by ball-milling to obtain a mixture of nano- and micro-scale particles. In chapter 6, this mixture is tested as a potential active cathode material for rapid-charge Li ion batteries, and also as a model system for studying the detailed kinetics of Li intercalation/de-intercalation in such electrodes. In chapter 7, cyclic voltammetry (CV) and EIS are compared as techniques for analyzing double layer capacitances of ionic liquids (ILs) at the surfaces of two carbon-based electrodes. These systems are relevant for energy storage supercapacitors and often are associated with unconventional electrochemical properties. In chapter 8, the electrochemical interfaces of a glassy carbon (GC) and a carbon nanotube (CNT) paper electrode have been studied in EmimBF 4 and BmimBF4 ILs using CV and EIS.

Mediator Recruitment to Heat Shock Genes Requires Dual Hsf1 Activation Domains and Mediator Tail Subunits Med15 and Med16*

PubMed Central

Kim, Sunyoung; Gross, David S.

2013-01-01

The evolutionarily conserved Mediator complex is central to the regulation of gene transcription in eukaryotes because it serves as a physical and functional interface between upstream regulators and the Pol II transcriptional machinery. Nonetheless, its role appears to be context-dependent, and the detailed mechanism by which it governs the expression of most genes remains unknown. Here we investigate Mediator involvement in HSP (heat shock protein) gene regulation in the yeast Saccharomyces cerevisiae. We find that in response to thermal upshift, subunits representative of each of the four Mediator modules (Head, Middle, Tail, and Kinase) are rapidly, robustly, and selectively recruited to the promoter regions of HSP genes. Their residence is transient, returning to near-background levels within 90 min. Hsf1 (heat shock factor 1) plays a central role in recruiting Mediator, as indicated by the fact that truncation of either its N- or C-terminal activation domain significantly reduces Mediator occupancy, whereas removal of both activation domains abolishes it. Likewise, ablation of either of two Mediator Tail subunits, Med15 or Med16, reduces Mediator recruitment to HSP promoters, whereas deletion of both abolishes it. Accompanying the loss of Mediator, recruitment of RNA polymerase II is substantially diminished. Interestingly, Mediator antagonizes Hsf1 occupancy of non-induced promoters yet facilitates enhanced Hsf1 association with activated ones. Collectively, our observations indicate that Hsf1, via its dual activation domains, recruits holo-Mediator to HSP promoters in response to acute heat stress through cooperative physical and/or functional interactions with the Tail module. PMID:23447536

Non-Saccharomyces yeasts protect against epithelial cell barrier disruption induced by Salmonella enterica subsp. enterica serovar Typhimurium.

PubMed

Smith, I M; Baker, A; Arneborg, N; Jespersen, L

2015-11-01

The human gastrointestinal epithelium makes up the largest barrier separating the body from the external environment. Whereas invasive pathogens cause epithelial barrier disruption, probiotic micro-organisms modulate tight junction regulation and improve epithelial barrier function. In addition, probiotic strains may be able to reduce epithelial barrier disruption caused by pathogenic species. The aim of this study was to explore non-Saccharomyces yeast modulation of epithelial cell barrier function in vitro. Benchmarking against established probiotic strains, we evaluated the ability of four nonpathogenic yeast species to modulate transepithelial electrical resistance (TER) across a monolayer of differentiated human colonocytes (Caco-2 cells). Further, we assessed yeast modulation of a Salmonella Typhimurium-induced epithelial cell barrier function insult. Our findings demonstrate distinct patterns of non-Saccharomyces yeast modulation of epithelial cell barrier function. While the established probiotic yeast Saccharomyces boulardii increased TER across a Caco-2 monolayer by 30%, Kluyveromyces marxianus exhibited significantly stronger properties of TER enhancement (50% TER increase). In addition, our data demonstrate significant yeast-mediated modulation of Salmonella-induced epithelial cell barrier disruption and identify K. marxianus and Metschnikowia gruessii as two non-Saccharomyces yeasts capable of protecting human epithelial cells from pathogen invasion. This study demonstrates distinct patterns of non-Saccharomyces yeast modulation of epithelial cell barrier function in vitro. Further, our data demonstrate significant yeast-mediated modulation of Salmonella Typhimurium-induced epithelial cell barrier disruption and identify Kluyveromyces marxianus and Metschnikowia gruessii as two non-Saccharomyces yeasts capable of protecting human epithelial cells from pathogen invasion. This study is the first to demonstrate significant non-Saccharomyces yeast-mediated epithelial cell barrier protection from Salmonella invasion, thus encouraging future efforts aimed at confirming the observed effects in vivo and driving further strain development towards novel yeast probiotics. © 2015 The Society for Applied Microbiology.

Real-time characterization of cannabinoid receptor 1 (CB1 ) allosteric modulators reveals novel mechanism of action.

PubMed

Cawston, Erin E; Redmond, William J; Breen, Courtney M; Grimsey, Natasha L; Connor, Mark; Glass, Michelle

2013-10-01

The cannabinoid receptor type 1 (CB1 ) has an allosteric binding site. The drugs ORG27569 {5-chloro-3-ethyl-N-[2-[4-(1-piperidinyl)phenyl]ethyl]-1H-indole-2-carboxamide} and PSNCBAM-1 {1-(4-chlorophenyl)-3-[3-(6-pyrrolidin-1-ylpyridin-2-yl)phenyl]urea} have been extensively characterized with regard to their effects on signalling of the orthosteric ligand CP55,940 {(-)-cis-3-[2-hydroxy-4-(1,1-dimethylheptyl)phenyl]-trans-4-(3-hydroxypropyl)cyclohexanol}, and studies have suggested that these allosteric modulators increase binding affinity but act as non-competitive antagonists in functional assays. To gain a deeper understanding of allosteric modulation of CB1 , we examined real-time signalling and trafficking responses of the receptor in the presence of allosteric modulators. Studies of CB1 signalling were carried out in HEK 293 and AtT20 cells expressing haemagglutinin-tagged human and rat CB1 . We measured real-time accumulation of cAMP, activation and desensitization of potassium channel-mediated cellular hyperpolarization and CB1 internalization. ORG27569 and PSNCBAM-1 produce a complex, concentration and time-dependent modulation of agonist-mediated regulation of cAMP levels, as well as an increased rate of desensitization of CB1 -mediated cellular hyperpolarization and a decrease in agonist-induced receptor internalization. Contrary to previous studies characterizing allosteric modulators at CB1, this study suggests that the mechanism of action is not non-competitive antagonism of signalling, but rather that enhanced binding results in an increased rate of receptor desensitization and reduced internalization, which results in time-dependent modulation of cAMP signalling. The observed effect of the allosteric modulators is therefore dependent on the time frame over which the signalling response occurs. This finding may have important consequences for the potential therapeutic application of these compounds. © 2013 The British Pharmacological Society.

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.

Cyclin-dependent kinase 8 module expression profiling reveals requirement of mediator subunits 12 and 13 for transcription of Serpent-dependent innate immunity genes in Drosophila.

PubMed

Kuuluvainen, Emilia; Hakala, Heini; Havula, Essi; Sahal Estimé, Michelle; Rämet, Mika; Hietakangas, Ville; Mäkelä, Tomi P

2014-06-06

The Cdk8 (cyclin-dependent kinase 8) module of Mediator integrates regulatory cues from transcription factors to RNA polymerase II. It consists of four subunits where Med12 and Med13 link Cdk8 and cyclin C (CycC) to core Mediator. Here we have investigated the contributions of the Cdk8 module subunits to transcriptional regulation using RNA interference in Drosophila cells. Genome-wide expression profiling demonstrated separation of Cdk8-CycC and Med12-Med13 profiles. However, transcriptional regulation by Cdk8-CycC was dependent on Med12-Med13. This observation also revealed that Cdk8-CycC and Med12-Med13 often have opposite transcriptional effects. Interestingly, Med12 and Med13 profiles overlapped significantly with that of the GATA factor Serpent. Accordingly, mutational analyses indicated that GATA sites are required for Med12-Med13 regulation of Serpent-dependent genes. Med12 and Med13 were also found to be required for Serpent-activated innate immunity genes in defense to bacterial infection. The results reveal a novel role for the Cdk8 module in Serpent-dependent transcription and innate immunity. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

Density of Trap States and Auger-mediated Electron Trapping in CdTe Quantum-Dot Solids.

PubMed

Boehme, Simon C; Azpiroz, Jon Mikel; Aulin, Yaroslav V; Grozema, Ferdinand C; Vanmaekelbergh, Daniël; Siebbeles, Laurens D A; Infante, Ivan; Houtepen, Arjan J

2015-05-13

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations. We find a high density of very efficient electron traps centered ∼0.42 eV above the valence band. Electrochemical filling of these traps increases the electron lifetime and the photoluminescence quantum yield by more than an order of magnitude. The trapping rate constant for holes is an order of magnitude lower that for electrons. These observations can be explained by Auger-mediated electron trapping. From density functional theory calculations we infer that the traps are formed by dicoordinated Te atoms at the quantum dot surface. The combination of our unique experimental determination of the density of trap states with the theoretical modeling of the quantum dot surface allows us to identify the trapping mechanism and chemical reaction at play during charge trapping in these quantum dots.

Destruction of organic pollutants by cerium(IV) MEO process: a study on the influence of process conditions for EDTA mineralization.

PubMed

Balaji, Subramanian; Chung, Sang Joon; Matheswaran, Manickam; Vasilivich, Kokovkin Vasily; Moon, Il Shik

2008-02-11

The mediated electrochemical oxidation (MEO) process with cerium(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in continuous organic feeding mode. A near complete destruction was observed for all the organics studied. The effects of various experimental conditions were evaluated with respect to EDTA mineralization. The key parameters varied in the process were concentration of EDTA (67-268 mM), temperature (70, 80 and 95 degrees C), concentrations of Ce(IV) (0.7, 0.8 and 0.95 M), nitric acid (2, 3 and 4M) and duration of organic addition (30 and 120 min). Under the experimental conditions of 80 degrees C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO(2) production and 95% based on TOC analyses for all the organic compounds studied. The in situ regeneration of mediator ion by the electrochemical cell was found to be good during the organic destruction within the range of experimental conditions studied. In the case of long term organic feeding (120 min) the destruction was calculated after the CO(2) evolution attained the steady state and under this condition the destruction efficiency was found to be 85% based on CO(2) evolution.

Construction of novel xanthine biosensor by using polymeric mediator/MWCNT nanocomposite layer for fish freshness detection.

PubMed

Dervisevic, Muamer; Custiuc, Esma; Çevik, Emre; Şenel, Mehmet

2015-08-15

A novel nanocomposite host matrix for enzyme immobilization of xanthine oxidase was developed by incorporating MWCNT in poly(GMA-co-VFc) copolymer film. In the food industry fish is a product with a very low commercial life, and a high variability as well elevated level of xanthine is an important biomarker as a sign of spoilage. The fabricated process was characterized by scanning electron microscopy (SEM), and the electrochemical behaviors of the biosensor were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The prepared enzyme electrodes exhibited maximum response at pH 7.0 and 45°C +0.35 V and reached 95% of steady-state current in about ∼ 4 s and its sensitivity was 16 mAM(-1). Linear ranges (2-28 μM, 28-46 and 46-86 μM), analytical performance and a low detection limit 0.12 μM obtained from the xanthine biosensor gives reliable results in measuring xanthine concentration in the fish meat. All the results indicating that the resulting biosensor exhibited a good response to xanthine that was related to the addition of MWCNT in the polymeric mediator film which played an important role in the biosensor performance. In addition, the biosensor exhibited high good storage stability and satisfactory anti-interference ability. Copyright © 2015 Elsevier Ltd. All rights reserved.

Identification of glia phenotype modulators based on select glial function regulatory signaling pathways.

PubMed

Lee, Sun-Hwa; Suk, Kyoungho

2018-04-20

Despite the considerable social and economic burden on the healthcare system worldwide due to neurodegenerative diseases, there are currently few disease-altering treatment options for many of these conditions. Therefore, new approaches for both prevention and intervention for neurodegenerative diseases are urgently required. Microglia-mediated neurotoxicity is one of the pathologic hallmarks common to Alzheimer's disease, Parkinson's disease, and amyotrophic lateral sclerosis. Current therapeutic approaches to target microglia-mediated neurotoxicity are focused on the identification of glia phenotype modulators (GPMs), which can inhibit the 'classical' pro-inflammatory and neurotoxic phenotypes of microglia. Areas covered: This article reviews selected microglial molecular targets and pathways involved in either neurotoxicity or neuroprotection and how their identification. Expert opinion: Microglial activation and their signaling pathways have important implications in the neurotoxicity and brain disorders. Pharmacological modulation of microglial activation may serve as a potential therapeutic approach for targeting microglia-mediated neurotoxicity. However, given that microglia change their activation states depending on the timing, stage, and severity of disease, and even aging, the appropriate window should be considered for this approach to be clinically effective. In the future, the identification of unknown extracellular signals and intracellular molecular switches that control phenotypic shifts may facilitate the development of novel therapeutics targeting microglia-mediated neurotoxicity.

Biomedical Potential of mTOR Modulation by Nanoparticles.

PubMed

Hulea, Laura; Markovic, Zoran; Topisirovic, Ivan; Simmet, Thomas; Trajkovic, Vladimir

2016-05-01

Modulation of the mammalian target of rapamycin (mTOR), the principal regulator of cellular homeostasis, underlies the biological effects of engineered nanoparticles, including regulation of cell death/survival and metabolic responses. Understanding the mechanisms and biological actions of nanoparticle-mediated mTOR modulation may help in developing safe and efficient nanotherapeutics to fight human disease. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

PubMed Central

2015-01-01

Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

Intracellular Ca2+ release mediates cationic but not anionic poly(amidoamine) (PAMAM) dendrimer-induced tight junction modulation.

