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Redox System (redox + system)

Distribution by Scientific Domains

Chemistry	33%
Polymers and Materials Science	24%
Life Sciences	24%
Medical Sciences	12%

Selected Abstracts

Maternal Alcohol Use During Pregnancy Causes Systemic Oxidation of the Glutathione Redox System

ALCOHOLISM, Issue 1 2010
Theresa W. Gauthier
Background:, Increased systemic oxidant stress contributes to a variety of maternal complications of pregnancy. Although the antioxidant glutathione (GSH) and its oxidized component glutathione disulfide (GSSG) have been demonstrated to be significantly altered in the adult alcoholic, the effects of maternal alcohol use during pregnancy on oxidant stress in the postpartum female remain under investigation. We hypothesized that maternal alcohol use would increase systemic oxidant stress in the pregnant female, evidenced by an oxidized systemic GSH redox potential. Methods:, As a subset analysis of a larger maternal language study, we evaluated the effects of alcohol consumption during pregnancy on the systemic GSH redox status of the postpartum female. Using an extensive maternal questionnaire, postpartum women where queried regarding their alcohol consumption during pregnancy. Any drinking, the occurrence of drinking >3 drinks/occasion, and heavy drinking of >5 drinks/occasion during pregnancy were noted. Using HPLC, maternal plasma samples were analyzed for GSH, oxidized GSSG and the redox potential of the GSH/GSSG antioxidant pair calculated. Results:, Maternal alcohol use occurred in 25% (83/321) of our study sample. Two in ten women reported consuming >3 drinks/occasion during pregnancy, while 1 in 10 women reported consuming alcohol at >5 drinks/occasion. Any alcohol use during pregnancy significantly decreased plasma GSH (p < 0.05), while alcohol at >3 drinks/occasion or >5 drinks/occasion significantly decreased plasma GSH concentration (p < 0.05), increased the percent of oxidized GSSG (p < 0.05), and substantially oxidized the plasma GSH redox potential (p < 0.05). Conclusions:, Alcohol use during pregnancy, particularly at levels >3 drinks/occasion, caused significant oxidation of the systemic GSH system in the postpartum women. The clinical ramifications of the observed alcohol-induced oxidation of the GSH redox system on high risk pregnancies or on the exposed offspring require more accurate identification and further investigation. [source]

Peroxide/Potassium Iodide Redox Systems for in situ Oxyiodination of Organic Compounds under Liquid-Phase and Solvent-Free Conditions

HELVETICA CHIMICA ACTA, Issue 2 2010
Gattu Venkateshwarlu
Abstract Iodination of certain aromatic amines and phenols are triggered by the oxidation of KI by peroxy compounds such as tert -butyl hydroperoxide (tBuOOH) under liquid-phase and solvent-free conditions by grinding the reactants in a mortar with a pestle. The reactions afforded corresponding iodo derivatives in good yield with high regioselectivity (Table,1). [source]

Nanodiamond Thin Film Electrodes: Metal Electro-Deposition and Stripping Processes

ELECTROANALYSIS, Issue 3 2003
Hian, Lau Chi
Abstract The properties of a nanodiamond thin film deposit formed on titanium substrates in a microwave-plasma enhanced CVD process, are investigated for applications in electroanalysis. The nanodiamond deposit consists of intergrown nano-sized platelets of diamond with a high sp2 carbon content giving it high electrical conductivity and electrochemical reactivity. Nanodiamond thin film electrodes (of approximately 2,,m thickness) are characterized by electron microscopy and electrochemical methods. First, for a reversible one electron redox system, Ru(NH3)63+/2+, nanodiamond is shown to give well-defined diffusion controlled voltammetric responses. Next, metal deposition processes are shown to proceed on nanodiamond with high reversibility and high efficiency compared to processes reported on boron-doped diamond. The nucleation of gold is shown to be facile at edge sites, which are abundant on the nanodiamond surface. For the deposition and stripping of both gold and copper, a stripping efficiency (the ratio of electro-dissolution charge to electro-deposition charge) of close to unity is detected even at low concentrations of analyte. The effect of thermal annealing in air is shown to drastically modify the electrode characteristics probably due to interfacial oxidation, loss of active sp2 sites, and loss of conductivity. [source]

Synthesis, Characterization and Electrochemistry of the Novel Dawson-Type Tungstophosphate [H4PW18O62]7, and First Transition Metal Ions Derivatives

