ENGINEERING IN LIFE SCIENCES (ELECTRONIC), Issue 2 2007
J. Dominik
Abstract Redox and size speciation of chromium in rivers contaminated with tannery wastewater was carried out to provide insight into its transport and removal mechanisms. Total chromium was determined with Inductively Coupled Plasma-Mass Spectrometry and Cr,(VI) with Catalytic Adsorption Stripping Voltammetry. For the size speciation, particles were retained with a cartridge filter (cut-off 1.2,,m) and the total filterable fraction was further fractionated with Tangential Flow Filtration to determine the concentrations of chromium associated with the High Molecular Weight Colloidal (HMWC), Low Molecular Weight Colloidal (LMWC) and Truly Dissolved (TD) fractions. Two fluvial systems of similar sizes, but located in contrasting climatic zones, were selected for comparison: the Sebou-Fez system in Morocco and Dunajec River-Czorsztyn Reservoir system in Poland. Particulate Cr dominated in the Sebou-Fez system (about 90,%); while in the Dunajec-Czorsztyn system, it represented only 17,53,% of the total chromium in raw water. Still, the partition coefficients [Kd] were of the same magnitude. Chromium,(III) was the only form detected in Sebou-Fez, whereas in Dunajec-Czorsztyn Cr,(VI) was also present with its proportion increasing downstream from the input of tannery wastewater due to the preferential removal of Cr,(III). In the filtered water in Morocco a large fraction of Cr occurred in the HMWC fraction (50,70,%) at the two most contaminated sites, while the LMWC and TD forms prevailed at the non-contaminated sites in the Sebou River. At a very high concentration, in the water in the proximity of tanneries (well above the theoretical saturation level) Cr precipitated as polynuclear Cr-hydroxide. In Dunajec-Czorsztyn, the partition of Cr,(III) was approximately equal between the HMWC, LMWC and TD fractions, in contrast to Cr,(VI) which occurred almost exclusively in the TD fraction. In both systems, Cr,(III) was rapidly removed from the water to the sediments. The confluence of the Sebou with the Fez and the Czorsztyn reservoir trapped efficiently Cr,(III) preventing its spreading over long distances. Cr,(VI) showed conservative behavior and bypassed the Czorsztyn Reservoir. This study provides a first set of data on the partitioning of Cr,(III) and Cr,(VI) between the particulate, the colloidal and truly dissolved fractions in fluvial systems contaminated with tannery effluents. It also suggests that, in these systems, truly dissolved Cr,(III) can be adequately modeled from the total filterable concentrations. [source]

Structures, Redox and Spectroscopic Properties of PdII and PtII Complexes Containing an Azo Functionality

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2009
Sayak Roy
No abstract is available for this article. [source]

Oxidorhenium(V) Complexes of a Family of Bipyridine-Like Ligands Including Pyridyltriazines and Pyrazinyltriazine: Oxygen-Atom Transfer, Metal Redox and Correlations

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2006
Samir Das
Abstract The title ligands (general abbreviation L) are bipyridine (bpy), its dimethyl (mbpy) and diphenyl (pbpy) derivatives, phenanthroline (phen), 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine (ppyt) and its dimethyl (mpyt) and pyrazinyl (ppzt) analogues. The concerned oxido complexes are [ReOCl3(L)],[ReOBr3(ppyt)] and [ReOBr3(ppzt)]. The chloro and bromo complexes of ppyt and ppzt were prepared by reacting these ligands with [ReOX3(AsPh3)2] (X = Cl, Br). The X-ray structures of [ReOCl3(ppyt)] and [ReOCl3(ppzt)] reveal that the ReCl3 fragment is meridionally disposed and that the L ligand is N,N -coordinated such that the pyridine/pyrazine nitrogen lies trans to the oxido oxygen atom. The Re,O lengths [1.656(10)/1.625(9) Å] correspond to approximate triple bonding. The rate of oxygen-atom transfer from [ReOX3(L)] to triphenylphosphane in solution follows second-order kinetics and is associated with a large and negative entropy of activation (approx. ,30 cal,K,1,mol,1). The initial attack is believed to involve the phosphane lone pair and Re,O ,*-orbitals. Electron withdrawal from the ReVO moiety by varying X or L facilitates oxygen-atom transfer. Thus, the rates follow the orders Br < Cl; mbpy < bpy < phen < pbpy << mpyt < ppyt < ppzt. The reduction potential of the quasireversible ReVIO/ReVO couple displays similar trends and the logarithmic rate constant of oxygen-atom transfer is found to correlate linearly with the reduction potential. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Redox-Based Resistive Switching Memories , Nanoionic Mechanisms, Prospects, and Challenges

ADVANCED MATERIALS, Issue 25-26 2009
Rainer Waser
This review article introduces resistive switching processes that are being considered for nanoelectronic nonvolatile memories. The three main classes are based on an electrochemical metallization mechanism, a valence change mechanism, and a thermochemical mechanism, respectively. The current understanding of the microscopic mechanisms is discussed and the scaling potential is outlined.. [source]

3,4-Ethylenedioxythiophene,Pyridine-Based Polymers: Redox or n-Type Electronic Conductivity?