PubMed

Avaritt, Brittany R; Swaan, Peter W

2014-09-01

Poly(amidoamine) (PAMAM) dendrimers show great promise for utilization as oral drug delivery vehicles. These polymers are capable of traversing epithelial barriers, and have been shown to translocate by both transcellular and paracellular routes. While many proof-of-concept studies have shown that PAMAM dendrimers improve intestinal transport, little information exists on the mechanisms of paracellular transport, specifically dendrimer-induced tight junction modulation. Using anionic G3.5 and cationic G4 PAMAM dendrimers with known absorption enhancers, we investigated tight junction modulation in Caco-2 monolayers by visualization and mannitol permeability and compared dendrimer-mediated tight junction modulation to that of established permeation enhancers. [(14)C]-Mannitol permeability in the presence and absence of phospholipase C-dependent signaling pathway inhibitors was also examined and indicated that this pathway may mediate dendrimer-induced changes in permeability. Differences between G3.5 and G4 in tight junction protein staining and permeability with inhibitors were evident, suggesting divergent mechanisms were responsible for tight junction modulation. These dissimilarities are further intimated by the intracellular calcium release caused by G4 but not G3.5. Based on our results, it is apparent that the underlying mechanisms of dendrimer permeability are complex, and the complexities are likely a result of the density and sign of the surface charges of PAMAM dendrimers. The results of this study will have implications on the future use of PAMAM dendrimers for oral drug delivery.

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

PubMed

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

2011-05-01

Prediction of oxidative drug metabolism at the early stages of drug discovery and development requires fast and accurate analytical techniques to mimic the in vivo oxidation reactions by cytochrome P450s (CYP). Direct electrochemical oxidation combined with mass spectrometry, although limited to the oxidation reactions initiated by charge transfer, has shown promise in the mimicry of certain CYP-mediated metabolic reactions. The electrochemical approach may further be utilized in an automated manner in microfluidics devices facilitating fast screening of oxidative drug metabolism. A wide range of in vivo oxidation reactions, particularly those initiated by hydrogen atom transfer, can be imitated through the electrochemically-assisted Fenton reaction. This reaction is based on O-O bond activation in hydrogen peroxide and oxidation by hydroxyl radicals, wherein electrochemistry is used for the reduction of molecular oxygen to hydrogen peroxide, as well as the reduction of Fe(3+) to Fe(2+). Metalloporphyrins, as surrogates for the prosthetic group in CYP, utilizing metallo-oxo reactive species, can also be used in combination with electrochemistry. Electrochemical reduction of metalloporphyrins in solution or immobilized on the electrode surface activates molecular oxygen in a manner analogous to the catalytical cycle of CYP and different metalloporphyrins can mimic selective oxidation reactions. Chemoselective, stereoselective, and regioselective oxidation reactions may be mimicked using electrodes that have been modified with immobilized enzymes, especially CYP itself. This review summarizes the recent attempts in utilizing electrochemistry as a versatile analytical and preparative technique in the mimicry of oxidative drug metabolism by CYP. © 2011 Bentham Science Publishers Ltd.

Molecular imaging of drug-modulated protein-protein interactions in living subjects.

PubMed

Paulmurugan, Ramasamy; Massoud, Tarik F; Huang, Jing; Gambhir, Sanjiv S

2004-03-15

Networks of protein interactions mediate cellular responses to environmental stimuli and direct the execution of many different cellular functional pathways. Small molecules synthesized within cells or recruited from the external environment mediate many protein interactions. The study of small molecule-mediated interactions of proteins is important to understand abnormal signal transduction pathways in cancer and in drug development and validation. In this study, we used split synthetic renilla luciferase (hRLUC) protein fragment-assisted complementation to evaluate heterodimerization of the human proteins FRB and FKBP12 mediated by the small molecule rapamycin. The concentration of rapamycin required for efficient dimerization and that of its competitive binder ascomycin required for dimerization inhibition were studied in cell lines. The system was dually modulated in cell culture at the transcription level, by controlling nuclear factor kappaB promoter/enhancer elements using tumor necrosis factor alpha, and at the interaction level, by controlling the concentration of the dimerizer rapamycin. The rapamycin-mediated dimerization of FRB and FKBP12 also was studied in living mice by locating, quantifying, and timing the hRLUC complementation-based bioluminescence imaging signal using a cooled charged coupled device camera. This split reporter system can be used to efficiently screen small molecule drugs that modulate protein-protein interactions and also to assess drugs in living animals. Both are essential steps in the preclinical evaluation of candidate pharmaceutical agents targeting protein-protein interactions, including signaling pathways in cancer cells.

Electrochemical detection of Francisella tularensis genomic DNA using solid-phase recombinase polymerase amplification.

PubMed

del Río, Jonathan Sabaté; Yehia Adly, Nouran; Acero-Sánchez, Josep Lluis; Henry, Olivier Y F; O'Sullivan, Ciara K

2014-04-15

Solid-phase isothermal DNA amplification was performed exploiting the homology protein recombinase A (recA). The system was primarily tested on maleimide activated microtitre plates as a proof-of-concept and later translated to an electrochemical platform. In both cases, forward primer for Francisella tularensis holarctica genomic DNA was surface immobilised via a thiol or an amino moiety and then elongated during the recA mediated amplification, carried out in the presence of specific target sequence and reverse primers. The formation of the subsequent surface tethered amplicons was either colorimetrically or electrochemically monitored using a horseradish peroxidase (HRP)-labelled DNA secondary probe complementary to the elongated strand. The amplification time was optimised to amplify even low amounts of DNA copies in less than an hour at a constant temperature of 37°C, achieving a limit of detection of 1.3×10(-13) M (4×10(6) copies in 50 μL) for the colorimetric assay and 3.3×10(-14) M (2×10(5) copies in 10 μL) for the chronoamperometric assay. The system was demonstrated to be highly specific with negligible cross-reactivity with non-complementary targets or primers. © 2013 Elsevier B.V. All rights reserved.

Advanced Anticorrosion Coating Materials Derived from Sunflower Oil with Bifunctional Properties.

PubMed

Balakrishnan, Thiruparasakthi; Sathiyanarayanan, Sadagopan; Mayavan, Sundar

2015-09-09

High-performance barrier films preventing permeation of moisture, aggressive chloride ions, and corrosive acids are important for many industries ranging from food to aviation. In the current study, pristine sunflower oil was used to form uniform adherent films on iron (Fe) via a simple single-step thermal treatment (without involving any initiator/mediator/catalyst). Oxidation of oil on heating results in a highly conjugated (oxidized) crystalline lamellar network with interlayer separation of 0.445 nm on Fe. The electrochemical corrosion tests proved that the coating exhibits superior anticorrosion performance with high coating resistance (>10(9) ohm cm2) and low capacitance values (<10(-10) F cm(-2)) as compared to bare Fe, graphene, and conducting polymer based coatings in 1 M hydrochloric acid solutions. The electrochemical analyses reveal that the oil coatings developed in this study provided a two-fold protection of passivation from the oxide layer and barrier from polymeric films. It is clearly observed that there is no change in structure, morphology, or electrochemical properties even after a prolonged exposure time of 80 days. This work indicates the prospect of developing highly inert, environmentally green, nontoxic, and micrometer level passivating barrier coatings from more sustainable and renewable sources, which can be of interest for numerous applications.

Development of a cyclic voltammetry method for the detection of Clostridium novyi in black disease.

PubMed

Liu, L L; Jiang, D N; Xiang, G M; Liu, C; Yu, J C; Pu, X Y

2014-03-17

Black disease is an acute disease of sheep and cattle. The pathogen is the obligate anaerobe, Clostridium novyi. Due to difficulties of anaerobic culturing in the country or disaster sites, a simple, rapid, and sensitive method is required. In this study, an electrochemical method, the cyclic voltammetry method, basing on loop-mediated isothermal amplification (LAMP), electrochemical ion bonding (positive dye, methylene blue), was introduced. DNA extracted from C. novyi specimens was amplified through the LAMP reaction. Then the products combined were with methylene blue, which lead to a reduction in the oxidation peak current (ipA) and the reduction peak current (ipC) of the cyclic voltammetry. The changes of ipA/ipC were real-time measured by special designed electrode, so the DNA was quantitatively detected. The results displayed that this electrochemical detection of C. novyi could be completed in 1-2 h with the lowest bacterial concentration of 10(2) colony forming units/mL, and high accuracy (96.5%), sensitivity (96%), and specificity (97%) compared to polymerase chain reation. The cyclic voltammetry method was a simple and fast method, with high sensitivity and high specificity, and has great potential to be a usable molecular tool for fast diagnosis of Black disease.

TMV-Cg Coat Protein stabilizes DELLA proteins and in turn negatively modulates salicylic acid-mediated defense pathway during Arabidopsis thaliana viral infection.

PubMed

Rodriguez, Maria Cecilia; Conti, Gabriela; Zavallo, Diego; Manacorda, Carlos Augusto; Asurmendi, Sebastian

2014-08-03

Plant viral infections disturb defense regulatory networks during tissue invasion. Emerging evidence demonstrates that a significant proportion of these alterations are mediated by hormone imbalances. Although the DELLA proteins have been reported to be central players in hormone cross-talk, their role in the modulation of hormone signaling during virus infections remains unknown. This work revealed that TMV-Cg coat protein (CgCP) suppresses the salicylic acid (SA) signaling pathway without altering defense hormone SA or jasmonic acid (JA) levels in Arabidopsis thaliana. Furthermore, it was observed that the expression of CgCP reduces plant growth and delays the timing of floral transition. Quantitative RT-qPCR analysis of DELLA target genes showed that CgCP alters relative expression of several target genes, indicating that the DELLA proteins mediate transcriptional changes produced by CgCP expression. Analyses by fluorescence confocal microscopy showed that CgCP stabilizes DELLA proteins accumulation in the presence of gibberellic acid (GA) and that the DELLA proteins are also stabilized during TMV-Cg virus infections. Moreover, DELLA proteins negatively modulated defense transcript profiles during TMV-Cg infection. As a result, TMV-Cg accumulation was significantly reduced in the quadruple-DELLA mutant Arabidopsis plants compared to wild type plants. Taken together, these results demonstrate that CgCP negatively regulates the salicylic acid-mediated defense pathway by stabilizing the DELLA proteins during Arabidopsis thaliana viral infection, suggesting that CgCP alters the stability of DELLAs as a mechanism of negative modulation of antiviral defense responses.

Cytokines and cytokine networks target neurons to modulate long-term potentiation.

PubMed

Prieto, G Aleph; Cotman, Carl W

2017-04-01

Cytokines play crucial roles in the communication between brain cells including neurons and glia, as well as in the brain-periphery interactions. In the brain, cytokines modulate long-term potentiation (LTP), a cellular correlate of memory. Whether cytokines regulate LTP by direct effects on neurons or by indirect mechanisms mediated by non-neuronal cells is poorly understood. Elucidating neuron-specific effects of cytokines has been challenging because most brain cells express cytokine receptors. Moreover, cytokines commonly increase the expression of multiple cytokines in their target cells, thus increasing the complexity of brain cytokine networks even after single-cytokine challenges. Here, we review evidence on both direct and indirect-mediated modulation of LTP by cytokines. We also describe novel approaches based on neuron- and synaptosome-enriched systems to identify cytokines able to directly modulate LTP, by targeting neurons and synapses. These approaches can test multiple samples in parallel, thus allowing the study of multiple cytokines simultaneously. Hence, a cytokine networks perspective coupled with neuron-specific analysis may contribute to delineation of maps of the modulation of LTP by cytokines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cytokines and cytokine networks target neurons to modulate long-term potentiation

PubMed Central

Prieto, G. Aleph; Cotman, Carl W.

2017-01-01

Cytokines play crucial roles in the communication between brain cells including neurons and glia, as well as in the brain-periphery interactions. In the brain, cytokines modulate long-term potentiation (LTP), a cellular correlate of memory. Whether cytokines regulate LTP by direct effects on neurons or by indirect mechanisms mediated by non-neuronal cells is poorly understood. Elucidating neuron-specific effects of cytokines has been challenging because most brain cells express cytokine receptors. Moreover, cytokines commonly increase the expression of multiple cytokines in their target cells, thus increasing the complexity of brain cytokine networks even after single-cytokine challenges. Here, we review evidence on both direct and indirect-mediated modulation of LTP by cytokines. We also describe novel approaches based on neuron- and synaptosome-enriched systems to identify cytokines able to directly modulate LTP, by targeting neurons and synapses. These approaches can test multiple samples in parallel, thus allowing the study of multiple cytokines simultaneously. Hence, a cytokine networks perspective coupled with neuron-specific analysis may contribute to delineation of maps of the modulation of LTP by cytokines. PMID:28377062

HIV Nef-mediated cellular phenotypes are differentially expressed as a function of intracellular Nef concentrations.

PubMed

Liu, X; Schrager, J A; Lange, G D; Marsh, J W

2001-08-31

Nef is a regulatory protein encoded by the genome of both human and simian immunodeficiency virus. Its expression in T cells leads to CD4 and major histocompatibility complex class I modulation and either enhancement or suppression of T cell activation. How this viral protein achieves multiple and at times opposing activities has been unclear. Through direct measurements of Nef and the Nef-GFP fusion protein, we find that these events are mediated by different Nef concentrations. Relative to the intracellular concentration that down-modulates surface CD4, an order of magnitude increase in Nef-GFP expression is required for a comparable modulation of major histocompatibility complex class I, and a further 3-fold increase is necessary to suppress T cell activation.

MED12 Regulates HSC-Specific Enhancers Independently of Mediator Kinase Activity to Control Hematopoiesis.