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2004
Israel-Martyr Mbomekalle
Abstract Following the synthesis of pure [H4PW18O62]7, (PW18), its derivatives monosubstituted with M (M = MoVI, VIV, VV, MnII, FeIII, CoII, NiII CuII and ZnII) were obtained. All compounds were characterized by elemental analysis, IR, UV/visible and 31P NMR spectroscopy. Their cyclic voltammetry properties were studied as a function of pH and systematically compared with those of their analogs derived from the symmetrical species, [P2W18O62]6,(P2W18). Comparison of the two unsubstituted precursors revealed that the merging of the first two waves of the monophosphate occurred in a less acidic medium than for the diphosphate. The observations point to the higher basicity of the reduced forms of PW18 compared with those of P2W18. The fingerprint pattern observed for ,2 -P2W17M derivatives in media of pH = 3 consisted of the splitting of the third W redox system into two one-electron closely spaced waves which is in contrast to the same system in ,1 -P2W17M. This peculiarity was also obtained for several of the present ,2 -PW17M systems in media of pH = 3 and confirmed that ,2 -substituted derivatives were indeed formed. The absence of this peculiar behavior in some other derivatives is consistent with smooth variations of acid-base properties from one derivative to the next. The electrocatalytic properties of all the compounds are illustrated by the reduction of nitrite by reduced PW18 and of nitrate by reduced ,2 -PW17Cu. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Studies on structural and functional divergence among seven WhiB proteins of Mycobacterium tuberculosis H37Rv

FEBS JOURNAL, Issue 1 2009
Md. Suhail Alam
The whiB -like genes (1-7) of Mycobacterium tuberculosis are involved in cell division, nutrient starvation, pathogenesis, antibiotic resistance and stress sensing. Although the biochemical properties of WhiB1, WhiB3 and WhiB4 are known, there is no information about the other proteins. Here, we elucidate in detail the biochemical and biophysical properties of WhiB2, WhiB5, WhiB6 and WhiB7 of M. tuberculosis and present a comprehensive comparative study on the molecular properties of all WhiB proteins. UV,Vis spectroscopy has suggested the presence of a redox-sensitive [2Fe,2S] cluster in each of the WhiB proteins, which remains stably bound to the proteins in the presence of 8 m urea. The [2Fe,2S] cluster of each protein was oxidation labile but the rate of cluster loss decreased under reducing environments. The [2Fe,2S] cluster of each WhiB protein responded differently to the oxidative effect of air and oxidized glutathione. In all cases, disassembly of the [2Fe,2S] cluster was coupled with the oxidation of cysteine-thiols and the formation of two intramolecular disulfide bonds. Both CD and fluorescence spectroscopy revealed that WhiB proteins are structurally divergent members of the same family. Similar to WhiB1, WhiB3 and WhiB4, apo WhiB5, WhiB6 and WhiB7 also reduced the disulfide of insulin, a model substrate. However, the reduction efficiency varied significantly. Surprisingly, WhiB2 did not reduce the insulin disulfide, even though its basic properties were similar to those of others. The structural and functional divergence among WhiB proteins indicated that each WhiB protein is a distinguished member of the same family and together they may represent a novel redox system for M. tuberculosis. [source]

Thioredoxin alters the matrix metalloproteinase/tissue inhibitors of metalloproteinase balance and stimulates human SK-N-SH neuroblastoma cell invasion

FEBS JOURNAL, Issue 2 2001
Antonietta R. Farina
Thioredoxin (Trx) inhibited tissue inhibitor of metalloproteinase (TIMP)-1 and TIMP-2 activity with an approximate IC50 of 0.3 µm, matrix metalloproteinase (MMP)-2 activity with an approximate IC50 of 2 µm but did not inhibit MMP-9 activity. This differential capacity of Trx to inhibit TIMP and MMP activity resulted in the promotion of MMP-2 and MMP-9 activity in the presence of molar TIMP excess. Inhibition of TIMP and MMP-2 activity by Trx was dependent upon thioredoxin reductase (TrxR), was abolished by Trx catalytic site mutation and did not result from TIMP or MMP-2 degradation. HepG2 hepatocellular carcinoma cells induced to secrete Trx inhibited TIMP activity in the presence of TrxR. SK-N-SH neuroblastoma cells secreted TrxR, which inhibited TIMP and MMP-2 activity in the presence of Trx. Trx stimulated SK-N-SH invasive capacity in vitro in the absence of exogenous TrxR. This study therefore identifies a novel extracellular role for the thioredoxin/thioredoxin reductase redox system in the differential inhibition of TIMP and MMP activity and provides a novel mechanism for altering the TIMP/MMP balance that is of potential relevance to tumor invasion. [source]

A Controllable Self-Assembly Method for Large-Scale Synthesis of Graphene Sponges and Free-Standing Graphene Films