ADVANCED MATERIALS, Issue 24 2002
C.J. DuBois
A family of polymers based on alternating bi-EDOT and pyridine units is reported. Poly(BEDOT-PyrPyr-Ph2), with a bandgap of 1.2 eV, has four electrochemically accessible colors (dark gray, burgundy, lime green, and light gray) each corresponding to a distinct redox state. In-situ conductance measurements illustrate high n-type doping conductances only thirty times less than those of the p-type doping conductances. [source]

Ferrocene Redox Controlled Reversible Immobilization of Ruthenium Carbene in Ionic Liquid: A Versatile Catalyst for Ring-Closing Metathesis

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009
Guiyan Liu
Abstract A ferrocene-tagged ruthenium carbene 15 that can be reversibly immobilized in an ionic liquid (IL) via the controlled oxidation and reduction of a ferrocene tag was prepared. This offers a new strategy which uses redox chemistry to control immobilization and to recycle both the catalyst and the IL. In this experiment, 11 recycles were performed for the ring-closing metathesis (RCM) of a substrate using 16 as the catalyst in an ionic liquid (IL). More importantly, after the reaction was completed, the ruthenium catalyst was easily separated from the supporting IL by just adding decamethylferrocene (DMFc) to reduce the cationic ferrocene and then extracting it with benzene. Thus, this recycle system offers an easy way to recycle both the ruthenium catalyst and the IL. [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

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]

Redox signalling in cardiovascular disease

PROTEOMICS - CLINICAL APPLICATIONS, Issue 6 2008
Rebecca L. Charles
Abstract Oxidative stress has almost universally and unequivocally been implicated in the pathogenesis of all major diseases, including those of the cardiovascular system. Oxidative stress in cells and cardiovascular biology was once considered only in terms of injury, disease and dysfunction. However, it is now appreciated that oxidants are also produced in healthy tissues, and they function as signalling molecules transmitting information throughout the cell. Conversely, when cells move to a more reduced state, as can occur when oxygen is limiting, this can also result in alterations in the function of biomolecules and subsequently cells. At the centre of this ,redox signalling' are oxidoreductive chemical reactions involving oxidants or reductants post translationally modifying proteins. These structural alterations allow changes in cellular redox state to be coupled to alterations in cell function. In this review, we consider aspects of redox signalling in the cardiovascular system, focusing on the molecular basis of redox sensing by proteins and the array of post-translational oxidative modifications that can occur. In addition, we discuss studies utilising proteomic methods to identify redox-sensitive cardiac proteins, as well as those using this technology more broadly to assess redox signalling in cardiovascular disease. [source]

Stereoselective One-Pot Synthesis of 1-Aminoindanes and 5,6-Fused Azacycles Using a Gold-Catalyzed Redox-Pinacol-Mannich-Michael Cascade,

ANGEWANDTE CHEMIE, Issue 9 2010
Hyun-Suk Yeom
Mannich und mehr: Eine Sequenz aus intramolekularer Redox-, Pinacol-, Mannich- und Michael-Reaktion führt unter Goldkatalyse zu verschiedenartigen Strukturen mit quartären Kohlenstoffzentren, z.,B. Spirocyclen, 1-Aminoindanen und anellierten 5,6-Azabicyclen. Die Reaktion zeichnet sich durch vollständige Atomökonomie, hohe Diastereoselektivität und eine erstaunliche Effizienz aus. [source]

ChemInform Abstract: One-Pot Synthesis of Linearly Fused N-Heterocycles from Their Angular Analogues and Studies of Their Redox and Electrochromic Properties.