PubMed

Aranda-Orgilles, Beatriz; Saldaña-Meyer, Ricardo; Wang, Eric; Trompouki, Eirini; Fassl, Anne; Lau, Stephanie; Mullenders, Jasper; Rocha, Pedro P; Raviram, Ramya; Guillamot, María; Sánchez-Díaz, María; Wang, Kun; Kayembe, Clarisse; Zhang, Nan; Amoasii, Leonela; Choudhuri, Avik; Skok, Jane A; Schober, Markus; Reinberg, Danny; Sicinski, Piotr; Schrewe, Heinrich; Tsirigos, Aristotelis; Zon, Leonard I; Aifantis, Iannis

2016-12-01

Hematopoietic-specific transcription factors require coactivators to communicate with the general transcription machinery and establish transcriptional programs that maintain hematopoietic stem cell (HSC) self-renewal, promote differentiation, and prevent malignant transformation. Mediator is a large coactivator complex that bridges enhancer-localized transcription factors with promoters, but little is known about Mediator function in adult stem cell self-renewal and differentiation. We show that MED12, a member of the Mediator kinase module, is an essential regulator of HSC homeostasis, as in vivo deletion of Med12 causes rapid bone marrow aplasia leading to acute lethality. Deleting other members of the Mediator kinase module does not affect HSC function, suggesting kinase-independent roles of MED12. MED12 deletion destabilizes P300 binding at lineage-specific enhancers, resulting in H3K27Ac depletion, enhancer de-activation, and consequent loss of HSC stemness signatures. As MED12 mutations have been described recently in blood malignancies, alterations in MED12-dependent enhancer regulation may control both physiological and malignant hematopoiesis. Copyright © 2016 Elsevier Inc. All rights reserved.

Perceived discrimination, psychological distress, and current smoking status: results from the Behavioral Risk Factor Surveillance System Reactions to Race module, 2004-2008.

PubMed

Purnell, Jason Q; Peppone, Luke J; Alcaraz, Kassandra; McQueen, Amy; Guido, Joseph J; Carroll, Jennifer K; Shacham, Enbal; Morrow, Gary R

2012-05-01

We examined the association between perceived discrimination and smoking status and whether psychological distress mediated this relationship in a large, multiethnic sample. We used 2004 through 2008 data from the Behavioral Risk Factor Surveillance System Reactions to Race module to conduct multivariate logistic regression analyses and tests of mediation examining associations between perceived discrimination in health care and workplace settings, psychological distress, and current smoking status. Regardless of race/ethnicity, perceived discrimination was associated with increased odds of current smoking. Psychological distress was also a significant mediator of the discrimination-smoking association. Our results indicate that individuals who report discriminatory treatment in multiple domains may be more likely to smoke, in part, because of the psychological distress associated with such treatment.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

The role of proteosome-mediated proteolysis in modulating potentially harmful transcription factor activity in Saccharomyces cerevisiae

PubMed Central

Bonzanni, Nicola; Zhang, Nianshu; Oliver, Stephen G.; Fisher, Jasmin

2011-01-01

Motivation: The appropriate modulation of the stress response to variable environmental conditions is necessary to maintain sustained viability in Saccharomyces cerevisiae. Particularly, controlling the abundance of proteins that may have detrimental effects on cell growth is crucial for rapid recovery from stress-induced quiescence. Results: Prompted by qualitative modeling of the nutrient starvation response in yeast, we investigated in vivo the effect of proteolysis after nutrient starvation showing that, for the Gis1 transcription factor at least, proteasome-mediated control is crucial for a rapid return to growth. Additional bioinformatics analyses show that potentially toxic transcriptional regulators have a significantly lower protein half-life, a higher fraction of unstructured regions and more potential PEST motifs than the non-detrimental ones. Furthermore, inhibiting proteasome activity tends to increase the expression of genes induced during the Environmental Stress Response more than those in the rest of the genome. Our combined results suggest that proteasome-mediated proteolysis of potentially toxic transcription factors tightly modulates the stress response in yeast. Contact: jasmin.fisher@microsoft.com Supplementary information: Supplementary data are available at Bioinformatics online. PMID:21685082

The Anti-Helminthic Niclosamide Inhibits Wnt/Frizzled1 Signaling†

PubMed Central

Chen, Minyong; Wang, Jiangbo; Lu, Jiuyi; Bond, Michael C.; Ren, Xiu-Rong; Lyerly, H. Kim; Barak, Larry S.; Chen, Wei

2009-01-01

Wnt proteins bind to seven-transmembrane Frizzled receptors to mediate the important developmental, morphogenetic, and tissue-regenerative effects of Wnt signaling. Dysregulated Wnt signaling is associated with many cancers. Currently there exist no drug candidates, or even tool compounds that modulate Wnt-mediated receptor trafficking, and subsequent Wnt signaling. We examined libraries of FDA-approved drugs for their utility as Frizzled internalization modulators, employing a primary imaged-based GFP-fluorescence assay that uses Frizzled1 endocytosis as the readout. We now report that the anti-helminthic niclosamide, a drug used for the treatment of tapeworm, promotes Frizzled1 endocytosis, down regulates Dishevelled-2 protein, and inhibits Wnt3A-stimulated β-catenin stabilization and LEF/TCF reporter activity. Additionally, following niclosamide mediated internalization, the Frizzled1 receptor co-localizes in vesicles containing Transferrin and agonist-activated β2-adrenergic receptor. Therefore, niclosamide may serve as a negative modulator of Wnt/Frizzled1 signaling by depleting up-stream signaling molecules (i.e. Frizzled and Dishevelled), and moreover may provide a valuable means to study the physiological consequences of Wnt signaling. PMID:19772353

Virus Infection and Death Receptor-Mediated Apoptosis.

PubMed

Zhou, Xingchen; Jiang, Wenbo; Liu, Zhongshun; Liu, Shuai; Liang, Xiaozhen

2017-10-27

Virus infection can trigger extrinsic apoptosis. Cell-surface death receptors of the tumor necrosis factor family mediate this process. They either assist persistent viral infection or elicit the elimination of infected cells by the host. Death receptor-mediated apoptosis plays an important role in viral pathogenesis and the host antiviral response. Many viruses have acquired the capability to subvert death receptor-mediated apoptosis and evade the host immune response, mainly by virally encoded gene products that suppress death receptor-mediated apoptosis. In this review, we summarize the current information on virus infection and death receptor-mediated apoptosis, particularly focusing on the viral proteins that modulate death receptor-mediated apoptosis.

Virus Infection and Death Receptor-Mediated Apoptosis

PubMed Central

Zhou, Xingchen; Jiang, Wenbo; Liu, Zhongshun; Liu, Shuai; Liang, Xiaozhen

2017-01-01

Virus infection can trigger extrinsic apoptosis. Cell-surface death receptors of the tumor necrosis factor family mediate this process. They either assist persistent viral infection or elicit the elimination of infected cells by the host. Death receptor-mediated apoptosis plays an important role in viral pathogenesis and the host antiviral response. Many viruses have acquired the capability to subvert death receptor-mediated apoptosis and evade the host immune response, mainly by virally encoded gene products that suppress death receptor-mediated apoptosis. In this review, we summarize the current information on virus infection and death receptor-mediated apoptosis, particularly focusing on the viral proteins that modulate death receptor-mediated apoptosis. PMID:29077026

Building an open academic environment – a new approach to empowering students in their learning of anatomy through ‘Shadow Modules’

PubMed Central

Scott, Jonathan L; Moxham, Bernard J; Rutherford, Stephen M

2014-01-01

Teaching and learning in anatomy is undertaken by a variety of methodologies, yet all of these pedagogies benefit from students discussing and reflecting upon their learning activities. An approach of particular potency is peer-mediated learning, through either peer-teaching or collaborative peer-learning. Collaborative, peer-mediated, learning activities help promote deep learning approaches and foster communities of practice in learning. Students generally flourish in collaborative learning settings but there are limitations to the benefits of collaborative learning undertaken solely within the confines of modular curricula. We describe the development of peer-mediated learning through student-focused and student-led study groups we have termed ‘Shadow Modules’. The ‘Shadow Module’ takes place parallel to the formal academically taught module and facilitates collaboration between students to support their learning for that module. In ‘Shadow Module’ activities, students collaborate towards curating existing online open resources as well as developing learning resources of their own to support their study. Through the use of communication technologies and web 2.0 tools these resources are able to be shared with their peers, thus enhancing the learning experience of all students following the module. The Shadow Module activities have the potential to lead to participants feeling a greater sense of engagement with the subject material, as well as improving their study and group-working skills and developing digital literacy. The outputs from Shadow Module collaborative work are open-source and may be utilised by subsequent student cohorts, thus building up a repository of learning resources designed by and for students. Shadow Module activities would benefit all pedagogies in the study of anatomy, and support students moving from being passive consumers to active participants in learning. PMID:24117249

Antibody induced CD4 down-modulation of T cells is site-specifically mediated by CD64+ cells

PubMed Central

Vogel, Stephanie; Grabski, Elena; Buschjäger, Daniela; Klawonn, Frank; Döring, Marius; Wang, Junxi; Fletcher, Erika; Bechmann, Ingo; Witte, Torsten; Durisin, Martin; Schraven, Burkhart; Mangsbo, Sara M.; Schönfeld, Kurt; Czeloth, Niklas; Kalinke, Ulrich

2015-01-01

Treatment of PBMC with the CD4-specific mAb BT-061 induces CD4 down-modulation of T cells. Here we report that addition of BT-061 to purified T cells did not confer this effect, whereas incubation of T cells in BT-061 coated wells restored CD4 down-modulation. These results implied that Fcγ receptor mediated cell-cell interactions played a role. In consistence with this hypothesis PBMC depleted of CD64+ monocytes did not confer CD4 down-modulation of BT-061 decorated T cells. Strikingly, CD4 down-modulation was observed in BT-061 treated synovial fluid punctuated from patients’ inflamed joints that comprised enhanced numbers of CD64+ cells. In contrast, in a circulating whole blood system injection of BT-061 did not induce CD4 down-modulation, due to CD64 saturation by serum IgG. Similarly, tonsil derived mononuclear cells devoid of CD64+ cells did not show CD4 down-modulation, whereas addition of blood derived monocytes restored the effect. Thus, the interaction of BT-061 decorated T cells with CD64+ cells is needed for CD4 down-modulation, implying that in patients BT-061 would primarily induce CD4 down-modulation at inflammatory sites. These results highlight the need not only to examine the interaction of a given mAb with single FcγR, but also the immunological environment that is appropriate to support such interactions. PMID:26670584

Fluorescent magnetic bead-based mast cell biosensor for electrochemical detection of allergens in foodstuffs.

PubMed

Jiang, Donglei; Zhu, Pei; Jiang, Hui; Ji, Jian; Sun, Xiulan; Gu, Wenshu; Zhang, Genyi

2015-08-15

In this study, a novel electrochemical rat basophilic leukemia cell (RBL-2H3) cell sensor, based on fluorescent magnetic beads, has been developed for the detection and evaluation of different allergens in foodstuffs. Fluorescein isothiocyanate (FITC) was successfully fused inside the SiO2 layer of SiO2 shell-coated Fe3O4 nanoparticles, which was superior to the traditional Fe3O4@SiO2@FITC modification process. The as-synthesized fluorescent magnetic beads were then encapsulated with lipidosome to form cationic magnetic fluorescent nanoparticles (CMFNPs) for mast cell magnetofection. The CMFNPs were then characterized by SEM, TEM, VSM, FTIR, and XRD analyses, and transfected into RBL-2H3 cells through a highly efficient, lipid-mediated magnetofection procedure. Magnetic glassy carbon electrode (MGCE), which possesses excellent reproducibility and regeneration qualities, was then employed to adsorb the CMFNP-transfected RBL-2H3 cells activated by an allergen antigen for electrochemical assay. Results show that the exposure of model antigen-dinitrophenol-bovine serum albumin (DNP-BSA) to anti-DNP IgE-sensitized mast cells induced a robust and long-lasting electrochemical impedance signal in a dose-dependent manner. The detection limit was identified at 3.3×10(-4) ng/mL. To demonstrate the utility of this mast cell-based biosensor for detection of real allergens in foodstuffs, Anti-Pen a1 IgE and Anti-PV IgE-activated cells were employed to quantify both shrimp allergen tropomyosin (Pen a 1) and fish allergen parvalbumin (PV). Results show high detection accuracy for these targets, with a limit of 0.03 μg/mL (shrimp Pen a 1) and 0.16 ng/mL (fish PV), respectively. To this effect, we conclude the proposed method is a facile, highly sensitive, innovative electrochemical method for the evaluation of food allergens. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparison of diffusivity data derived from electrochemical and NMR investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ system in ionic liquids.

PubMed

Solangi, Amber; Bond, Alan M; Burgar, Iko; Hollenkamp, Anthony F; Horne, Michael D; Rüther, Thomas; Zhao, Chuan

2011-06-02

Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport limitations imposed by the higher viscosity of iodide RTILs.

Comparative study of the effect of pharmaceutical additives on the elimination of antibiotic activity during the treatment of oxacillin in water by the photo-Fenton, TiO2-photocatalysis and electrochemical processes.