ADVANCED FUNCTIONAL MATERIALS, Issue 12 2010
Fei Liu
Abstract A simple method to prepare large-scale graphene sponges and free-standing graphene films using a speed vacuum concentrator is presented. During the centrifugal evaporation process, the graphene oxide (GO) sheets in the aqueous suspension are assembled to generate network-linked GO sponges or a series of multilayer GO films, depending on the temperature of a centrifugal vacuum chamber. While sponge-like bulk GO materials (GO sponges) are produced at 40,°C, uniform free-standing GO films of size up to 9,cm2 are generated at 80,°C. The thickness of GO films can be controlled from 200,nm to 1,µm based on the concentration of the GO colloidal suspension and evaporation temperature. The synthesized GO films exhibit excellent transparency, typical fluorescent emission signal, and high flexibility with a smooth surface and condensed density. Reduced GO sponges and films with less than 5,wt% oxygen are produced through a thermal annealing process at 800,°C with H2/Ar flow. The structural flexibility of the reduced GO sponges, which have a highly porous, interconnected, 3D network, as well as excellent electrochemical properties of the reduced GO film with respect to electrode kinetics for the [Fe(CN)6]3,/4, redox system, are demonstrated. [source]

Catalyst-Free Efficient Growth, Orientation and Biosensing Properties of Multilayer Graphene Nanoflake Films with Sharp Edge Planes,

ADVANCED FUNCTIONAL MATERIALS, Issue 21 2008
Nai Gui Shang
Abstract We report a novel microwave plasma enhanced chemical vapor deposition strategy for the efficient synthesis of multilayer graphene nanoflake films (MGNFs) on Si substrates. The constituent graphene nanoflakes have a highly graphitized knife-edge structure with a 2,3,nm thick sharp edge and show a preferred vertical orientation with respect to the Si substrate as established by near-edge X-ray absorption fine structure spectroscopy. The growth rate is approximately 1.6,µm min,1, which is 10 times faster than the previously reported best value. The MGNFs are shown to demonstrate fast electron-transfer (ET) kinetics for the Fe(CN)63,/4, redox system and excellent electrocatalytic activity for simultaneously determining dopamine (DA), ascorbic acid (AA) and uric acid (UA). Their biosensing DA performance in the presence of common interfering agents AA and UA is superior to other bare solid-state electrodes and is comparable only to that of edge plane pyrolytic graphite. Our work here, establishes that the abundance of graphitic edge planes/defects are essentially responsible for the fast ET kinetics, active electrocatalytic and biosensing properties. This novel edge-plane-based electrochemical platform with the high surface area and electrocatalytic activity offers great promise for creating a revolutionary new class of nanostructured electrodes for biosensing, biofuel cells and energy-conversion applications. [source]

Induction of cellular resistance against Kupffer cell,derived oxidant stress: A novel concept of hepatoprotection by ischemic preconditioning

HEPATOLOGY, Issue 2 2003
Rolf J. Schauer
Ischemic preconditioning (IP) triggers protection of the liver from prolonged subsequent ischemia. However, the underlying protective mechanisms are largely unknown. We investigated whether and how IP protects the liver against reperfusion injury caused by Kupffer cell (KC)-derived oxidants. IP before 90 minutes of warm ischemia of rat livers in vivo significantly reduced serum alanine aminotransferase (AST) levels and leukocyte adherence to sinusoids and postsinusoidal venules during reperfusion. This protective effect was mimicked by postischemic intravenous infusion of glutathione (GSH), an antioxidative strategy against KC-derived H2O2. Interestingly, no additional protection was achieved by infusion of GSH to preconditioned animals. These findings and several additional experiments strongly suggest IP mediated antioxidative effects: IP prevented oxidant cell injury in isolated perfused rat livers after selective KC activation by zymosan. Moreover, IP prevented cell injury and pertubations of the intracellular GSH/GSSG redox system caused by direct infusion of H2O2 (0.5 mmol/L). IP-mediated resistance against H2O2 could neither be blocked by the adenosine A2a antagonist DMPX nor mimicked by A2a agonist CGS21680. In contrast, H2O2 resistance was abolished by the p38 mitogen-activated protein kinase (p38 MAPK) inhibitor SB203580, but induced when p38 MAPK was directly activated by anisomycin. In conclusion, we propose a novel concept of hepatoprotection by IP: protection of liver cells by enhancing their resistance against KC-derived H2O2. Activation of p38 MAPK and preservation of the intracellular GSH/oxidized glutathione (GSSG) redox system, but not adenosine A2a receptor stimulation, seems to be pivotal for the development of H2O2 resistance in preconditioned livers. [source]