CHEMINFORM, Issue 27 2010
Mominul Sinan
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Tris-Cyclometalated Iridium(III) Complexes of Carbazole(fluorenyl)pyridine Ligands: Synthesis, Redox and Photophysical Properties, and Electrophosphorescent Light-Emitting Diodes

CHEMISTRY - A EUROPEAN JOURNAL, Issue 5 2007
Sylvia Bettington Dr.
Abstract Using ligands synthesized by Suzuki cross-coupling methodology, new phosphorescent homoleptic tris-cyclometalated complexes have been obtained, namely fac -[Ir(Cz-2-FlnPy)3] (1,d,f) and fac -[Ir(Cz-3-FlnPy)3] (2,d,f), which are solution-processible triplet emitters (Cz denotes N -hexylcarbazole, n is the number of 9,9,-dihexylfluorene (Fl) units (n=0,1,2) and Py is pyridine). In all cases, Py and Fl are substituted at the 2- and 2,7-positions, respectively, and Cz moieties are substituted by either Py or Fl at the 2- or 3-positions, in series 1 and 2, respectively. The oxidation potential of 1,d studied by cyclic voltammetry (=0.14,V, versus Ag/AgNO3, CH2Cl2) is less positive (i.e. raised HOMO level) compared to that of the isomer 2,d (=0.30,V), where the Cz-nitrogen is meta to the Ir center. Ligand-centered oxidations occur at more positive potentials, leading to 7+ oxidation states with good chemical reversibility and electrochemical quasi-reversibility, for example, for 2,f =0.45 (1e), 0.95 (3e), 1.24,V (3e). Striking differences are seen in the solution-state photophysical data between complexes [Ir(Cz-2-Py)3] (1,d) and [Ir(Cz-3-Py)3] (2,d), in which the Cz moiety is bonded directly to the metal center: for the latter there is an 85,nm blue-shift in emission, a decrease in the luminescence lifetime and an increase in the PLQY value. Organic light emitting devices were made by spin-coating using polyspirobifluorene:bis(triphenyl)diamine (PSBF:TAD) copolymer as host and the complexes 1,d or 2,d as dopants. Turn-on voltages are low (3,4,V). With 1,d orange light is emitted at ,max=590,nm with an EQE of 1.3,% (at 7.5,mA,cm,2) and an emission intensity (luminance) of 4354,cd,m,2 (at 267,mA,m,2). The green emission from 2,d devices (,max=500,nm) is due to the reduced electron-donating ability of the carbazole unit in 2,d. Recording the EL spectra of the 1,d device at 6,V (current density, 100,mA,cm,2) established that the time to half brightness was about 9,h under continuous operation with no change in the spectral profile, confirming the high chemical stability of the complex. [source]

Optical, Redox, and NLO Properties of Tricyanovinyl Oligothiophenes: Comparisons between Symmetric and Asymmetric Substitution Patterns

CHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2006
Juan Casado Dr.
Abstract A series of tricyanovinyl (TCV)-substituted oligothiophenes was synthesized and investigated with a number of physical methods including UV/Vis, IR, and Raman spectroscopy, nonlinear optical (NLO) measurements, X-ray diffraction, and cyclic voltammetry. Mono- or disubstituted oligomers were prepared by the reaction of tetracyanoethylene with mono- or dilithiated oligomers. The comparative effects of the symmetric and asymmetric substitutions in the electronic and molecular properties have been addressed. These oligomers display dramatic reductions in both their optical and electrochemical band gaps in comparison with unsubstituted molecules. The analysis of the electronic properties of the molecules was assisted by density functional theory calculations, which are in excellent agreement with the experimental data. TCV substitution influences the energies of the frontier orbitals, especially with respect to the stabilization of LUMO orbitals. X-ray structural characterization of a monosubstituted oligomer exhibits ,-stacking with favorable intermolecular interactions. NLO results agree with the role of the intramolecular charge-transfer feature in the asymmetric samples. These results furthermore exalt the role of conformational flexibility in the disubstituted compounds and reveal an unexpected nonlinear optical activity for symmetric molecules. Regarding the electronic structure, the interpretation of the vibrational data reflects the balanced interplay between aromatic and quinoid forms, finely tuned by the chain length and substitution pattern. The electronic and structural properties are consistent with the semiconducting properties exhibited by these materials in thin film transistors (TFTs). [source]

Electrolyte Effects on Charge Transport Behavior of [Os(bpy)2(PVP)10Cl]Cl and [Ru(bpy)2(PVP)10Cl]Cl Redox Polymers in Ultra-Thin Films of Polyions

ELECTROANALYSIS, Issue 18 2005
Bingquan Wang
Abstract Metallopolymer films have important applications in electrochemical catalysis. The alternate electrostatic layer-by-layer method was used to assemble films of [Ru(bpy)2(PVP)10Cl]Cl (denoted as ClRu-PVP) and [Os(bpy)2(PVP)10Cl]Cl (ClOs-PVP) metallopolymers onto pyrolytic graphite electrodes. Film thickness estimated by quartz crystal microbalance was 6,8,nm. The effects of pH, electrolyte species and concentration on the electrochemical properties of these electroactive polymers were studied using cyclic voltammetry (CV). Behavior in various electrolytes was compared. Also the mass changes within the ultra-thin film during redox of Os2+/3+ were characterized by in situ electrochemical quartz crystal microbalance (EQCM). The results indicate rapid reversible electron transfer, and show that both ClRu-PVP and ClOs-PVP have compact surface structures while ClOs-PVP is a little denser than ClRu-PVP. Although hydrogen ions do not participate in the chemical reaction of either film, the movement of Na+ cation and water accompanies the redox process of ClOs-PVP films. [source]