PubMed

Serna-Galvis, Efraim A; Silva-Agredo, Javier; Giraldo, Ana L; Flórez-Acosta, Oscar A; Torres-Palma, Ricardo A

2016-01-15

Synthetic pharmaceutical effluents loaded with the β-lactam antibiotic oxacillin were treated using advanced oxidation processes (the photo-Fenton system and TiO2 photocatalysis) and chloride mediated electrochemical oxidation (with Ti/IrO2 anodes). Combinations of the antibiotic with excipients (mannitol or tartaric acid), an active ingredient (calcium carbonate, i.e. bicarbonate ions due to the pH) and a cleaning agent (sodium lauryl ether sulfate) were considered. Additionally, urban wastewater that had undergone biological treatment was doped with oxacillin and treated with the tested systems. The evolution of antimicrobial activity was monitored as a parameter of processes efficiency. Although the two advanced oxidation processes (AOPs) differ only in the way they produce OH, marked differences were observed between them. There were also differences between the AOPs and the electrochemical system. Interestingly, each additive had a different effect on each treatment. For water loaded with mannitol, electrochemical treatment was the most suitable option because the additive did not significantly affect the efficiency of the system. Due to the formation of a complex with Fe(3+), tartaric acid accelerated the elimination of antibiotic activity during the photo-Fenton process. For TiO2 photocatalysis, the presence of bicarbonate ions contributed to antibiotic activity elimination through the possible formation of carbonate and bicarbonate radicals. Sodium lauryl ether sulfate negatively affected all of the processes. However, due to the higher selectivity of HOCl compared with OH, electrochemical oxidation showed the least inhibited efficiency. For the urban wastewater doped with oxacillin, TiO2 photocatalysis was the most efficient process. These results will help select the most suitable technology for the treatment of water polluted with β-lactam antibiotics. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Mediator Tail Module Is Required for Tac1-Activated CDR1 Expression and Azole Resistance in Candida albicans.

PubMed

Liu, Zhongle; Myers, Lawrence C

2017-11-01

The human fungal pathogen Candida albicans develops drug resistance after long-term exposure to azole drugs in the treatment of chronic candidiasis. Gain-of-function (GOF) mutations in the transcription factor Tac1 and the consequent expression of its targets, drug efflux pumps Cdr1 and Cdr2, are a common mechanism by which C. albicans acquires fluconazole resistance. The mechanism by which GOF mutations hyperactivate Tac1 is currently unknown. Here, we define a transcriptional activation domain (TAD) at the C terminus of Tac1. GOF mutations within the Tac1 TAD, outside the context of full-length Tac1, generally do not enhance its absolute potential as a transcriptional activator. Negative regulation of the Tac1 TAD by the Tac1 middle region is necessary for the activating effect of GOF mutations or fluphenazine to be realized. We have found that full-length Tac1, when hyperactivated by xenobiotics or GOF mutations, facilitates the recruitment of the Mediator coactivator complex to the CDR1 promoter. Azole resistance and the activation of Tac1 target genes, such as CDR1 , are dependent on the Tac1 TAD and subunits of the Mediator tail module. The dependence of different Tac1 target promoters on the Mediator tail module, however, varies widely. Lastly, we show that hyperactivation of Tac1 is correlated with its Mediator-dependent phosphorylation, a potentially useful biomarker for Tac1 hyperactivation. The role of Mediator in events downstream of Tac1 hyperactivation in fluconazole-resistant clinical isolates is complex and provides opportunities and challenges for therapeutic intervention. Copyright © 2017 American Society for Microbiology.

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.

Context-Dependent Modulation of GABAAR-Mediated Tonic Currents.

PubMed

Patel, Bijal; Bright, Damian P; Mortensen, Martin; Frølund, Bente; Smart, Trevor G

2016-01-13

Tonic GABA currents mediated by high-affinity extrasynaptic GABAA receptors, are increasingly recognized as important regulators of cell and neuronal network excitability. Dysfunctional GABAA receptor signaling that results in modified tonic GABA currents is associated with a number of neurological disorders. Consequently, developing compounds to selectively modulate the activity of extrasynaptic GABAA receptors underlying tonic inhibition is likely to prove therapeutically useful. Here, we examine the GABAA receptor subtype selectivity of the weak partial agonist, 5-(4-piperidyl)isoxazol-3-ol (4-PIOL), as a potential mechanism for modulating extrasynaptic GABAA receptor-mediated tonic currents. By using recombinant GABAA receptors expressed in HEK293 cells, and native GABAA receptors of cerebellar granule cells, hippocampal neurons, and thalamic relay neurons, 4-PIOL evidently displayed differential agonist and antagonist-type profiles, depending on the extrasynaptic GABAA receptor isoforms targeted. For neurons, this resulted in differential modulation of GABA tonic currents, depending on the cell type studied, their respective GABAA receptor subunit compositions, and critically, on the ambient GABA levels. Unexpectedly, 4-PIOL revealed a significant population of relatively low-affinity γ2 subunit-containing GABAA receptors in the thalamus, which can contribute to tonic inhibition under specific conditions when GABA levels are raised. Together, these data indicate that partial agonists, such as 4-PIOL, may be useful for modulating GABAA receptor-mediated tonic currents, but the direction and extent of this modulation is strongly dependent on relative expression levels of different extrasynaptic GABAA receptor subtypes, and on the ambient GABA levels. A background level of inhibition (tonic) is important in the brain for controlling neuronal excitability. Increased levels of tonic inhibition are associated with some neurological disorders but there are no specific ligands capable of selectively reducing tonic inhibition. Here we explore the use of a GABA partial agonist as a selective chemical tool in three different brain regions. We discover that the activity of a partial agonist is heavily dependent upon the GABAA receptor subunit composition underpinning tonic inhibition, and on the ambient levels of GABA in the brain. Copyright © 2016 Patel et al.

Context-Dependent Modulation of GABAAR-Mediated Tonic Currents

PubMed Central

Patel, Bijal; Bright, Damian P.; Mortensen, Martin; Frølund, Bente

2016-01-01

Tonic GABA currents mediated by high-affinity extrasynaptic GABAA receptors, are increasingly recognized as important regulators of cell and neuronal network excitability. Dysfunctional GABAA receptor signaling that results in modified tonic GABA currents is associated with a number of neurological disorders. Consequently, developing compounds to selectively modulate the activity of extrasynaptic GABAA receptors underlying tonic inhibition is likely to prove therapeutically useful. Here, we examine the GABAA receptor subtype selectivity of the weak partial agonist, 5-(4-piperidyl)isoxazol-3-ol (4-PIOL), as a potential mechanism for modulating extrasynaptic GABAA receptor-mediated tonic currents. By using recombinant GABAA receptors expressed in HEK293 cells, and native GABAA receptors of cerebellar granule cells, hippocampal neurons, and thalamic relay neurons, 4-PIOL evidently displayed differential agonist and antagonist-type profiles, depending on the extrasynaptic GABAA receptor isoforms targeted. For neurons, this resulted in differential modulation of GABA tonic currents, depending on the cell type studied, their respective GABAA receptor subunit compositions, and critically, on the ambient GABA levels. Unexpectedly, 4-PIOL revealed a significant population of relatively low-affinity γ2 subunit-containing GABAA receptors in the thalamus, which can contribute to tonic inhibition under specific conditions when GABA levels are raised. Together, these data indicate that partial agonists, such as 4-PIOL, may be useful for modulating GABAA receptor-mediated tonic currents, but the direction and extent of this modulation is strongly dependent on relative expression levels of different extrasynaptic GABAA receptor subtypes, and on the ambient GABA levels. SIGNIFICANCE STATEMENT A background level of inhibition (tonic) is important in the brain for controlling neuronal excitability. Increased levels of tonic inhibition are associated with some neurological disorders but there are no specific ligands capable of selectively reducing tonic inhibition. Here we explore the use of a GABA partial agonist as a selective chemical tool in three different brain regions. We discover that the activity of a partial agonist is heavily dependent upon the GABAA receptor subunit composition underpinning tonic inhibition, and on the ambient levels of GABA in the brain. PMID:26758848

Modulation of Central Synapses by Astrocyte-Released ATP and Postsynaptic P2X Receptors

PubMed Central

Pankratov, Yuriy

2017-01-01

Communication between neuronal and glial cells is important for neural plasticity. P2X receptors are ATP-gated cation channels widely expressed in the brain where they mediate action of extracellular ATP released by neurons and/or glia. Recent data show that postsynaptic P2X receptors underlie slow neuromodulatory actions rather than fast synaptic transmission at brain synapses. Here, we review these findings with a particular focus on the release of ATP by astrocytes and the diversity of postsynaptic P2X-mediated modulation of synaptic strength and plasticity in the CNS. PMID:28845311

Dopamine modulates an intrinsic mGluR5-mediated depolarization underlying prefrontal persistent activity

PubMed Central

Sidiropoulou, Kyriaki; Lu, Fang-Min; Fowler, Melissa A.; Xiao, Rui; Phillips, Christopher; Ozkan, Emin D.; Zhu, Michael X.; White, Francis J.; Cooper, Donald C.

2009-01-01

Intrinsic properties of neurons that enable them to maintain depolarized, persistently activated states in the absence of sustained input are poorly understood. In short-term memory tasks, individual prefrontal cortical (PFC) neurons are capable of maintaining persistent action potential output during delay periods between informative cues and behavioral responses. Dopamine and drugs of abuse alter PFC function and working memory possibly by modulating intrinsic neuronal properties. Here we use patch-clamp recording of layer 5 PFC pyramidal neurons to identify an action potential burst-evoked intrinsic mGluR5-mediated postsynaptic depolarization that initiates an activated state. Depolarization occurs in the absence of recurrent synaptic activity and is reduced by a postsynaptic dopamine D1/5 receptor pathway. The depolarization is substantially diminished following behavioral sensitization to cocaine; moreover the D1/5 receptor modulation is lost. We propose the burst-evoked intrinsic depolarization to be a novel form of short-term cellular memory that is modulated by dopamine and cocaine experience. PMID:19169252

Nitrogen modulation of legume root architecture signaling pathways involves phytohormones and small regulatory molecules.

PubMed

Mohd-Radzman, Nadiatul A; Djordjevic, Michael A; Imin, Nijat

2013-10-01

Nitrogen, particularly nitrate is an important yield determinant for crops. However, current agricultural practice with excessive fertilizer usage has detrimental effects on the environment. Therefore, legumes have been suggested as a sustainable alternative for replenishing soil nitrogen. Legumes can uniquely form nitrogen-fixing nodules through symbiotic interaction with specialized soil bacteria. Legumes possess a highly plastic root system which modulates its architecture according to the nitrogen availability in the soil. Understanding how legumes regulate root development in response to nitrogen availability is an important step to improving root architecture. The nitrogen-mediated root development pathway starts with sensing soil nitrogen level followed by subsequent signal transduction pathways involving phytohormones, microRNAs and regulatory peptides that collectively modulate the growth and shape of the root system. This review focuses on the current understanding of nitrogen-mediated legume root architecture including local and systemic regulations by different N-sources and the modulations by phytohormones and small regulatory molecules.

Exogenous γ-aminobutyric acid (GABA) affects pollen tube growth via modulating putative Ca2+-permeable membrane channels and is coupled to negative regulation on glutamate decarboxylase

PubMed Central

Yu, Guang-Hui; Zou, Jie; Feng, Jing; Peng, Xiong-Bo; Wu, Ju-You; Wu, Ying-Liang; Palanivelu, Ravishankar; Sun, Meng-Xiang

2014-01-01

γ-Aminobutyric acid (GABA) is implicated in pollen tube growth, but the molecular and cellular mechanisms that it mediates are largely unknown. Here, it is shown that exogenous GABA modulates putative Ca2+-permeable channels on the plasma membranes of tobacco pollen grains and pollen tubes. Whole-cell voltage-clamp experiments and non-invasive micromeasurement technology (NMT) revealed that the influx of Ca2+ increases in pollen tubes in response to exogenous GABA. It is also demonstrated that glutamate decarboxylase (GAD), the rate-limiting enzyme of GABA biosynthesis, is involved in feedback controls of Ca2+-permeable channels to fluctuate intracellular GABA levels and thus modulate pollen tube growth. The findings suggest that GAD activity linked with Ca2+-permeable channels relays an extracellular GABA signal and integrates multiple signal pathways to modulate tobacco pollen tube growth. Thus, the data explain how GABA mediates the communication between the style and the growing pollen tubes. PMID:24799560

Soluble HLA-G dampens CD94/NKG2A expression and function and differentially modulates chemotaxis and cytokine and chemokine secretion in CD56bright and CD56dim NK cells.

PubMed

Morandi, Fabio; Ferretti, Elisa; Castriconi, Roberta; Dondero, Alessandra; Petretto, Andrea; Bottino, Cristina; Pistoia, Vito

2011-11-24

Soluble HLA-G (sHLA-G) inhibits natural killer (NK) cell functions. Here, we investigated sHLA-G-mediated modulation of (1) chemokine receptor and NK receptor expression and function and (2) cytokine and chemokine secretion in CD56bright and CD56dim NK cells. sHLA-G-treated or untreated peripheral blood (PB) and tonsil NK cells were analyzed for chemokine receptor and NK receptor expression by flow cytometry. sHLA-G down-modulated (1) CXCR3 on PB and tonsil CD56bright and CD56dim, (2) CCR2 on PB and tonsil CD56bright, (3) CX3CR1 on PB CD56dim, (4) CXCR5 on tonsil CD56dim, and (5) CD94/NKG2A on PB and tonsil CD56brigh) and CD56dim NK cells. Such sHLA-G-mediated down-modulations were reverted by adding anti-HLA-G or anti-ILT2 mAbs. sHLA-G inhibited chemotaxis of (1) PB NK cells toward CXCL10, CXCL11, and CX3CL1 and (2) PB CD56bright NK cells toward CCL2 and CXCL10. IFN-γ secretion induced by NKp46 engagement was inhibited by NKG2A engagement in untreated but not in sHLA-G-treated NK cells. sHLA-G up-regulated secretion of (1) CCL22 in CD56bright and CD56dim and (2) CCL2, CCL8, and CXCL2-CXCL3 in CD56dim PB NK cells. Signal transduction experiments showed sHLA-G-mediated down-modulation of Stat5 phosphorylation in PB NK cells. In conclusion, our data delineated novel mechanisms of sHLA-G-mediated inhibition of NK-cell functions.

Ultrasound-Mediated Biophotonic Imaging: A Review of Acousto-Optical Tomography and Photo-Acoustic Tomography

PubMed Central

Wang, Lihong V.