Reduction of dissolved oxygen in boiler water using new redox polymers

JOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2010
Christophe Waterlot
Abstract New polymers were used as catalysts for the removal of dissolved oxygen in boiler water. These polymers, based upon hydroquinone-quinone redox system, were prepared by polymerization of methyl 4-(2,5-dimethoxybenzyl)cinnamate and copolymerization of this monomer with 4-(4,-vinylphenethyl)-1,10-phenanthroline. The resulting product was used to synthesize polymers containing transition metal ions. Nuclear magnetic resonance, infrared spectroscopy, and elemental analysis were achieved to characterize monomers and/or electron-transfer polymers. These polymers were used for the removal of oxygen from water. It was shown that the oxygen content was reduced to less than 0.1 mg L,1 in , 70 s. Based on the obtained results, the redox capacity of two polymers were determined. It was established that the poly-4-(2,5-dihydroxybenzyl)cinnamic acid reached a redox capacity of 69.7 mg of O2 per gram of polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]

Ceric ammonium sulfate/sodium disulfite initiated grafting of acrylamide on to Cassia reticulata seed gum

JOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008
Vandana Singh
Abstract Ceric ammonium sulfate/sodium disulfite redox system was evaluated for the poly(acrylamide) (PAM) grafting on to Cassia reticulata (CR) seed gum. Grafting conditions were optimized and the maximum %Grafting (%G) and %Efficiency (%E) achieved were 152 and 97.2%, respectively, using [disulfite] 0.005M; [ceric ammonium sulfate] 0.026M; [acrylamide] 0.11M; [gum] 0.125 g/25mL at 40 ± 0.2°C. Representative CR-grafted gum (CRPAM) was characterized by Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Under identical conditions, the redox initiator could result 142.6 %G and 91.2 %E on to guar gum (GG). Various physical properties of the CR gum/grafted CR gum, such as viscosity, water retention, and saline retention, were studied and compared with GG/grafted GG to find out the potential industrial use of CR gum and PAM- grafted -CR gum. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source]

Kinetics of graft copolymerization of poly(hexanedioic acid ethylene glycol) and methyl acrylate initiated by potassium diperiodatocuprate(III)

JOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007
Libin Bai
Abstract A redox system, potassium diperiodatocuprate(III) [DPC]/poly(hexanedioic acid ethylene glycol) (PEA) system, was employed to initiate graft copolymers of methyl acrylate (MA) and PEA in alkaline medium. The results indicate that the equation of the polymerization rate (Rp) is as follows: Rp = k [MA]1.62[Cu(III)]0.69, and that the overall activation energy of graft polymerization is 42.5 kJ/mol. The total conversion at different conditions (concentration of reactants, temperature, concentration of the DPC, and reaction time) was also investigated. The infrared spectra proved that the graft copolymers were synthesized successfully. Some basic properties of the graft copolymer were studied by instrumental analyses, including thermogravimetry and scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2376,2381, 2007 [source]

Characterization of new acrylic bone cements prepared with oleic acid derivatives

JOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2002
Blanca Vázquez
Abstract Acrylic bone-cement formulations were prepared with the use of a new tertiary aromatic amine derived from oleic acid, and also by incorporating an acrylic monomer derived from the same acid with the aim of reducing the leaching of toxic residuals and improving mechanical properties. 4-N,N dimethylaminobenzyl oleate (DMAO) was used as an activator in the benzoyl-peroxide radical cold curing of polymethyl methacrylate. Cements that contained DMAO exhibited much lower polymerization exotherm values, ranging between 55 and 62 °C, with a setting time around 16,17 min, depending on the amine/BPO molar ratio of the formulation. On curing a commercial bone cement, Palacos® R with DMAO, a decrease of 20 °C in peak temperature and an increase in setting time of 7 min were obtained, the curing parameters remaining well within limits permitted by the standards. In a second stage, partial substitution of MMA by oleyloxyethyl methacrylate (OMA) in the acrylic formulations was performed, the polymerization being initiated with the DMAO/BPO redox system. These formulations exhibited longer setting times and lower peak temperatures with respect to those based on PMMA. The glass transition temperature of the experimental cements were lower than that of PMMA cement because of the presence of long aliphatic chains of both activator and monomer in the cement matrix. Number average molecular weights of the cured cements were in the range of 1.2×105. PMMA cements cured with DMAO/BPO revealed a significant (p<0.001) increase in the strain to failure and a significant (p<0.001) decrease in Young's modulus in comparison to Palacos® R, whereas ultimate tensile strength remained unchanged. When the monomer OMA was incorporated, low concentrations of OMA provided a significant increase in tensile strength and elastic modulus without impairing the strain to failure. The results demonstrate that the experimental cements based on DMAO and OMA have excellent promise for use as orthopaedic and/or dental grouting materials. © 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 88,97, 2002; DOI 10.1002/jbm.10092 [source]