Amperometric Ion Sensing Using Polypyrrole Membranes

ELECTROANALYSIS, Issue 5-6 2003
Agata Michalska
Abstract Oxidation/reduction of conducting polymers, coupled with ion exchange between the polymer and electrolyte solution can be utilized for amperometric ion sensing. Electrochemically deposited "model" polypyrrole membranes doped by chloride (PPyCl) and hexacyanoferrate (PPyFeCN) anions were studied from the point of view of their advantages and limits for amperometric determination of electroinactive anions and cations, respectively. Monotonous dependences of the current on electrolyte concentration were obtained for short reading times after potential step application (in the range of ms). The experimental conditions were optimized to obtain linear dependences: log (current) vs. log (KCl concentration) within the range 10,6,1,M. The advantages of the amperometric method over the potentiometric one are highlighted: much lower effect of redox and pH interferences, wider concentration range, elimination of long conditioning procedure. [source]

Partial oxidation and oxidative polymerization of metallothionein

ELECTROPHORESIS, Issue 20 2008
Hajo Haase
Abstract One mechanism for regulation of metal binding to metallothionein (MT) involves the non-enzymatic or enzymatic oxidation of its thiols to disulfides. Formation and speciation of oxidized MT have not been investigated in detail despite the biological significance of this redox biochemistry. While metal ion-bound thiols in MT are rather resistant towards oxidation, free thiols are readily oxidized. MT can be partially oxidized to a state in which some of its thiols remain reduced and bound to metal ions. Analysis of the oxidation products with SDS-PAGE and a thiol-specific labeling technique, employing eosin-5-iodoacetamide, demonstrates higher-order aggregates of MT with intermolecular disulfide linkages. The polymerization follows either non-enzymatic or enzymatic oxidation, indicating that it is a general property of oxidized MT. Supramolecular assemblies of MT add new perspectives to the complex redox and metal equilibria of this protein. [source]

Multicomponent Supramolecular Devices: Synthesis, Optical, and Electronic Properties of Bridged Bis-dirhodium and -diruthenium Complexes,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2006
Anne Petitjean
Abstract Four ruthenium- and rhodium-based metal,metal-bonded multicomponent systems have been synthesized, and their absorption, redox, spectroelectrochemical and structural properties have been studied. The absorption spectra of the four bis-dimetallic compounds M2LM2, where L is a bridging ligand and M is rhodium or ruthenium, exhibit very strong bands in the UV, visible and, for the diruthenium species, near-IR region. The low-energy absorption bands are assigned to charge-transfer transitions involving a metal,metal bonding orbital as the donor and an orbital centered on the bis-tetradentate aromatic ligands as the acceptor (metal,metal to ligand charge transfer, M2LCT). Each compound exhibits reversible bridging-ligand-centered reductions at mild potentials and several reversible oxidation processes. The oxidation signals of the two equivalent dimetallic centers of each bis-dimetallic compound are split, with the splitting , a measure of the electronic coupling , depending on both the metal and bridging ligand. The mixed-valence species of the dirhodium species was investigated, and the electronic coupling matrix element calculated from the experimental intervalence band parameters for one of them (86 cm,1) indicates a significant inter-component electronic interaction which compares well with good electron conducting anionic bridges such as cyanides. Although none of these compounds is luminescent, the M2LCT excited state of one of the bis-dirhodium complexes is relatively long-lived (about 6 ,s) in degassed acetonitrile at room temperature. The results presented here are promising for the development of linear poly-dimetallic complexes built on longer naphthyridine-based strands, with significant long-range electronic coupling and molecular-wire-like behavior. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Hydrolysis of Toxic Natural Glucosides Catalyzed by Cyclodextrin Dicyanohydrins