2004-01-01

This article reviews two types of ultrasound-mediated biophotonic imaging–acousto-optical tomography (AOT, also called ultrasound-modulated optical tomography) and photo-acoustic tomography (PAT, also called opto-acoustic or thermo-acoustic tomography)–both of which are based on non-ionizing optical and ultrasonic waves. The goal of these technologies is to combine the contrast advantage of the optical properties and the resolution advantage of ultrasound. In these two technologies, the imaging contrast is based primarily on the optical properties of biological tissues, and the imaging resolution is based primarily on the ultrasonic waves that either are provided externally or produced internally, within the biological tissues. In fact, ultrasonic mediation overcomes both the resolution disadvantage of pure optical imaging in thick tissues and the contrast and speckle disadvantages of pure ultrasonic imaging. In our discussion of AOT, the relationship between modulation depth and acoustic amplitude is clarified. Potential clinical applications of ultrasound-mediated biophotonic imaging include early cancer detection, functional imaging, and molecular imaging. PMID:15096709

LPS-treated bone marrow-derived dendritic cells induce immune tolerance through modulating differentiation of CD4+ regulatory T cell subpopulations mediated by 3G11 and CD127.

PubMed

Zhou, Fang; Zhang, Guang-Xian; Rostami, Abdolmohamad

2017-06-01

Intravenous transfer of LPS-treated bone marrow-derived dendritic cells blocks development of autoimmunity induced by CD4 + T cells in vivo. However, cellular mechanisms of dendritic cell-mediated immune tolerance have not yet been fully elucidated. Here, we report that there are two new subpopulations of CD4 + CD25 + FoxP3 + GITR + regulatory T cells (CD127 + 3G11 + and CD127 + 3G11 - cells). LPS-treated dendritic cells facilitate development of CD4 + CD127 + 3G11 - regulatory T cells but inhibit that of CD4 + CD127 + 3G11 + regulatory T cells. LPS-induced tolerogenic dendritic cells may cause immune tolerance through modulating balance of different subsets of CD4 + regulatory T cells mediated by CD127 and 3G11. Our results imply a new potential cellular mechanism of dendritic cell-mediated immune tolerance.

Inducible MicroRNA-3570 Feedback Inhibits the RIG-I-Dependent Innate Immune Response to Rhabdovirus in Teleost Fish by Targeting MAVS/IPS-1.

PubMed

Xu, Tianjun; Chu, Qing; Cui, Junxia; Bi, Dekun

2018-01-15

Effectively recognizing invading viruses and subsequently inducing innate antiviral immunity are essential for host antiviral defense. Although these processes are closely regulated by the host to maintain immune balance, viruses have evolved the ability to downregulate or upregulate these processes for their survival. MicroRNAs (miRNAs) are a family of small noncoding RNAs that play vital roles in modulating host immune response. Accumulating evidence demonstrates that host miRNAs as mediators are involved in regulating viral replication and host antiviral immunity in mammals. However, the underlying regulatory mechanisms in fish species are still poorly understood. Here, we found that rhabdovirus infection significantly upregulated host miR-3570 expression in miiuy croaker macrophages. Induced miR-3570 negatively modulated RNA virus-triggered type I interferon (IFN) and antiviral gene production, thus facilitating viral replication. Furthermore, miR-3570 was found to target and posttranscriptionally downregulate mitochondrial antiviral signaling protein (MAVS), which functions as a platform for innate antiviral signal transduction. Moreover, we demonstrated that miR-3570 suppressed the expression of MAVS, thereby inhibiting MAVS-mediated NF-κB and IRF3 signaling. The collective results demonstrated a novel regulation mechanism of MAVS-mediated immunity during RNA viral infection by miRNA. IMPORTANCE RNA viral infection could upregulate host miR-3570 expression in miiuy croaker macrophages. Induced miR-3570 negatively modulates RNA virus-triggered type I IFN and antiviral gene production, thus facilitating viral replication. Remarkably, miR-3570 could target and inhibit MAVS expression, which thus modulates MAVS-mediated NF-κB and IRF3 signaling. The collective results of this study suggest a novel regulation mechanism of MAVS-mediated immunity during RNA viral infection by miR-3570. Thus, a novel mechanism for virus evasion in fish is proposed. Copyright © 2018 American Society for Microbiology.

Fasting is a physiological stimulus of vagus-mediated enhancement of nociception in the female rat.

PubMed

Khasar, S G; Reichling, D B; Green, P G; Isenberg, W M; Levine, J D

2003-01-01

The vagus nerve modulates nociception by a mechanism dependent upon gonadal hormones and the adrenal medulla. In the present study we tested the hypothesis that this modulation is dynamically controlled by physiological stimulation of structures innervated by the subdiaphragmatic vagus. Specifically, food deprivation (fasting) was employed to increase activity in the subdiaphragmatic vagus, and the experiments were performed mainly in female rats because our previous observations suggested that baseline activity in the pathway is lower in females than in males. Consistent with the hypothesis, after a 48-h fast, female rats exhibited increased nociceptive behavior in the formalin test. In contrast, fasting had no effect on formalin-evoked nociceptive behavior in male rats. The fasting-induced effect on nociception appears to be mediated by the vagus nerve since it is prevented by subdiaphragmatic vagotomy. Also similar to the previously characterized vagus-mediated modulation, the effect of fasting in the female is blocked by gonadectomy or adrenal medullectomy, and hormone replacement with 17beta-estradiol in gonadectomized female rats restored the effect of fasting. Decreased glucose metabolism apparently does not play a significant role in the effect of fasting on nociception, since the effect was unchanged when 5% glucose was provided in the drinking water throughout the fasting period. On the other hand, increasing the bulk content of the stomach (without providing nutrients) by infusion of petrolatum significantly attenuated the effect of fasting during the interphase period of the formalin response, suggesting that decreased gut distention, and possibly motility, are important in fasting-induced enhancement of nociception. These results indicate that fasting is a physiological activator of the vagus-mediated pain modulation pathway. This suggests the possibility that, especially in females, natural periodic changes in gut distention and motility may control an ongoing vagus-mediated adjustment in the organism's nociceptive sensitivity.

Photo-electrochemical communication between cyanobacteria (Leptolyngbia sp.) and osmium redox polymer modified electrodes.

PubMed

Hasan, Kamrul; Bekir Yildiz, Huseyin; Sperling, Eva; Conghaile, Peter Ó; Packer, Michael A; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

2014-12-07

Photosynthetic microbial fuel cells (PMFCs) are an emerging technology for renewable solar energy conversion. Major efforts have been made to explore the electrogenic activity of cyanobacteria, mostly using practically unsustainable reagents. Here we report on photocurrent generation (≈8.64 μA cm(-2)) from cyanobacteria immobilized on electrodes modified with an efficient electron mediator, an Os(2+/3+) redox polymer. Upon addition of ferricyanide to the electrolyte, cyanobacteria generate the maximum current density of ≈48.2 μA cm(-2).

Mechanistic understanding of monosaccharide-air flow battery electrochemistry

NASA Astrophysics Data System (ADS)

Scott, Daniel M.; Tsang, Tsz Ho; Chetty, Leticia; Aloi, Sekotilani; Liaw, Bor Yann

Recently, an inexpensive monosaccharide-air flow battery configuration has been demonstrated to utilize a strong base and a mediator redox dye to harness electrical power from the partial oxidation of glucose. Here the mechanistic understanding of glucose oxidation in this unique glucose-air power source is further explored by acid-base titration experiments, 13C NMR, and comparison of results from chemically different redox mediators (indigo carmine vs. methyl viologen) and sugars (fructose vs. glucose) via studies using electrochemical techniques. Titration results indicate that gluconic acid is the main product of the cell reaction, as supported by evidence in the 13C NMR spectra. Using indigo carmine as the mediator dye and fructose as the energy source, an abiotic cell configuration generates a power density of 1.66 mW cm -2, which is greater than that produced from glucose under similar conditions (ca. 1.28 mW cm -2). A faster transition from fructose into the ene-diol intermediate than from glucose likely contributed to this difference in power density.

Interfacial Mechanism in Lithium-Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics.

PubMed

Lang, Shuang-Yan; Xiao, Rui-Juan; Gu, Lin; Guo, Yu-Guo; Wen, Rui; Wan, Li-Jun

2018-06-08

Lithium-sulfur batteries possess favorable potential for energy-storage applications due to their high specific capacity and the low cost of sulfur. Intensive understanding of the interfacial mechanism, especially the polysulfide formation and transformation under complex electrochemical environment, is crucial for the build-up of advanced batteries. Here we report the direct visualization of interfacial evolution and dynamic transformation of the sulfides mediated by the lithium salts via real-time atomic force microscopy monitoring inside a working battery. The observations indicate that the lithium salts influence the structures and processes of sulfide deposition/decomposition during discharge/charge. Moreover, the distinct ion interaction and diffusion in electrolytes manipulate the interfacial reactions determining the kinetics of the sulfide transformation. Our findings provide deep insights into surface dynamics of lithium-sulfur reactions revealing the salt-mediated mechanisms at nanoscale, which contribute to the profound understanding of the interfacial processes for the optimized design of lithium-sulfur batteries.

Discharging a Li-S battery with ultra-high sulphur content cathode using a redox mediator.

PubMed

Kim, Kwi Ryong; Lee, Kug-Seung; Ahn, Chi-Yeong; Yu, Seung-Ho; Sung, Yung-Eun

2016-08-30

Lithium-sulphur batteries are under intense research due to the high specific capacity and low cost. However, several problems limit their commercialization. One of them is the insulating nature of sulphur, which necessitates a large amount of conductive agent and binder in the cathode, reducing the effective sulphur load as well as the energy density. Here we introduce a redox mediator, cobaltocene, which acts as an electron transfer agent between the conductive surface and the polysulphides in the electrolyte. We confirmed that cobaltocene could effectively convert polysulphides to Li2S using scanning electron microscope, X-ray absorption near-edge structure and in-situ X-ray diffraction studies. This redox mediator enabled excellent electrochemical performance in a cathode with ultra-high sulphur content (80 wt%). It delivered 400 mAh g(-1)cathode capacity after 50 cycles, which is equivalent to 800 mAh g(-1)S in a typical cathode with 50 wt% sulphur. Furthermore, the volumetric capacity was also dramatically improved.

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.)

Insulin modulates norepinephrine-mediated melatonin synthesis in cultured rat pineal gland

USDA-ARS?s Scientific Manuscript database

The mammalian pineal gland synthesizes melatonin in a circadian manner, peaking during the dark phase. This synthesis is primarily regulated by sympathetic innervations via noradrenergic fibers, but is also modulated by many peptidergic and hormonal systems. A growing number of studies reveal a comp...

Perceived Discrimination, Psychological Distress, and Current Smoking Status: Results From the Behavioral Risk Factor Surveillance System Reactions to Race Module, 2004–2008

PubMed Central

Peppone, Luke J.; Alcaraz, Kassandra; McQueen, Amy; Guido, Joseph J.; Carroll, Jennifer K.; Shacham, Enbal; Morrow, Gary R.

2012-01-01

Objectives. We examined the association between perceived discrimination and smoking status and whether psychological distress mediated this relationship in a large, multiethnic sample. Methods. We used 2004 through 2008 data from the Behavioral Risk Factor Surveillance System Reactions to Race module to conduct multivariate logistic regression analyses and tests of mediation examining associations between perceived discrimination in health care and workplace settings, psychological distress, and current smoking status. Results. Regardless of race/ethnicity, perceived discrimination was associated with increased odds of current smoking. Psychological distress was also a significant mediator of the discrimination–smoking association. Conclusions. Our results indicate that individuals who report discriminatory treatment in multiple domains may be more likely to smoke, in part, because of the psychological distress associated with such treatment. PMID:22420821

A dendritic cell-stromal axis maintains immune responses in lymph nodes

PubMed Central

Kumar, Varsha; Dasoveanu, Dragos C.; Chyou, Susan; Tzeng, Te-Chen; Rozo, Cristina; Liang, Yong; Stohl, William; Fu, Yang-Xin; Ruddle, Nancy; Lu, Theresa T.

2015-01-01

Summary Within secondary lymphoid tissues, stromal reticular cells support lymphocyte function, and targeting reticular cells is a potential strategy for controlling pathogenic lymphocytes in disease. However, the mechanisms that regulate reticular cell function are not well understood. Here we found that during an immune response in lymph nodes, dendritic cells (DCs) maintain reticular cell survival in multiple compartments. DC-derived lymphotoxin beta receptor (LTβR) ligands were critical mediators, and LTβR signaling on reticular cells mediated cell survival by modulating podoplanin (PDPN). PDPN modulated integrin-mediated cell adhesion, which maintained cell survival. This DC-stromal axis maintained lymphocyte survival and the ongoing immune response. Our findings provide insight into the functions of DCs, LTβR, and PDPN and delineate a DC-stromal axis that can potentially be targeted in autoimmune or lymphoproliferative diseases. PMID:25902483

Modeling of signaling crosstalk-mediated drug resistance and its implications on drug combination.

PubMed

Sun, Xiaoqiang; Bao, Jiguang; You, Zhuhong; Chen, Xing; Cui, Jun

2016-09-27

The efficacy of pharmacological perturbation to the signaling transduction network depends on the network topology. However, whether and how signaling dynamics mediated by crosstalk contributes to the drug resistance are not fully understood and remain to be systematically explored. In this study, motivated by a realistic signaling network linked by crosstalk between EGF/EGFR/Ras/MEK/ERK pathway and HGF/HGFR/PI3K/AKT pathway, we develop kinetic models for several small networks with typical crosstalk modules to investigate the role of the architecture of crosstalk in inducing drug resistance. Our results demonstrate that crosstalk inhibition diminishes the response of signaling output to the external stimuli. Moreover, we show that signaling crosstalk affects the relative sensitivity of drugs, and some types of crosstalk modules that could yield resistance to the targeted drugs were identified. Furthermore, we quantitatively evaluate the relative efficacy and synergism of drug combinations. For the modules that are resistant to the targeted drug, we identify drug targets that can not only increase the relative drug efficacy but also act synergistically. In addition, we analyze the role of the strength of crosstalk in switching a module between drug-sensitive and drug-resistant. Our study provides mechanistic insights into the signaling crosstalk-mediated mechanisms of drug resistance and provides implications for the design of synergistic drug combinations to reduce drug resistance.