Maternal Alcohol Use During Pregnancy Causes Systemic Oxidation of the Glutathione Redox System

Redox and antioxidant systems of the malaria parasite Plasmodium falciparum

MOLECULAR MICROBIOLOGY, Issue 5 2004
Sylke Müller
Summary The malaria parasite Plasmodium falciparum is highly adapted to cope with the oxidative stress to which it is exposed during the erythrocytic stages of its life cycle. This includes the defence against oxidative insults arising from the parasite's metabolism of haemoglobin which results in the formation of reactive oxygen species and the release of toxic ferriprotoporphyrin IX. Central to the parasite's defences are superoxide dismutases and thioredoxin-dependent peroxidases; however, they lack catalase and glutathione peroxidases. The vital importance of the thioredoxin redox cycle (comprising NADPH, thioredoxin reductase and thioredoxin) is emphasized by the confirmation that thioredoxin reductase is essential for the survival of intraerythrocytic P. falciparum. The parasites also contain a fully functional glutathione redox system and the low-molecular-weight thiol glutathione is not only an important intracellular thiol redox buffer but also a cofactor for several redox active enzymes such as glutathione S-transferase and glutaredoxin. Recent findings have shown that in addition to these cytosolic redox systems the parasite also has an important mitochondrial antioxidant defence system and it is suggested that lipoic acid plays a pivotal part in defending the organelle from oxidative damage. [source]

Conductance through a redox system in the Coulomb blockade regime: Many-particle effects and influence of electronic correlations

PHYSICA STATUS SOLIDI - RAPID RESEARCH LETTERS, Issue 1-2 2010
Sabine Tornow
Abstract We investigate the transport characteristics of a redox system weakly coupled to leads in the Coulomb blockade regime. The redox system comprises a donor and acceptor separated by an insulating bridge in a solution. It is modeled by a two-site extended Hubbard model which includes on-site and inter-site Coulomb interactions and the coupling to a bosonic bath. The current,voltage characteristics is calculated at high temperatures using a rate equation approach. For high voltages exceeding the Coulomb repulsion at the donor site the calculated transport characteristics exhibit pronounced deviations from the behavior expected from single-electron transport. Depending on the relative sizes of the effective on-site and inter-site Coulomb interactions on one side and the reorganization energy on the other side we find either negative differential resistance or current enhancement. Schematic view of the redox system with donor (D) and acceptor (A) coupled to the leads L and R. The electronic degrees of freedom of the DA system are coupled to the environment comprising internal vibrations and the solvent dynamics. The current is calculated as a function of the bias voltage Vb and gate voltage Vg. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

POLYMER INTERNATIONAL, Issue 10 2004
Yinghai Liu
Abstract A novel redox system, potassium ditelluratoargentate(III) (DTA),cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA,cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two-step single-electron-transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X-ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry [source]

Biological effects of a nano red elemental selenium

BIOFACTORS, Issue 1 2001
Jin-Song Zhang
A novel selenium form, nano red elemental selenium (Nano-Se) was prepared by adding bovine serum albumin to the redox system of selenite and glutathione. Nano-Se has a 7-fold lower acute toxicity than sodium selenite in mice (LD50 113 and 15 mg Se/kg body weight respectively). In Se-deficient rat, both Nano-Se and selenite can increase tissue selenium and GPx activity. The biological activities of Nano-Se and selenite were compared in terms of cell proliferation, enzyme induction and protection against free racial-mediated damage in human hepatoma HepG2 cells. Nano-Se and selenite are similarly cell growth inhibited and stimulated synthesis of glutathione peroxidase (GPx), phospholipid hydroperoxide glutathione peroxidase (PHGPx) and thioredoxin reductase (TR). When HepG2 cells were co-treated with selenium and glutathione, Nano-Se showed less pro-oxidative effects than selenite, as measured by cell growth. These results demonstrate that Nano-Se has a similar bioavailability in the rat and antioxidant effects on cells. [source]

High-resolution structure of the antibiotic resistance protein NimA from Deinococcus radiodurans

ACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 6 2008
Hanna-Kirsti S. Leiros
Many anaerobic human pathogenic bacteria are treated using 5-nitroimidazole-based (5-Ni) antibiotics, a class of inactive prodrugs that contain a nitro group. The nitro group must be activated in an anaerobic one-electron reduction and is therefore dependent on the redox system in the target cells. Antibiotic resistance towards 5-Ni drugs is found to be related to the nim genes (nimA, nimB, nimC, nimD, nimE and nimF), which are proposed to encode a reductase that is responsible for converting the nitro group of the antibiotic into a nonbactericidal amine. A mechanism for the Nim enzyme has been proposed in which two-electron reduction of the nitro group leads to the generation of nontoxic derivatives and confers resistance against these antibiotics. The cofactor was found to be important in the mechanism and was found to be covalently linked to the reactive His71. In this paper, the 1.2,Å atomic resolution crystal structure of the 5-nitroimidazole antibiotic resistance protein NimA from Deinococcus radiodurans (DrNimA) is presented. A planar cofactor is clearly visible and well defined in the electron-density map adjacent to His71, the identification of the cofactor and its properties are discussed. [source]

Azaanthraquinone inhibits respiration and in vitro growth of long slender bloodstream forms of Trypanosoma congolense

CELL BIOCHEMISTRY AND FUNCTION, Issue 3 2002
Andrew Jonathan Nok
Abstract An ethanolic extract of Mitracarpus scaber was found to possess in vitro and in vivo trypanocidal activity against Trypanosoma congolense. At a dosage of 50,mg kg,1 day,1 in normal saline for 5 days, the extract cured Balbc mice infected with T. congolense without any relapse. The isolated active component benz(g)isoquinoline 5,10 dione (Azaanthraquinone) (AQ) purified from the extract was found to inhibit glucose-dependent cellular respiration and glycerol-3-phosphate-dependent mitochondrial O2 assimilation of the long bloodstream forms of Trypanosoma congolense. On account of the pattern of inhibition, the target could be the mitochondrial electron transport system composed of glyceraldehyde 3-phosphate dehydrogenase (G3PDH). The azaanthraquinone specifically inhibited the reduced coenzyme Q1 -dependent O2 uptake of the mitochondria with respect to ubiquinone. The susceptible site could be due to ubiquinone redox system which links the two enzyme activities. Copyright © 2002 John Wiley & Sons, Ltd. [source]

Evaluation of Thin Film Titanium Nitride Electrodes for Electroanalytical Applications

ELECTROANALYSIS, Issue 10 2007
Carolina Nunes, Kirchner
Abstract Titanium nitride is a hard and inert conducting material that has yet not been widely used as electrode material for electroanalytical applications although there are highly developed protocols available to produce well adherent micro and nanostructured electrodes. In this paper the possibilities of using titanium nitride thin films for electroanalytical applications is investigated. Scanning electrochemical microscope (SECM) was used for analysis of the redox kinetics of a selected fast redox couple at thin films of titanium nitride (TiN) in different thicknesses. The investigation was carried out by approaching an amperometric ultramicroelectrode (UME) to the TiN film while the soluble redox couple (ferrocenemethanol/ferrociniummethanol) served as mediator in a SECM configuration. The substrate was biased at a potential so that it rereduces the species being produced at the UME, thus controlling the feedback effect. Normalized current,distance curves were fitted to the theoretical model in order to find the apparent heterogeneous standard rate constant (k°) at the sample. The data are further supported by structural investigation of the TiN films using scanning force microscopy and X-ray photoelectron spectroscopy. It was found that the kinetics are little influenced by prolonged storage in air. The heterogeneous standard rate constants in 2,mM ferrocenemethanol were (0.73±0.05)×10,3,cm s,1 for 20,nm TiN thin layer, (1.5±0.2)×10,3,cm s,1 for 100,nm TiN thin layer and (1.3±0.2)×10,3,cm s,1 for 300,nm TiN thin layer after prolonged storage in air. Oxidative surface treatment (in order to remove organic adsorbates) decreased the kinetics in agreement with a thicker oxide layer on the material. The results suggest that their direct use for amperometric detection of reversible redox systems in particular at miniaturized configurations may be advantageous. [source]

Carbon Nanotubes Paste Electrodes.

ELECTROANALYSIS, Issue 7-8 2007
A New Alternative for the Development of Electrochemical Sensors
Abstract In this work we summarize the recent activities of our group regarding the analytical performance of a new composite material, the so-called carbon nanotubes paste electrode (CNTPE) obtained by dispersion of multiwall carbon nanotubes in mineral oil. The electrocatalytic properties towards different redox systems, especially those involved in important enzymatic reactions are discussed. Significant shifting in the overpotentials for the oxidation and/or reduction of hydrogen peroxide, NADH, phenol, catechol, dopamine, ascorbic acid, uric acid and hydroquinone are obtained at CNTPE in comparison with the analogous graphite paste electrode (CPE). The usefulness of the electrode as a matrix for immobilizing enzymes is also demonstrated. Highly sensitive and selective glucose quantification is accomplished even without using permselective films or redox mediators. Enzymatic biosensors obtained by incorporation of lactate oxidase, polyphenol oxidase and alcohol dehydrogenase/NAD+ within the composite material have allowed the successful quantification of lactate, phenol, dopamine, catechin and ethanol. The sensitive quantification of traces of oligonucleotides and double stranded calf thymus DNA by adsorptive stripping is reported. The confined DNA layer demonstrated to be stable either in air, acetate or phosphate buffer. The advantages of incorporating copper particles for the quantification of amino acids and albumin is also discussed. [source]