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 4 2008
Jeannette Bjerre
Abstract The hydrolysis of toxic 7-hydroxycoumarin glucosides and other aryl and alkyl glucosides, catalyzed by modified ,- and ,-cyclodextrin dicyanohydrins, was investigated using different UV, redox, or HPAEC detection assays. The catalyzed reactions all followed Michaelis,Menten kinetics, and an impressive rate increase of up to 7569 (kcat/kuncat) was found for the hydroxycoumarin glucoside substrate 4-MUGP. Good and moderate degrees of catalysis (kcat/kuncat) of up to 1259 were found for the natural glucosides phloridzin and skimmin. By using a newly developed catechol detection UV-assay, a weak degree of catalysis was also found for the toxic hydroxycoumarin esculin. A novel synthesized diaminomethyl ,-cyclodextrin showed a weak catalysis of p -nitrophenyl ,- D -glucopyranoside hydrolysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Reactive oxygen species are signalling molecules for skeletal muscle adaptation

EXPERIMENTAL PHYSIOLOGY, Issue 1 2010
Scott K. Powers
Increased reactive oxygen species (ROS) production is crucial to the remodelling that occurs in skeletal muscle in response to both exercise training and prolonged periods of disuse. This review discusses the redox-sensitive signalling pathways that are responsible for this ROS-induced skeletal muscle adaptation. We begin with a discussion of the sites of ROS production in skeletal muscle fibres. This is followed by an overview of the putative redox-sensitive signalling pathways that promote skeletal muscle adaptation. Specifically, this discussion highlights redox-sensitive kinases, phosphatases and the transcription factor nuclear factor-,B. We also discuss the evidence that connects redox signalling to skeletal muscle adaptation in response to increased muscular activity (i.e. exercise training) and during prolonged periods of muscular inactivity (i.e. immobilization). In an effort to stimulate further research, we conclude with a discussion of unanswered questions about redox signalling in skeletal muscle. [source]

Oxygen sensing in hypoxic pulmonary vasoconstriction: using new tools to answer an age-old question

EXPERIMENTAL PHYSIOLOGY, Issue 1 2008
Gregory B. Waypa
Hypoxic pulmonary vasoconstriction (HPV) becomes activated in response to alveolar hypoxia and, although the characteristics of HPV have been well described, the underlying mechanism of O2 sensing which initiates the HPV response has not been fully established. Mitochondria have long been considered as a putative site of oxygen sensing because they consume O2 and therefore represent the intracellular site with the lowest oxygen tension. However, two opposing theories have emerged regarding mitochondria-dependent O2 sensing during hypoxia. One model suggests that there is a decrease in mitochondrial reactive oxygen species (ROS) levels during the transition from normoxia to hypoxia, resulting in the shift in cytosolic redox to a more reduced state. An alternative model proposes that hypoxia paradoxically increases mitochondrial ROS signalling in pulmonary arterial smooth muscle. Experimental resolution of the question of whether the mitochondrial ROS levels increase or decrease during hypoxia has been problematic owing to the technical limitations of the tools used to assess oxidant stress as well as the pharmacological agents used to inhibit the mitochondrial electron transport chain. However, recent developments in genetic techniques and redox-sensitive probes may allow us eventually to reach a consensus concerning the O2 sensing mechanism underlying HPV. [source]

Binding of ligands originates small perturbations on the microscopic thermodynamic properties of a multicentre redox protein

FEBS JOURNAL, Issue 9 2005
Carlos A. Salgueiro
NMR and visible spectroscopy coupled to redox measurements were used to determine the equilibrium thermodynamic properties of the four haems in cytochrome c3 under conditions in which the protein was bound to ligands, the small anion phosphate and the protein rubredoxin with the iron in the active site replaced by zinc. Comparison of these results with data for the isolated cytochrome shows that binding of ligands causes only small changes in the reduction potentials of the haems and their pairwise interactions, and also that the redox-sensitive acid,base centre responsible for the redox,Bohr effect is essentially unaffected. Although neither of the ligands tested is a physiological partner of cytochrome c3, the small changes observed for the thermodynamic properties of cytochrome c3 bound to these ligands vs. the unbound state, indicate that the thermodynamic properties measured for the isolated protein are relevant for a physiological interpretation of the role of this cytochrome in the bioenergetic metabolism of Desulfovibrio. [source]