Polysaccharide of Black cumin (Nigella sativa) modulates molecular signaling cascade of gastric ulcer pathogenesis.

PubMed

Manjegowda, Srikanta Belagihalli; Rajagopal, Harsha Mysore; Dharmesh, Shylaja Mallaiah

2017-08-01

Gastric ulcer is a multi-step disease and healing requires a complex process including repair and re-architecture of gastric mucosa with the involvement of molecular events. Current study was designed to understand the gastric ulcer healing mechanism of rhamnogalacturonan-I type pectic polysaccharide of black cumin (BCPP) utilizing acetic acid induced gastric ulcers in rats. BCPP fed groups at 200mg/kg b.w. for 10days showed up to 85% healing of gastric ulcers with modulation of key molecular events involved in ulcer healing process such as increase in gastric mucin content, cyclooxygenase-2 (Cox-2) and prostaglandin E 2 (PGE 2 ). The increase in extracellular signal-regulated kinase-2 (ERK-2) indicated that, BCPP could induce PGE-2 synthesis by increasing ERK-2 mediated COX-2 activity. Increase in matrix metalloproteinase-2 (MMP-2) and decrease in MMP-9 levels in BCPP treated groups indicated differential regulation of MMP-2 and 9, an essential event required for gastric mucosal re-modulation. BCPP containing bound phenolics (26mg/g) might have also played a role in increasing speed and quality of ulcer healing by inhibiting H + , K + -ATPase and decreasing free radical mediated oxidation and cellular damages. Overall, studies showed that the polysaccharide can mediate ulcer healing by modulating signaling pathways involved in either ulcer aggravation or healing process. Copyright © 2017. Published by Elsevier B.V.

The C-module-binding factor supports amplification of TRE5-A retrotransposons in the Dictyostelium discoideum genome.

PubMed

Bilzer, Annika; Dölz, Heike; Reinhardt, Alexander; Schmith, Anika; Siol, Oliver; Winckler, Thomas

2011-01-01

Retrotransposable elements are molecular parasites that have invaded the genomes of virtually all organisms. Although retrotransposons encode essential proteins to mediate their amplification, they also require assistance by host cell-encoded machineries that perform functions such as DNA transcription and repair. The retrotransposon TRE5-A of the social amoeba Dictyostelium discoideum generates a notable amount of both sense and antisense RNAs, which are generated from element-internal promoters, located in the A module and the C module, respectively. We observed that TRE5-A retrotransposons depend on the C-module-binding factor (CbfA) to maintain high steady-state levels of TRE5-A transcripts and that CbfA supports the retrotransposition activity of TRE5-A elements. The carboxy-terminal domain of CbfA was found to be required and sufficient to mediate the accumulation of TRE5-A transcripts, but it did not support productive retrotransposition of TRE5-A. This result suggests different roles for CbfA protein domains in the regulation of TRE5-A retrotransposition frequency in D. discoideum cells. Although CbfA binds to the C module in vitro, the factor regulates neither C-module nor A-module promoter activity in vivo. We speculate that CbfA supports the amplification of TRE5-A retrotransposons by suppressing the expression of an as yet unidentified component of the cellular posttranscriptional gene silencing machinery.

Flavonoid Naringenin: A Potential Immunomodulator for Chlamydia trachomatis Inflammation

PubMed Central

Yilma, Abebayehu N.; Singh, Shree R.; Morici, Lisa; Dennis, Vida A.

2013-01-01

Chlamydia trachomatis, the agent of bacterial sexually transmitted infections, can manifest itself as either acute cervicitis, pelvic inflammatory disease, or a chronic asymptomatic infection. Inflammation induced by C. trachomatis contributes greatly to the pathogenesis of disease. Here we evaluated the anti-inflammatory capacity of naringenin, a polyphenolic compound, to modulate inflammatory mediators produced by mouse J774 macrophages infected with live C. trachomatis. Infected macrophages produced a broad spectrum of inflammatory cytokines (GM-CSF, TNF, IL-1β, IL-1α, IL-6, IL-12p70, and IL-10) and chemokines (CCL4, CCL5, CXCL1, CXCL5, and CXCL10) which were downregulated by naringenin in a dose-dependent manner. Enhanced protein and mRNA gene transcript expressions of TLR2 and TLR4 in addition to the CD86 costimulatory molecule on infected macrophages were modulated by naringenin. Pathway-specific inhibition studies disclosed that p38 mitogen-activated-protein kinase (MAPK) is involved in the production of inflammatory mediators by infected macrophages. Notably, naringenin inhibited the ability of C. trachomatis to phosphorylate p38 in macrophages, suggesting a potential mechanism of its attenuation of concomitantly produced inflammatory mediators. Our data demonstrates that naringenin is an immunomodulator of inflammation triggered by C. trachomatis, which possibly may be mediated upstream by modulation of TLR2, TLR4, and CD86 receptors on infected macrophages and downstream via the p38 MAPK pathway. PMID:23766556

Electrochemical degradation, kinetics & performance studies of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Das, Debanjan

Linear and Non-linear electrochemical characterization techniques and equivalent circuit modelling were carried out on miniature and sub-commercial Solid Oxide Fuel Cell (SOFC) stacks as an in-situ diagnostic approach to evaluate and analyze their performance under the presence of simulated alternative fuel conditions. The main focus of the study was to track the change in cell behavior and response live, as the cell was generating power. Electrochemical Impedance Spectroscopy (EIS) was the most important linear AC technique used for the study. The distinct effects of inorganic components usually present in hydrocarbon fuel reformates on SOFC behavior have been determined, allowing identification of possible "fingerprint" impedance behavior corresponding to specific fuel conditions and reaction mechanisms. Critical electrochemical processes and degradation mechanisms which might affect cell performance were identified and quantified. Sulfur and siloxane cause the most prominent degradation and the associated electrochemical cell parameters such as Gerisher and Warburg elements are applied respectively for better understanding of the degradation processes. Electrochemical Frequency Modulation (EFM) was applied for kinetic studies in SOFCs for the very first time for estimating the exchange current density and transfer coefficients. EFM is a non-linear in-situ electrochemical technique conceptually different from EIS and is used extensively in corrosion work, but rarely used on fuel cells till now. EFM is based on exploring information obtained from non-linear higher harmonic contributions from potential perturbations of electrochemical systems, otherwise not obtained by EIS. The baseline fuel used was 3 % humidified hydrogen with a 5-cell SOFC sub-commercial planar stack to perform the analysis. Traditional methods such as EIS and Tafel analysis were carried out at similar operating conditions to verify and correlate with the EFM data and ensure the validity of the obtained information. The obtained values closely range from around 11 mA cm-2 - 16 mA cm -2 with reasonable repeatability and excellent accuracy. The potential advantages of EFM compared to traditional methods were realized and our primary aim at demonstrating this technique on a SOFC system are presented which can act as a starting point for future research efforts in this area. Finally, an approach based on in-situ State of Health tests by EIS was formulated and investigated to understand the most efficient fuel conditions for suitable long term operation of a solid oxide fuel cell stack under power generation conditions. The procedure helped to reflect the individual effects of three most important fuel characteristics CO/H2 volumetric ratio, S/C ratio and fuel utilization under the presence of a simulated alternative fuel at 0.4 A cm-2. Variation tests helped to identify corresponding electrochemical/chemical processes, narrow down the most optimum operating regimes considering practical behavior of simulated reformer-SOFC system arrangements. At the end, 8 different combinations of the optimized parameters were tested long term with the stack, and the most efficient blend was determined.

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

DOE PAGES

Gao, Min -Rui; Chan, Maria K. Y.; Sun, Yugang

2015-07-03

In this study, layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of -103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10 -3more » mA cm -2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance.« less

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

PubMed Central

Gao, Min-Rui; Chan, Maria K.Y.; Sun, Yugang

2015-01-01

Layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of −103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10−3 mA cm−2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance. PMID:26138031

Real-Time Plasmonic Monitoring of Single Gold Amalgam Nanoalloy Electrochemical Formation and Stripping.

PubMed

Wang, Jun-Gang; Fossey, John S; Li, Meng; Xie, Tao; Long, Yi-Tao

2016-03-01

Direct electrodeposition of mercury onto gold nanorods on an ITO substrate, without reducing agents, is reported. The growth of single gold amalgam nanoalloy particles and subsequent stripping was monitored in real-time monitoring by plasmonic effects and single-nanoparticle dark-field spectroelectrochemistry techniques. Time-dependent scattering spectral information conferred insight into the growth and stripping mechanism of a single nanoalloy particle. Four critical stages were observed: First, rapid deposition of Hg atoms onto Au nanorods; second, slow diffusion of Hg atoms into Au nanorods; third, prompt stripping of Hg atoms from Au nanorods; fourth, moderate diffusion from the inner core of Au nanorods. Under high Hg(2+) concentrations, homogeneous spherical gold amalgam nanoalloys were obtained. These results demonstrate that the morphology and composition of individual gold amalgam nanoalloys can be precisely regulated electrochemically. Moreover, gold amalgam nanoalloys with intriguing optical properties, such as modulated plasmonic lifetimes and quality factor Q, could be obtained. This may offer opportunities to extend applications in photovoltaic energy conversion and chemical sensing.

Inhibition of Mild Steel Corrosion in Hydrochloric Acid Solution by New Coumarin

PubMed Central

Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Hammed, Leiqaa A.; Al-Amiery, Ahmed A.; San, Ng Hooi; Musa, Ahmed Y.

2014-01-01

A new coumarin derivative, N,N′-((2E,2′E)-2,2′-(1,4-phenylenebis(methanylylidene))bis(hydrazinecarbonothioyl))bis(2-oxo-2H-chromene-3-carboxamide) PMBH, was synthesized and its chemical structure was elucidated and confirmed using spectroscopic techniques (Infrared spectroscopy IR, Proton nuclear magnetic resonance, 1H-NMR and carbon-13 nuclear magnetic resonance 13C-NMR). The corrosion inhibition effect of PMBH on mild steel in 1.0 M HCl was investigated using corrosion potential (ECORR), potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) measurements. The obtained results indicated that PMBH has promising inhibitive effects on the corrosion of mild steel in 1.0 M HCl across all of the conditions examined. Scanning electron microscopy (SEM) was used to investigate the morphology of the mild steel before and after immersion in 1.0 M HCl solution containing 0.5 mM of PMBH. Surface analysis revealed improvement of corrosion resistance in presence of PMBH. PMID:28788680

Inhibition of Mild Steel Corrosion in Hydrochloric Acid Solution by New Coumarin.

PubMed

Kadhum, Abdul Amir H; Mohamad, Abu Bakar; Hammed, Leiqaa A; Al-Amiery, Ahmed A; San, Ng Hooi; Musa, Ahmed Y

2014-06-05

A new coumarin derivative, N , N '-((2E,2'E)-2,2'-(1,4-phenylenebis (methanylylidene))bis(hydrazinecarbonothioyl))bis(2-oxo-2H-chromene-3-carboxamide) PMBH, was synthesized and its chemical structure was elucidated and confirmed using spectroscopic techniques (Infrared spectroscopy IR, Proton nuclear magnetic resonance, 1 H-NMR and carbon-13 nuclear magnetic resonance 13 C-NMR). The corrosion inhibition effect of PMBH on mild steel in 1.0 M HCl was investigated using corrosion potential ( E CORR ), potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) measurements. The obtained results indicated that PMBH has promising inhibitive effects on the corrosion of mild steel in 1.0 M HCl across all of the conditions examined. Scanning electron microscopy (SEM) was used to investigate the morphology of the mild steel before and after immersion in 1.0 M HCl solution containing 0.5 mM of PMBH. Surface analysis revealed improvement of corrosion resistance in presence of PMBH.

CMOS Amperometric ADC With High Sensitivity, Dynamic Range and Power Efficiency for Air Quality Monitoring.

PubMed

Li, Haitao; Boling, C Sam; Mason, Andrew J

2016-08-01

Airborne pollutants are a leading cause of illness and mortality globally. Electrochemical gas sensors show great promise for personal air quality monitoring to address this worldwide health crisis. However, implementing miniaturized arrays of such sensors demands high performance instrumentation circuits that simultaneously meet challenging power, area, sensitivity, noise and dynamic range goals. This paper presents a new multi-channel CMOS amperometric ADC featuring pixel-level architecture for gas sensor arrays. The circuit combines digital modulation of input currents and an incremental Σ∆ ADC to achieve wide dynamic range and high sensitivity with very high power efficiency and compact size. Fabricated in 0.5 [Formula: see text] CMOS, the circuit was measured to have 164 dB cross-scale dynamic range, 100 fA sensitivity while consuming only 241 [Formula: see text] and 0.157 [Formula: see text] active area per channel. Electrochemical experiments with liquid and gas targets demonstrate the circuit's real-time response to a wide range of analyte concentrations.

A high-mobility electronic system at an electrolyte-gated oxide surface

DOE PAGES

Gallagher, Patrick; Lee, Menyoung; Petach, Trevor A.; ...