Analysis of the Voltammetric Response of Electroactive Guests in the Presence of Non-Electroactive Hosts at Moderate Concentrations

ELECTROANALYSIS, Issue 18 2004
Sandra Mendoza
Abstract In this work, we present a method to analyze the voltammetric response of reversible redox systems involving molecules that, bearing m non-interactive electroactive sites, can undergo fast complexation equilibria with host molecules present at concentrations of the same order of magnitude as those of the electroactive guest. The approach focuses on systems for which the relative values of the binding constants for the oxidized and reduced forms of the guest result in the displacement of the voltammetric response of the electroactive molecule as the concentration of the host is increased in the electrolytic solution. This behavior is commonly known as "one wave shift behavior". Based on a series of assumptions, the method allows calculation of all the thermodynamic parameters that describe the electrochemical and complexation equilibria of a given host-guest system. The main strength of the suggested method, however, relies on the fact that it only requires cyclic voltammetry data and that it can be used for systems in which large concentrations of the host can not be employed either due to important changes of the ionic strength or to solubility problems. Although the accuracy of the obtained information is limited by the quality of the data provided by the technique, and by the assumptions employed, it certainly represents an excellent starting point for subsequent refinement either using digital simulations or an independent experimental technique. [source]

Supramolecular Derivatives of 9,10-Anthraquinone.

ELECTROANALYSIS, Issue 5-6 2003
Complexing Properties, Electrochemistry at Regular-, Low Ionic Strength
Abstract Three newly synthesized polyanthraquinone derivatives: 7,13-bis(9,10-dioxo-1-anthryl)-1,4,10-trioxa-7,13-diazacyclopentadecane, (AQ)A215C5, 7,16-bis(9,10-dioxo-1-anthryl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, (AQ)A218C6, and tris[(9,10-diokso-1-antryl)-aminoethyl]amine, (AQNet)3N, were examined by cyclic and normal pulse voltammetry. All anthraquinone groups in these compounds were electroactive and formed the radicals and dianions similarly to simple anthraquinone. The differences between the voltammograms obtained in the absence and presence of supporting electrolyte are discussed, and the diffusion coefficients of the compounds and the rates of the chemical reactions following the first reduction step were evaluated. (AQNet)3N appears to be a good model compound for multi electron transfers in aprotic solvents. It offers two consecutive nearly reversible 3-electron redox systems: 0/,3 and ,3/,6. The interactions of the radicals and dianions of the above compounds with alkali metal cations were examined. [source]

Metalloporphyrin solubility: A trigger for catalyzing reductive dechlorination of tetrachloroethylene

ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2004
Ishai Dror
Abstract Metalloporphyrins are well known for their electron-transfer roles in many natural redox systems. In addition, several metalloporphyrins and related tetrapyrrole macrocycles complexed with various core metals have been shown to catalyze the reductive dechlorination of certain organic compounds, thus demonstrating the potential for using naturally occurring metalloporphyrins to attenuate toxic and persistent chlorinated organic pollutants in the environment. However, despite the great interest in reductive dechlorination reactions and the wide variety of natural and synthetic porphyrins currently available, only soluble porphyrins, which comprise a small fraction of this particular family of organic macrocycles, have been used as electron-transfer shuttles in these reactions. Results from the present study clearly demonstrate that metalloporphyrin solubility is a key factor in their ability to catalyze the reductive dechlorination of tetrachloroethylene and its daughter compounds. Additionally, we show that certain insoluble and nonreactive metalloporphyrins can be activated as catalysts merely by changing solution conditions to bring about their dissolution. Furthermore, once a metalloporphyrin is fully dissolved and activated, tetrachloroethylene transformation proceeds rapidly, giving nonchlorinated and less toxic alkenes as the major reaction products. Results from the present study suggest that if the right environmental conditions exist or can be created, specific metalloporphyrins may provide a solution for cleaning up sites that are contaminated with chlorinated organic pollutants. [source]

Preparation, Structure, and Electrochemical Properties of Reduced Graphene Sheet Films