Molecular characterization of artemin and ferritin from Artemia franciscana

FEBS JOURNAL, Issue 1 2003
Tao Chen
Embryos of the brine shrimp, Artemia franciscana, exhibit remarkable resistance to physiological stress, which is temporally correlated with the presence of two proteins, one a small heat shock/,-crystallin protein termed p26 and the other called artemin, of unknown function. Artemin was sequenced previously by Edman degradation, and its relationship to ferritin, an iron storage protein, established. The isolation from an Artemia expressed sequence tag library of artemin and ferritin cDNAs extends this work. Artemin cDNA was found to contain an ORF of 693 nucleotides, and its deduced amino-acid sequence, except for the initiator methionine, was identical with that determined previously. Ferritin cDNA is 725 bp in length with an ORF of 516 nucleotides. Artemin amino-acid residues 32,185 are most similar to ferritin, but artemin is enriched in cysteines. The abundance of cysteines and their intramolecular spatial distribution suggest that artemin protects embryos against oxidative damage and/or that its function is redox regulated. The conserved regions in artemin and ferritin monomers are structurally similar to one another and both proteins assemble into oligomers. However, modeling of the quaternary structure indicated that artemin multimers lack the central space used for metal storage that characterizes ferritin oligomers, implying different roles for this protein. Probing of Northern blots revealed two artemin transcripts, one of 3.5 kb and another of 2.2 kb. These transcripts decreased in parallel and had almost disappeared by 16 h of development. The ferritin transcript of 0.8 kb increased slightly during reinitiation of development, then declined, and was almost completely gone by 16 h. Clearly, the loss of artemin and ferritin during embryo development is due to transcriptional regulation and proteolytic degradation of the proteins. [source]

Azidothymidine causes functional and structural destruction of mitochondria, glutathione deficiency and HIV-1 promoter sensitization

FEBS JOURNAL, Issue 11 2002
Tokio Yamaguchi
Mitochondrial functional and structural impairment and generation of oxidative stress have been implicated in aging, various diseases and chemotherapies. This study analyzed azidothymidine (AZT)-caused failures in mitochondrial functions, in redox regulation and activation of the HIV-1 gene expression. We monitored intracellular concentrations of ATP and glutathione (GSH) as the indicators of energy production and redox conditions, respectively, during the time-course experiments with U937 and MOLT4 human lymphoid cells in the presence of AZT (0.05 mg·mL,1) or H2O2 (0.01 mm) for 15,25 days. Mitochondrial DNA integrity and NF-,B-driven HIV-1 promoter activity were also assessed. ATP concentration began to decrease within several days after exposure to AZT or H2O2, and the decrease continued to reach 30,40% of the normal level. However, decline of GSH was detectable after a retention period for at least 5,6 days, and progressed likewise. PCR analyses found that mitochondrial DNA destruction occurred when the ATP and GSH depletion had progressed, detecting a difference in the deletion pattern between AZT and H2O2 -treated cells. The GSH decrease coincided with HIV-1 promoter sensitization detected by enhanced DNA binding ability of NF-,B and induction of the gene expression upon H2O2 -rechallenge. Our results suggest that, in the process of AIDS myopathy development, AZT or oxidative agents directly impair the energy-producing system of mitochondria, causing dysfunction of cellular redox control, which eventually leads to loss of the mitochondrial DNA integrity. The mechanism of cellular redox condition-mediated NF-,B activation is discussed. [source]

Bacterial motility: links to the environment and a driving force for microbial physics

FEMS MICROBIOLOGY ECOLOGY, Issue 1 2006
James G. Mitchell
Abstract Bacterial motility was recognized 300 years ago. Throughout this history, research into motility has led to advances in microbiology and physics. Thirty years ago, this union helped to make run and tumble chemotaxis the paradigm for bacterial movement. This review highlights how this paradigm has expanded and changed, and emphasizes the following points. The absolute magnitude of swimming speed is ecologically important because it helps determine vulnerability to Brownian motion, sensitivity to gradients, the type of receptors used and the cost of moving, with some bacteria moving at 1 mm s,1. High costs for high speeds are offset by the benefit of resource translocation across submillimetre redox and other environmental gradients. Much of environmental chemotaxis appears adapted to respond to gradients of micrometres, rather than migrations of centimetres. In such gradients, control of ion pumps is particularly important. Motility, at least in the ocean, is highly intermittent and the speed is variable within a run. Subtleties in flagellar physics provide a variety of reorientation mechanisms. Finally, while careful physical analysis has contributed to our current understanding of bacterial movement, tactic bacteria are increasingly widely used as experimental and theoretical model systems in physics. [source]

Sulfur assimilation and glutathione metabolism under cadmium stress in yeast, protists and plants