2015-03-12

Electrolyte gating is a powerful technique for accumulating large carrier densities at a surface. Yet this approach suffers from significant sources of disorder: electrochemical reactions can damage or alter the sample, and the ions of the electrolyte and various dissolved contaminants sit Angstroms from the electron system. Accordingly, electrolyte gating is well suited to studies of superconductivity and other phenomena robust to disorder, but of limited use when reactions or disorder must be avoided. Here we demonstrate that these limitations can be overcome by protecting the sample with a chemically inert, atomically smooth sheet of hexagonal boron nitride. We illustratemore » our technique with electrolyte-gated strontium titanate, whose mobility when protected with boron nitride improves more than 10-fold while achieving carrier densities nearing 10 14 cm –2. In conclusion, our technique is portable to other materials, and should enable future studies where high carrier density modulation is required but electrochemical reactions and surface disorder must be minimized.« less

From tunable core-shell nanoparticles to plasmonic drawbridges: Active control of nanoparticle optical properties

PubMed Central

Byers, Chad P.; Zhang, Hui; Swearer, Dayne F.; Yorulmaz, Mustafa; Hoener, Benjamin S.; Huang, Da; Hoggard, Anneli; Chang, Wei-Shun; Mulvaney, Paul; Ringe, Emilie; Halas, Naomi J.; Nordlander, Peter; Link, Stephan; Landes, Christy F.

2015-01-01

The optical properties of metallic nanoparticles are highly sensitive to interparticle distance, giving rise to dramatic but frequently irreversible color changes. By electrochemical modification of individual nanoparticles and nanoparticle pairs, we induced equally dramatic, yet reversible, changes in their optical properties. We achieved plasmon tuning by oxidation-reduction chemistry of Ag-AgCl shells on the surfaces of both individual and strongly coupled Au nanoparticle pairs, resulting in extreme but reversible changes in scattering line shape. We demonstrated reversible formation of the charge transfer plasmon mode by switching between capacitive and conductive electronic coupling mechanisms. Dynamic single-particle spectroelectrochemistry also gave an insight into the reaction kinetics and evolution of the charge transfer plasmon mode in an electrochemically tunable structure. Our study represents a highly useful approach to the precise tuning of the morphology of narrow interparticle gaps and will be of value for controlling and activating a range of properties such as extreme plasmon modulation, nanoscopic plasmon switching, and subnanometer tunable gap applications. PMID:26665175

Al-based anti-corrosion and T-permeation barrier development for future DEMO blankets

NASA Astrophysics Data System (ADS)

Krauss, W.; Konys, J.; Holstein, N.; Zimmermann, H.

2011-10-01

In the Helium-Cooled-Liquid-Lead (HCLL) design of Test-Blanket-Modules (TBM's) for a future fusion power plant Pb-15.7Li is used as liquid breeder which is in direct contact with the structure material, e.g. EUROFER steel. Compatibility testing showed that high corrosion attack appears and that the dissolved steel components form precipitates with a high risk of system blockages. A reliable operation needs coatings as corrosion barriers. The earlier developed Hot-Dip Aluminisation (HDA) process has shown that Al-based scales can act as anti-corrosion as well as T-permeation barriers. Meanwhile two advanced electro-chemically based processes for deposition of Al-scales were successfully developed. The first (ECA = Electro-Chemical Al-deposition) is working with an organic electrolyte and the second one (ECX = Electro-Chemical-X-metal-deposition) is based on ionic liquids. Coatings in the μm-range were deposited homogeneously with exact controllable thicknesses. Metallurgical investigations showed the successful generation of protective scales and compatibility testing demonstrated the barrier function.

Wireless programmable electrochemical drug delivery micropump with fully integrated electrochemical dosing sensors.

PubMed

Sheybani, Roya; Cobo, Angelica; Meng, Ellis

2015-08-01

We present a fully integrated implantable electrolysis-based micropump with incorporated EI dosing sensors. Wireless powering and data telemetry (through amplitude and frequency modulation) were utilized to achieve variable flow control and a bi-directional data link with the sensors. Wireless infusion rate control (0.14-1.04 μL/min) and dose sensing (bolus resolution of 0.55-2 μL) were each calibrated separately with the final circuit architecture and then simultaneous wireless flow control and dose sensing were demonstrated. Recombination detection using the dosing system, as well as, effects of coil separation distance and misalignment in wireless power and data transfer were studied. A custom-made normally closed spring-loaded ball check valve was designed and incorporated at the reservoir outlet to prevent backflow of fluids as a result of the reverse pressure gradient caused by recombination of electrolysis gases. Successful delivery, infusion rate control, and dose sensing were achieved in simulated brain tissue.

Dopant-Modulating Mechanism of Lithium Adsorption and Diffusion at the Graphene /Li2S Interface

NASA Astrophysics Data System (ADS)

Guo, Lichao; Li, Jiajun; Wang, Huayu; Zhao, Naiqin; Shi, Chunsheng; Ma, Liying; He, Chunnian; He, Fang; Liu, Enzuo

2018-02-01

Graphene modification is one of the most effective routes to enhance the electrochemical properties of the transition-metal sulfide anode for Li-ion batteries and the Li2S cathode for Li-S batteries. Boron, nitrogen, oxygen, phosphorus, and sulfur doping greatly affect the electrochemical properties of Li2S /graphene . Here, we investigate the interfacial binding energy, lithium adsorption energy, interface diffusion barrier, and electronic structure by first-principles calculations to unveil the diverse effects of different dopants during interfacial lithiation reactions. The interfacial lithium storage follows the pseudocapacitylike mechanism with intercalation character. Two different mechanisms are revealed to enhance the interfacial lithium adsorption and diffusion, which are the electron-deficiency host doping and the vacancylike structure evolutions with bond breaking. The synergistic effect between different dopants with diverse doping effects is also proposed. The results give a theoretical basis for the materials design with doped graphene as advanced materials modification for energy storage.

Micellar Electrolytes in Organic Electrochemical Transistors

NASA Astrophysics Data System (ADS)

Cicoira, Fabio; Giuseppe, Tarabella; Nanda, Gaurav; Iannotta, Salvatore; Santato, Clara

2012-02-01

Organic electrochemical transistors (OECTs) are promising for applications in sensing and bioelectronics. OECTs consist of a conducting polymer film (transistor channel) in contact with an electrolyte. A gate electrode immersed in the electrolyte controls the doping/dedoping level of the conducting polymer. OECTs can be operated in aqueous electrolytes, making possible the implementation of organic electronic materials at the interface with biology. The inherent signal amplification of OECTs has the potential to yield sensors with low detection limits and high sensitivity. In this talk we will present recent studies on OECTs using ionic surfactants (such as hexadecyl-trimethyl-ammonium bromide) as electrolytes. As the conducting polymer we used PEDOT:PSS, i.e. (Poly,3-4 ethylenedioxythiopene) doped with Poly(styrene sulphonate). Interestingly, ionic surfactant electrolytes result in large transistor current modulation, especially beyond the critical micellar concentration (CMC). Since micelles play a primary role in biological processes and drug-delivery systems, the use for micellar electrolytes opens new exciting opportunities for the use of OECTs in bioelectronics.

Aldosterone modulates thiazide-sensitive sodium chloride cotransporter abundance via DUSP6-mediated ERK1/2 signaling pathway.

PubMed

Feng, Xiuyan; Zhang, Yiqian; Shao, Ningjun; Wang, Yanhui; Zhuang, Zhizhi; Wu, Ping; Lee, Matthew J; Liu, Yingli; Wang, Xiaonan; Zhuang, Jieqiu; Delpire, Eric; Gu, Dingying; Cai, Hui

2015-05-15

Thiazide-sensitive sodium chloride cotransporter (NCC) plays an important role in maintaining blood pressure. Aldosterone is known to modulate NCC abundance. Previous studies reported that dietary salts modulated NCC abundance through either WNK4 [with no lysine (k) kinase 4]-SPAK (Ste20-related proline alanine-rich kinase) or WNK4-extracellular signal-regulated kinase-1 and -2 (ERK1/2) signaling pathways. To exclude the influence of SPAK signaling pathway on the role of the aldosterone-mediated ERK1/2 pathway in NCC regulation, we investigated the effects of dietary salt changes and aldosterone on NCC abundance in SPAK knockout (KO) mice. We found that in SPAK KO mice low-salt diet significantly increased total NCC abundance while reducing ERK1/2 phosphorylation, whereas high-salt diet decreased total NCC while increasing ERK1/2 phosphorylation. Importantly, exogenous aldosterone administration increased total NCC abundance in SPAK KO mice while increasing DUSP6 expression, an ERK1/2-specific phosphatase, and led to decreasing ERK1/2 phosphorylation without changing the ratio of phospho-T53-NCC/total NCC. In mouse distal convoluted tubule (mDCT) cells, aldosterone increased DUSP6 expression while reducing ERK1/2 phosphorylation. DUSP6 Knockdown increased ERK1/2 phosphorylation while reducing total NCC expression. Inhibition of DUSP6 by (E)-2-benzylidene-3-(cyclohexylamino)-2,3-dihydro-1H-inden-1-one increased ERK1/2 phosphorylation and reversed the aldosterone-mediated increments of NCC partly by increasing NCC ubiquitination. Therefore, these data suggest that aldosterone modulates NCC abundance via altering NCC ubiquitination through a DUSP6-dependent ERK1/2 signal pathway in SPAK KO mice and part of the effects of dietary salt changes may be mediated by aldosterone in the DCTs.

Aldosterone modulates thiazide-sensitive sodium chloride cotransporter abundance via DUSP6-mediated ERK1/2 signaling pathway

PubMed Central

Feng, Xiuyan; Zhang, Yiqian; Shao, Ningjun; Wang, Yanhui; Zhuang, Zhizhi; Wu, Ping; Lee, Matthew J.; Liu, Yingli; Wang, Xiaonan; Zhuang, Jieqiu; Delpire, Eric; Gu, Dingying

2015-01-01

Thiazide-sensitive sodium chloride cotransporter (NCC) plays an important role in maintaining blood pressure. Aldosterone is known to modulate NCC abundance. Previous studies reported that dietary salts modulated NCC abundance through either WNK4 [with no lysine (k) kinase 4]-SPAK (Ste20-related proline alanine-rich kinase) or WNK4-extracellular signal-regulated kinase-1 and -2 (ERK1/2) signaling pathways. To exclude the influence of SPAK signaling pathway on the role of the aldosterone-mediated ERK1/2 pathway in NCC regulation, we investigated the effects of dietary salt changes and aldosterone on NCC abundance in SPAK knockout (KO) mice. We found that in SPAK KO mice low-salt diet significantly increased total NCC abundance while reducing ERK1/2 phosphorylation, whereas high-salt diet decreased total NCC while increasing ERK1/2 phosphorylation. Importantly, exogenous aldosterone administration increased total NCC abundance in SPAK KO mice while increasing DUSP6 expression, an ERK1/2-specific phosphatase, and led to decreasing ERK1/2 phosphorylation without changing the ratio of phospho-T53-NCC/total NCC. In mouse distal convoluted tubule (mDCT) cells, aldosterone increased DUSP6 expression while reducing ERK1/2 phosphorylation. DUSP6 Knockdown increased ERK1/2 phosphorylation while reducing total NCC expression. Inhibition of DUSP6 by (E)-2-benzylidene-3-(cyclohexylamino)-2,3-dihydro-1H-inden-1-one increased ERK1/2 phosphorylation and reversed the aldosterone-mediated increments of NCC partly by increasing NCC ubiquitination. Therefore, these data suggest that aldosterone modulates NCC abundance via altering NCC ubiquitination through a DUSP6-dependent ERK1/2 signal pathway in SPAK KO mice and part of the effects of dietary salt changes may be mediated by aldosterone in the DCTs. PMID:25761881

New method for characterizing electron mediators in microbial systems using a thin-layer twin-working electrode cell.

PubMed

Hassan, Md Mahamudul; Cheng, Ka Yu; Ho, Goen; Cord-Ruwisch, Ralf

2017-01-15

Microbial biofilms are significant ecosystems where the existence of redox gradients drive electron transfer often via soluble electron mediators. This study describes the use of two interfacing working electrodes (WEs) to simulate redox gradients within close proximity (250µm) for the detection and quantification of electron mediators. By using a common counter and reference electrode, the potentials of the two WEs were independently controlled to maintain a suitable "voltage window", which enabled simultaneous oxidation and reduction of electron mediators as evidenced by the concurrent anodic and cathodic currents, respectively. To validate the method, the electrochemical properties of different mediators (hexacyanoferrate, HCF, riboflavin, RF) were characterized by stepwise shifting the "voltage window" (ranging between 25 and 200mV) within a range of potentials after steady equilibrium current of both WEs was established. The resulting differences in electrical currents between the two WEs were recorded across a defined potential spectrum (between -1V and +0.5V vs. Ag/AgCl). Results indicated that the technique enabled identification (by the distinct peak locations at the potential scale) and quantification (by the peak of current) of the mediators for individual species as well as in an aqueous mixture. It enabled a precise determination of mid-potentials of the externally added mediators (HCF, RF) and mediators produced by pyocyanin-producing Pseudomonas aeruginosa (WACC 91) culture. The twin working electrode described is particularly suitable for studying mediator-dependent microbial electron transfer processes or simulating redox gradients as they exist in microbial biofilms. Copyright © 2016 Elsevier B.V. All rights reserved.

Two programmed cell death systems in Escherichia coli: an apoptotic-like death is inhibited by the mazEF-mediated death pathway.

PubMed

Erental, Ariel; Sharon, Idith; Engelberg-Kulka, Hanna

2012-01-01

In eukaryotes, the classical form of programmed cell death (PCD) is apoptosis, which has as its specific characteristics DNA fragmentation and membrane depolarization. In Escherichia coli a different PCD system has been reported. It is mediated by the toxin-antitoxin system module mazEF. The E. coli mazEF module is one of the most thoroughly studied toxin-antitoxin systems. mazF encodes a stable toxin, MazF, and mazE encodes a labile antitoxin, MazE, which prevents the lethal effect of MazF. mazEF-mediated cell death is a population phenomenon requiring the quorum-sensing pentapeptide NNWNN designated Extracellular Death Factor (EDF). mazEF is triggered by several stressful conditions, including severe damage to the DNA. Here, using confocal microscopy and FACS analysis, we show that under conditions of severe DNA damage, the triggered mazEF-mediated cell death pathway leads to the inhibition of a second cell death pathway. The latter is an apoptotic-like death (ALD); ALD is mediated by recA and lexA. The mazEF-mediated pathway reduces recA mRNA levels. Based on these results, we offer a molecular model for the maintenance of an altruistic characteristic in cell populations. In our model, the ALD pathway is inhibited by the altruistic EDF-mazEF-mediated death pathway.