ADVANCED FUNCTIONAL MATERIALS, Issue 17 2009
Longhua Tang
Abstract This paper describes the preparation, characterization, and electrochemical properties of reduced graphene sheet films (rGSFs), investigating especially their electrochemical behavior for several redox systems and electrocatalytic properties towards oxygen and some small molecules. The reduced graphene sheets (rGSs) are produced in high yield by a soft chemistry route involving graphite oxidation, ultrasonic exfoliation, and chemical reduction. Transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy clearly demonstrate that graphene was successfully synthesized and modified at the surface of a glassy carbon electrode. Several redox species, such as Ru(NH3)63+/2+, Fe(CN)63,/4,, Fe3+/2+ and dopamine, are used to probe the electrochemical properties of these graphene films by using the cyclic voltammetry method. The rGSFs demonstrate fast electron-transfer (ET) kinetics and possess excellent electrocatalytic activity toward oxygen reduction and certain biomolecules. In our opinion, this microstructural and electrochemical information can serve as an important benchmark for graphene-based electrode performances. [source]

Synthesis and characterization of polyacrylamides containing meso -2,3-dimercaptosuccinic acid end groups

ADVANCES IN POLYMER TECHNOLOGY, Issue 1 2010
Cemal Özero
Abstract By using meso -2,3-dimercaptosuccinic acid-cerium(IV) sulfate and meso -2,3-dimercaptosuccinic acid-potassium permanganate redox systems, the polymerization reaction of acrylamide (AAm) monomer was examined in aqueous acidic medium at low temperatures. Water-soluble polyacrylamides bearing meso -2,3-dimercaptosuccinic acid end groups were synthesized using meso -2,3-dimercaptosuccinic acid as a reducing agent. The effects of parameters such as the molar ratio of acrylamide to initiator, temperature, polymerization time, and sulfuric acid concentration on the yields and molecular weights of polymers were investigated. The augmentation in initiator concentration resulted in a decrease in molecular weight but an increase in the yield of polymers. The increase in reaction temperature from 20 to 60°C led to a decrease in the yield from 56.80% to 20.58%. Ce(IV) and Mn(VII) ions are reduced to Ce(III) and Mn(II) ions in the polymerization reaction and the synthesized acrylamide polymers containing meso -2,3-dimercaptosuccinic acid end groups can absorb these ions at the end of the polymerization reaction. Ultraviolet-visible and atomic absorption measurements of polymer solutions were performed to indicate complexation between polyacrylamide and Ce(III) ions or Mn(II) ions. © 2010 Wiley Periodicals, Inc. Adv Polym Techn 29:45,53, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20180 [source]

Redox-based endoplasmic reticulum dysfunction in neurological diseases

JOURNAL OF NEUROCHEMISTRY, Issue 1 2008
Gábor Bánhegyi
Abstract The redox homeostasis of the endoplasmic reticulum lumen is characteristically different from that of the other subcellular compartments. The concerted action of membrane transport processes and oxidoreductase enzymes maintain the oxidized state of the thiol-disulfide and the reducing state of the pyridine nucleotide redox systems, which are prerequisites for the normal functions of the organelle. The powerful thiol-oxidizing machinery allows oxidative protein folding but continuously challenges the local antioxidant defense. Alterations of the cellular redox environment either in oxidizing or reducing direction affect protein processing and may induce endoplasmic reticulum stress and unfolded protein response. The activated signaling pathways attempt to restore the balance between protein loading and processing and induce apoptosis if the attempt fails. Recent findings strongly support the involvement of this mechanism in brain ischemia, neuronal degenerative diseases and traumatic injury. The redox changes in the endoplasmic reticulum are integral parts of the pathomechanism of neurological diseases, either as causative agents, or as complications. [source]

Redox and antioxidant systems of the malaria parasite Plasmodium falciparum

The chemistry behind redox regulation with a focus on sulphur redox systems

PHYSIOLOGIA PLANTARUM, Issue 3 2008
Claus Jacob
Sulphur metabolism in plants provides a wealth of natural products, including several chemically unusual substances, such as thiosulphinates, polysulphides and isothiocyanates. Many of these reactive sulphur species (RSS) exhibit a distinct redox behaviour in vitro, which translates into a rather interesting biological activity in vivo, such as antibiotic, fungicidal, pesticidal or anticancer activity. While the molecular basis for such activity has long remained obscure, research into sulphur-based redox systems during the past 5,10 years has achieved a better knowledge of the in vitro properties of RSS and has led to an improved understanding of their impact on intracellular redox signalling and control pathways in living cells. It has become apparent that the redox chameleon sulphur occurs in biological systems in about 10 different oxidation states, which give rise to an extensive and complicated network of sulphur-based redox events. Together, natural sulphur products from plants and their intracellular targets provide the basis for innovative design of novel antibiotics, fungicides, pesticides and anticancer agents. [source]