FEMS MICROBIOLOGY REVIEWS, Issue 4 2005
David Mendoza-Cózatl
Abstract Glutathione (,-glu-cys-gly; GSH) is usually present at high concentrations in most living cells, being the major reservoir of non-protein reduced sulfur. Because of its unique redox and nucleophilic properties, GSH serves in bio-reductive reactions as an important line of defense against reactive oxygen species, xenobiotics and heavy metals. GSH is synthesized from its constituent amino acids by two ATP-dependent reactions catalyzed by ,-glutamylcysteine synthetase and glutathione synthetase. In yeast, these enzymes are found in the cytosol, whereas in plants they are located in the cytosol and chloroplast. In protists, their location is not well established. In turn, the sulfur assimilation pathway, which leads to cysteine biosynthesis, involves high and low affinity sulfate transporters, and the enzymes ATP sulfurylase, APS kinase, PAPS reductase or APS reductase, sulfite reductase, serine acetyl transferase, O -acetylserine/O -acetylhomoserine sulfhydrylase and, in some organisms, also cystathionine ,-synthase and cystathionine ,-lyase. The biochemical and genetic regulation of these pathways is affected by oxidative stress, sulfur deficiency and heavy metal exposure. Cells cope with heavy metal stress using different mechanisms, such as complexation and compartmentation. One of these mechanisms in some yeast, plants and protists is the enhanced synthesis of the heavy metal-chelating molecules GSH and phytochelatins, which are formed from GSH by phytochelatin synthase (PCS) in a heavy metal-dependent reaction; Cd2+ is the most potent activator of PCS. In this work, we review the biochemical and genetic mechanisms involved in the regulation of sulfate assimilation-reduction and GSH metabolism when yeast, plants and protists are challenged by Cd2+. [source]

Energetics of overall metabolic reactions of thermophilic and hyperthermophilic Archaea and Bacteria

FEMS MICROBIOLOGY REVIEWS, Issue 2 2001
Jan P. Amend
Abstract Thermophilic and hyperthermophilic Archaea and Bacteria have been isolated from marine hydrothermal systems, heated sediments, continental solfataras, hot springs, water heaters, and industrial waste. They catalyze a tremendous array of widely varying metabolic processes. As determined in the laboratory, electron donors in thermophilic and hyperthermophilic microbial redox reactions include H2, Fe2+, H2S, S, S2O32,, S4O62,, sulfide minerals, CH4, various mono-, di-, and hydroxy-carboxylic acids, alcohols, amino acids, and complex organic substrates; electron acceptors include O2, Fe3+, CO2, CO, NO3,, NO2,, NO, N2O, SO42,, SO32,, S2O32,, and S. Although many assimilatory and dissimilatory metabolic reactions have been identified for these groups of microorganisms, little attention has been paid to the energetics of these reactions. In this review, standard molal Gibbs free energies (,Gr°) as a function of temperature to 200°C are tabulated for 370 organic and inorganic redox, disproportionation, dissociation, hydrolysis, and solubility reactions directly or indirectly involved in microbial metabolism. To calculate values of ,Gr° for these and countless other reactions, the apparent standard molal Gibbs free energies of formation (,G°) at temperatures to 200°C are given for 307 solids, liquids, gases, and aqueous solutes. It is shown that values of ,Gr° for many microbially mediated reactions are highly temperature dependent, and that adopting values determined at 25°C for systems at elevated temperatures introduces significant and unnecessary errors. The metabolic processes considered here involve compounds that belong to the following chemical systems: H,O, H,O,N, H,O,S, H,O,N,S, H,O,Cinorganic, H,O,C, H,O,N,C, H,O,S,C, H,O,N,S,Camino acids, H,O,S,C,metals/minerals, and H,O,P. For four metabolic reactions of particular interest in thermophily and hyperthermophily (knallgas reaction, anaerobic sulfur and nitrate reduction, and autotrophic methanogenesis), values of the overall Gibbs free energy (,Gr) as a function of temperature are calculated for a wide range of chemical compositions likely to be present in near-surface and deep hydrothermal and geothermal systems. [source]

The relationship between Chironomus plumosus burrows and the spatial distribution of pore-water phosphate, iron and ammonium in lake sediments

FRESHWATER BIOLOGY, Issue 2 2007
JÖRG LEWANDOWSKI
Summary 1. To study the influence of chironomids on the distribution of pore-water concentrations of phosphate, iron and ammonium, we conducted a laboratory experiment using mesocosms equipped with two-dimensional pore-water samplers, filled with lake sediment and populated with different densities of Chironomus plumosus. 2. Specially designed mesocosms were used in the study. A 6-mm deep space between the front plate and the pore-water sampler at the back plate was just thick enough to allow the chironomids to live undisturbed, yet thin enough to force all the burrows into a two-dimensional plane. 3. The courses of the burrows were observed during the experiment as oxidised zones surrounding them, as well as being identified with an X-ray image taken at the end of the experiment. 4. We investigated the relationship between C. plumosus burrows and spatial patterns of pore-water composition. Concentrations of the three ions were significantly less around ventilated burrows (54% to 24%), as bioirrigation caused a convective exchange of pore-water enriched with dissolved species compared with the overlying water, and also because oxygen imported into the sediment resulting in nitrification of ammonium, oxidation of iron(II) and a co-precipitation of phosphate with Fe(III) oxyhydroxides. 5. In mesocosms with chironomids, new (redox) interfaces occurred with diffusive pore-water gradients perpendicular to the course of burrows and the site of major phosphate, ammonium and iron(II) release shifted from the sediment surface to the burrow walls. [source]