Ebola Virus Modulates Transforming Growth Factor β Signaling and Cellular Markers of Mesenchyme-Like Transition in Hepatocytes

PubMed Central

Wahl-Jensen, Victoria; Safronetz, David; Trost, Brett; Hoenen, Thomas; Arsenault, Ryan; Feldmann, Friederike; Traynor, Dawn; Postnikova, Elena; Kusalik, Anthony; Napper, Scott; Blaney, Joseph E.; Feldmann, Heinz; Jahrling, Peter B.

2014-01-01

ABSTRACT Ebola virus (EBOV) causes a severe hemorrhagic disease in humans and nonhuman primates, with a median case fatality rate of 78.4%. Although EBOV is considered a public health concern, there is a relative paucity of information regarding the modulation of the functional host response during infection. We employed temporal kinome analysis to investigate the relative early, intermediate, and late host kinome responses to EBOV infection in human hepatocytes. Pathway overrepresentation analysis and functional network analysis of kinome data revealed that transforming growth factor (TGF-β)-mediated signaling responses were temporally modulated in response to EBOV infection. Upregulation of TGF-β signaling in the kinome data sets correlated with the upregulation of TGF-β secretion from EBOV-infected cells. Kinase inhibitors targeting TGF-β signaling, or additional cell receptors and downstream signaling pathway intermediates identified from our kinome analysis, also inhibited EBOV replication. Further, the inhibition of select cell signaling intermediates identified from our kinome analysis provided partial protection in a lethal model of EBOV infection. To gain perspective on the cellular consequence of TGF-β signaling modulation during EBOV infection, we assessed cellular markers associated with upregulation of TGF-β signaling. We observed upregulation of matrix metalloproteinase 9, N-cadherin, and fibronectin expression with concomitant reductions in the expression of E-cadherin and claudin-1, responses that are standard characteristics of an epithelium-to-mesenchyme-like transition. Additionally, we identified phosphorylation events downstream of TGF-β that may contribute to this process. From these observations, we propose a model for a broader role of TGF-β-mediated signaling responses in the pathogenesis of Ebola virus disease. IMPORTANCE Ebola virus (EBOV), formerly Zaire ebolavirus, causes a severe hemorrhagic disease in humans and nonhuman primates and is the most lethal Ebola virus species, with case fatality rates of up to 90%. Although EBOV is considered a worldwide concern, many questions remain regarding EBOV molecular pathogenesis. As it is appreciated that many cellular processes are regulated through kinase-mediated phosphorylation events, we employed temporal kinome analysis to investigate the functional responses of human hepatocytes to EBOV infection. Administration of kinase inhibitors targeting signaling pathway intermediates identified in our kinome analysis inhibited viral replication in vitro and reduced EBOV pathogenesis in vivo. Further analysis of our data also demonstrated that EBOV infection modulated TGF-β-mediated signaling responses and promoted “mesenchyme-like” phenotypic changes. Taken together, these results demonstrated that EBOV infection specifically modulates TGF-β-mediated signaling responses in epithelial cells and may have broader implications in EBOV pathogenesis. PMID:24942569

Development of new corrosion inhibitor tested on mild steel supported by electrochemical study

NASA Astrophysics Data System (ADS)

Habeeb, Hussein Jwad; Luaibi, Hasan Mohammed; Dakhil, Rifaat Mohammed; Kadhum, Abdul Amir H.; Al-Amiery, Ahmed A.; Gaaz, Tayser Sumer

2018-03-01

Mild steel is a metal which is commonly used in industrials and manufacturing of equipment for most industries round the world. It is cheaper cost compared with the other metals and its durable, hard and easy-to-wear physical properties make it a major choice in the manufacture of equipment parts. The main problem through the uses of mild steel in industry is its resistance against corrosion, especially in acidic solutions. This case led to raise the cost of maintenance of equipment that used mild steel and as a result increased costs for the company. Organic corrosive inhibitors that also act as green chemicals, 4-hydroxybenzylideneaminomethyl-5-ethyl-1,3,4-thiadiazol have been synthesized. This inhibitor is tested as corrosion inhibitor on a mild steel sample MS in 1 M hydrochloric acid solution (HCl) using electrochemical measurements test includes PD (Potentiodynamic), EIS (Electrochemical impedance spectroscopy), OCP (Open circuit potential) and EFM (electrochemical frequency modulation). The obtained results indicate that 4-hydroxybenzylideneaminomethyl-5-ethyl-1,3,4-thiadiazol acts as a good corrosion inhibitor for mild steel sample in HCl solution with efficiency above 90%. Changes in the impedance parameters postulated adsorption on the mild steel specimens' surfaces of, which it going to the formation of protective coating layer. It also shows that 4-hydroxybenzylideneaminomethyl-5-ethyl-1,3,4-thiadiazol corrosion inhibitors are effective in helping to reduce and slow down the corrosion process that occurs on mild steel surface in hydrochloric acid solution. Increase of corrosion inhibitor concentration provides a protective layer of mild steel. However, this protective layer becomes weak when the temperature of the solution increases.

Improving the electrochemical performances of Li-rich Li1.20Ni0.13Co0.13Mn0.54O2 through a cooperative doping of Na+ and PO43- with Na3PO4

NASA Astrophysics Data System (ADS)

Liu, Yi; Ning, De; Zheng, Lirong; Zhang, Qinghua; Gu, Lin; Gao, Rui; Zhang, Jicheng; Franz, Alexandra; Schumacher, Gerhard; Liu, Xiangfeng

2018-01-01

Li-rich layered oxide cathodes suffer from poor rate capability, voltage decay and inferior cycling stability. Herein, we propose a novel synergistic strategy to improve the electrochemical performances of Li-rich Li1.20Ni0.13Co0.13Mn0.54O2 by the co-doping of Na+ and PO43-. The co-doping of Na+ for Li and PO43- for Mn is simultaneously achieved using Na3PO4 as a dopant. The co-doping of Na+ and PO43- not only enhances the high-rate performance (106.4 mAhg-1@10C) and capacity retention (93.8%@1C@100 cycles) but also mitigates the voltage decay owing to the synergistic effect of Na+ and PO43- co-doping. The synergistic mechanism is unraveled based on neutron diffraction, aberration-corrected scanning transmission electron microscope, X-ray photoelectron spectroscopy, ex-situ X-ray absorption spectra, ex-situ X-ray diffraction, electrochemical impedance spectroscopy and electrochemical measurements. The co-doping of Na+ and PO43- enlarges the interlayer spacing and suppresses Li/Ni mixing which increases Li+ diffusivity and enhances the rate capability. Meanwhile, the co-doping of Na+ and PO43- shrinks the thickness of the slabs, weakens the TM-O covalency and alleviates the volume change in the charge/discharge process which improves the layered structure stability and the cycling performances. This study presents some new insights into designing high performance cathode materials through a cooperative modulation of different crystal sites doping.

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

Fuel Cell/Electrochemical Cell Voltage Monitor

NASA Technical Reports Server (NTRS)

Vasquez, Arturo

2012-01-01

A concept has been developed for a new fuel cell individual-cell-voltage monitor that can be directly connected to a multi-cell fuel cell stack for direct substack power provisioning. It can also provide voltage isolation for applications in high-voltage fuel cell stacks. The technology consists of basic modules, each with an 8- to 16-cell input electrical measurement connection port. For each basic module, a power input connection would be provided for direct connection to a sub-stack of fuel cells in series within the larger stack. This power connection would allow for module power to be available in the range of 9-15 volts DC. The relatively low voltage differences that the module would encounter from the input electrical measurement connection port, coupled with the fact that the module's operating power is supplied by the same substack voltage input (and so will be at similar voltage), provides for elimination of high-commonmode voltage issues within each module. Within each module, there would be options for analog-to-digital conversion and data transfer schemes. Each module would also include a data-output/communication port. Each of these ports would be required to be either non-electrical (e.g., optically isolated) or electrically isolated. This is necessary to account for the fact that the plurality of modules attached to the stack will normally be at a range of voltages approaching the full range of the fuel cell stack operating voltages. A communications/ data bus could interface with the several basic modules. Options have been identified for command inputs from the spacecraft vehicle controller, and for output-status/data feeds to the vehicle.

Direct Antimicrobial Susceptibility Testing of Gram-Negative Bacilli in Blood Cultures by an Electrochemical Method

PubMed Central

Huang, Ay Huey; Wu, Jiunn Jong; Weng, Yu Mei; Ding, Hwia Cheng; Chang, Tsung Chain

1998-01-01

Nonfastidious aerobic gram-negative bacilli (GNB) are commonly isolated from blood cultures. The feasibility of using an electrochemical method for direct antimicrobial susceptibility testing of GNB in positive blood cultures was evaluated. An aliquot (10 μl) of 1:10-diluted positive blood cultures containing GNB was inoculated into the Bactometer module well (bioMérieux Vitek, Hazelwood, Mo.) containing 1 ml of Mueller-Hinton broth supplemented with an antibiotic. Susceptibility tests were performed in a breakpoint broth dilution format, with the results being categorized as resistant, intermediate, or susceptible. Seven antibiotics (ampicillin, cephalothin, gentamicin, amikacin, cefamandole, cefotaxime, and ciprofloxacin) were used in this study, with each agent being tested at the two interpretive breakpoint concentrations. The inoculated modules were incubated at 35°C, and the change in impedance in each well was continuously monitored for 24 h by the Bactometer. The MICs of the seven antibiotics for each blood isolate were also determined by the standardized broth microdilution method. Of 146 positive blood cultures (1,022 microorganism-antibiotic combinations) containing GNB tested by the direct method, the rates of very major, major, and minor errors were 0, 1.1, and 2.5%, respectively. The impedance method was simple; no centrifugation, preincubation, or standardization of the inocula was required, and the susceptibility results were normally available within 3 to 6 h after inoculation. The rapid method may allow proper antimicrobial treatment almost 30 to 40 h before the results of the standard methods are available. PMID:9738038

Wireless Instantaneous Neurotransmitter Concentration Sensing System (WINCS) for intraoperative neurochemical monitoring.

PubMed

Kimble, Christopher J; Johnson, David M; Winter, Bruce A; Whitlock, Sidney V; Kressin, Kenneth R; Horne, April E; Robinson, Justin C; Bledsoe, Jonathan M; Tye, Susannah J; Chang, Su-Youne; Agnesi, Filippo; Griessenauer, Christoph J; Covey, Daniel; Shon, Young-Min; Bennet, Kevin E; Garris, Paul A; Lee, Kendall H

2009-01-01

The Wireless Instantaneous Neurotransmitter Concentration Sensing System (WINCS) measures extracellular neurotransmitter concentration in vivo and displays the data graphically in nearly real time. WINCS implements two electroanalytical methods, fast-scan cyclic voltammetry (FSCV) and fixed-potential amperometry (FPA), to measure neurotransmitter concentrations at an electrochemical sensor, typically a carbon-fiber microelectrode. WINCS comprises a battery-powered patient module and a custom software application (WINCSware) running on a nearby personal computer. The patient module impresses upon the electrochemical sensor either a constant potential (for FPA) or a time-varying waveform (for FSCV). A transimpedance amplifier converts the resulting current to a signal that is digitized and transmitted to the base station via a Bluetooth radio link. WINCSware controls the operational parameters for FPA or FSCV, and records the transmitted data stream. Filtered data is displayed in various formats, including a background-subtracted plot of sequential FSCV scans - a representation that enables users to distinguish the signatures of various analytes with considerable specificity. Dopamine, glutamate, adenosine and serotonin were selected as analytes for test trials. Proof-of-principle tests included in vitro flow-injection measurements and in vivo measurements in rat and pig. Further testing demonstrated basic functionality in a 3-Tesla MRI unit. WINCS was designed in compliance with consensus standards for medical electrical device safety, and it is anticipated that its capability for real-time intraoperative monitoring of neurotransmitter release at an implanted sensor will prove useful for advancing functional neurosurgery.

Alkaline static feed electrolyzer based oxygen generation system

NASA Technical Reports Server (NTRS)

Noble, L. D.; Kovach, A. J.; Fortunato, F. A.; Schubert, F. H.; Grigger, D. J.

1988-01-01

In preparation for the future deployment of the Space Station, an R and D program was established to demonstrate integrated operation of an alkaline Water Electrolysis System and a fuel cell as an energy storage device. The program's scope was revised when the Space Station Control Board changed the energy storage baseline for the Space Station. The new scope was aimed at the development of an alkaline Static Feed Electrolyzer for use in an Environmental Control/Life Support System as an oxygen generation system. As a result, the program was divided into two phases. The phase 1 effort was directed at the development of the Static Feed Electrolyzer for application in a Regenerative Fuel Cell System. During this phase, the program emphasized incorporation of the Regenerative Fuel Cell System design requirements into the Static Feed Electrolyzer electrochemical module design and the mechanical components design. The mechanical components included a Pressure Control Assembly, a Water Supply Assembly and a Thermal Control Assembly. These designs were completed through manufacturing drawing during Phase 1. The Phase 2 effort was directed at advancing the Alkaline Static Feed Electrolyzer database for an oxygen generation system. This development was aimed at extending the Static Feed Electrolyzer database in areas which may be encountered from initial fabrication through transportation, storage, launch and eventual Space Station startup. During this Phase, the Program emphasized three major areas: materials evaluation, electrochemical module scaling and performance repeatability and Static Feed Electrolyzer operational definition and characterization.