Mapping the archaeological soil archive of sand and gravel mineral reserves in Britain

GEOARCHAEOLOGY: AN INTERNATIONAL JOURNAL, Issue 1 2009
Ingrid Ward
Primary sand and gravel deposits in Britain play an important role in preserving our cultural heritage and are also a valuable aggregate resource. While an understanding of the extrinsic properties of the soil archive (such as pH, redox, groundwater) can provide a firstorder assessment of the potential risk to any archaeologically sensitive deposits, we have very poor definition of spatial variations in the extrinsic properties of soil that influence archaeological preservation at a regional and national scale. Developments in digital geological mapping, remote sensing, and geochemical survey data undertaken by the British Geological Survey (BGS) have, however, significantly extended capabilities in this respect and can potentially be used to provide a primary assessment of the sensitivity of the present soil archive and the potential risk from changes to the soil process on cultural material in areas earmarked for aggregate extraction. Two of the major factors affecting archaeological preservation,soil acidification and groundwater,can be mapped or predicted at scales of better than 1:50,000 across increasingly large parts of the country using a combination of regional hydrogeological, geophysical, and geochemical data. Additional data from site investigations may further refine preservation potential as a function of changes in redox potential and acidity. These data, maps and models can be used to (1) better establish a baseline for archaeological preservation at a regional and national scale and (2) improve our understanding of how the physical and chemical properties of the near surface environment can be managed to sustainably preserve archaeological materials in areas impacted by sand and gravel extraction. © 2009 Wiley Periodicals, Inc. [source]

Redox Processes and Water Quality of Selected Principal Aquifer Systems

GROUND WATER, Issue 2 2008
P.B. McMahon
Reduction/oxidation (redox) conditions in 15 principal aquifer (PA) systems of the United States, and their impact on several water quality issues, were assessed from a large data base collected by the National Water-Quality Assessment Program of the USGS. The logic of these assessments was based on the observed ecological succession of electron acceptors such as dissolved oxygen, nitrate, and sulfate and threshold concentrations of these substrates needed to support active microbial metabolism. Similarly, the utilization of solid-phase electron acceptors such as Mn(IV) and Fe(III) is indicated by the production of dissolved manganese and iron. An internally consistent set of threshold concentration criteria was developed and applied to a large data set of 1692 water samples from the PAs to assess ambient redox conditions. The indicated redox conditions then were related to the occurrence of selected natural (arsenic) and anthropogenic (nitrate and volatile organic compounds) contaminants in ground water. For the natural and anthropogenic contaminants assessed in this study, considering redox conditions as defined by this framework of redox indicator species and threshold concentrations explained many water quality trends observed at a regional scale. An important finding of this study was that samples indicating mixed redox processes provide information on redox heterogeneity that is useful for assessing common water quality issues. Given the interpretive power of the redox framework and given that it is relatively inexpensive and easy to measure the chemical parameters included in the framework, those parameters should be included in routine water quality monitoring programs whenever possible. [source]

Arsenic in Glacial Aquifers: Sources and Geochemical Controls

GROUND WATER, Issue 4 2005
Walton R. Kelly
A total of 176 wells in sand-and-gravel glacial aquifers in central Illinois were sampled for arsenic (As) and other chemical parameters. The results were combined with archived and published data from several hundred well samples to determine potential sources of As and the potential geochemical controls on its solubility and mobility. There was considerable spatial variability in the As concentrations. High concentrations were confined to areas smaller than 1 km in diameter. Arsenic and well depth were uncorrelated. Arsenic solubility appeared to be controlled by oxidation-reduction (redox) conditions, especially the presence of organic matter. Geochemical conditions in the aquifers are typically reducing, but only in the most reducing water does As accumulate in solution. In wells in which total organic carbon (TOC) was below 2 mg/L and sulfate (SO42,) was present, As concentrations were low or below the detection limit (0.5 ,g/L). Arsenic concentrations >10 ,g/L were almost always found in wells where TOC was >2 mg/L and SO42, was absent or at low concentrations, indicating post,SO42,reducing conditions. Iron (Fe) is common in the aquifer sediments, and Fe oxide reduction appears to be occurring throughout the aquifers. Arsenic is likely released from the solid phase as Fe oxide is reduced. [source]