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Reduced State (reduced + state)
Selected AbstractsHow Does Structural Reform Affect Regional Development?ECONOMIC GEOGRAPHY, Issue 4 2000Resolving Contradictory Theory with Evidence from India Abstract: Regional theory offers little coherent guidance on the prospects for interregional development after structural reform in developing nations. In this paper I suggest a basic set of hypotheses in which the neoliberal nation-state is simultaneously a reduced state (less concerned about promoting regional balance) and an enlarged state (directing development toward selected regions). Under the new regulatory structure the location of post-reform investments may be expected to favor the coast, advanced regions, and existing metropolises (especially the edge areas); these expectations may be more true for foreign direct investments than domestic investments (especially the direct investments of the state). I use disaggregated pre- and post-reform industrial data from India to test the hypotheses. The results offer partial to full support for all hypotheses, providing evidence of the return of cumulative causation, and raising concerns about the political economy of future development in the lagging regions. [source] Oxygen sensing in hypoxic pulmonary vasoconstriction: using new tools to answer an age-old questionEXPERIMENTAL PHYSIOLOGY, Issue 1 2008Gregory 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] Contribution of exofacial thiol groups in the reducing activity of Lactococcus lactisFEBS JOURNAL, Issue 10 2010D. Michelon Lactococcus lactis can decrease the redox potential at pH 7 (Eh7) from 200 to ,200 mV in oxygen free Man,Rogosa,Sharpe media. Neither the consumption of oxidizing compounds or the release of reducing compounds during lactic acid fermentation were involved in the decrease in Eh7 by the bacteria. Thiol groups located on the bacterial cell surface appear to be the main components that are able to establish a greater exchange current between the Pt electrode and the bacteria. After the final Eh7 (,200 mV) was reached, only thiol-reactive reagents could restore the initial Eh7 value. Inhibition of the proton motive force showed no effect on maintaining the final Eh7 value. These results suggest that maintaining the exofacial thiol (,SH) groups in a reduced state does not depend on an active mechanism. Thiol groups appear to be displayed by membrane proteins or cell wall-bound proteins and may participate in protecting cells against oxidative stress. [source] Solution structure of the functional domain of Paracoccus denitrificans cytochrome c552 in the reduced stateFEBS JOURNAL, Issue 13 2000Primo, Pristov In order to determine the solution structure of Paracoccus denitrificans cytochrome c552 by NMR, we cloned and isotopically labeled a 10.5-kDa soluble fragment (100 residues) containing the functional domain of the 18.2-kDa membrane-bound protein. Using uniformly 15N-enriched samples of cytochrome c552 in the reduced state, a variety of two-dimensional and three-dimensional heteronuclear double-resonance NMR experiments was employed to achieve complete 1H and 15N assignments. A total of 1893 distance restraints was derived from homonuclear 2D-NOESY and heteronuclear 3D-NOESY spectra; 1486 meaningful restraints were used in the structure calculations. After restrained energy minimization a family of 20 structures was obtained with rmsd values of 0.56 ± 0.10 Å and 1.09 ± 0.09 Å for the backbone and heavy atoms, respectively. The overall topology is similar to that seen in previously reported models of this class of proteins. The global fold consists of two long helices at the N-terminus and C-terminus and three shorter helices surrounding the heme moiety; the helices are connected by well-defined loops. Comparison with the X-ray structure shows some minor differences in the positions of the Trp57 and Phe65 side-chain rings as well as the heme propionate groups. [source] Hydrology and nitrogen balance of a seasonally inundated Danish floodplain wetlandHYDROLOGICAL PROCESSES, Issue 3 2004Hans Estrup Andersen Abstract This paper characterizes a seasonally inundated Danish floodplain wetland in a state close to naturalness and includes an analysis of the major controls on the wetland water and nitrogen balances. The main inputs of water are precipitation and percolation during ponding and unsaturated conditions. Lateral saturated subsurface flow is low. The studied floodplain owes its wetland status to the hydraulic properties of its sediments: the low hydraulic conductivity of a silt,clay deposit on top of the floodplain maintains ponded water during winter, and parts of autumn and spring. A capillary fringe extends to the soil surface, and capillary rise from groundwater during summer maintains near-saturated conditions in the root zone, and allows a permanently very high evapotranspiration rate. The average for the growing season of 1999 is 3·6 mm day,1 and peak rate is 5·6 mm day,1. In summer, the evapotranspiration is to a large degree supplied by subsurface storage in a confined peat layer underlying the silt,clay. The floodplain sediments are in a very reduced state as indicated by low sulphate concentrations. All nitrate transported into the wetland is thus denitrified. However, owing to modest water exchange with surrounding groundwater and surface water, denitrification is low; 71 kg NO3,N ha,1 during the study period of 1999. Reduction of nitrate diffusing into the sediments during water ponding accounts for 75% of nitrate removal. Biomass production and nitrogen uptake in above-ground vegetation is high,8·56 t dry matter ha,1 year,1 and 103 kg N ha,1 year,1. Subsurface ammonium concentrations are high, and convective upward transport into the root zone driven by evapotranspiration amounted to 12·8 kg N ha,1year,1. The floodplain wetland sediments have a high nitrogen content, and conditions are very favourable for mineralization. Mineralization thus constitutes 72% of above-ground plant uptake. The study demonstrates the necessity of identifying controlling factors, and to combine surface flow with vadose and groundwater flow processes in order to fully comprehend the flow and nitrogen dynamics of this type of wetland. Copyright © 2004 John Wiley & Sons, Ltd. [source] Poly(O -anisidine) coatings electrodeposited onto AL-2024: Synthesis, characterization, and corrosion protection evaluationADVANCES IN POLYMER TECHNOLOGY, Issue 4 2004Kunal Shah Abstract Poly(O -anisidine) coating was successfully electrodeposited onto Al-2024. Cyclic voltammetry and reflection absorption infrared spectroscopy (RAIR) analysis were carried out in order to fully understand the formation and structure of the resulting polymer coating. RAIR spectrum showed the characteristics peaks of poly(O -anisidine). As the reaction time was varied, the CV peak shifted from 0.75 to 0.81 V vs. SCE suggesting that a change in structure of the polymer from a reduced state to a partially oxidized form has occurred. UV spectrum showed two peaks at 320 and 620 nm suggesting the presence of conjugation on the polymer backbone. The deposition of the poly(O -anisidine) onto the substrate was controlled by nucleation and growth mechanism. DC polarization technique was used to evaluate the corrosion protection offered by poly(O -anisidine) coatings. Preliminarily data shows that these coatings help to ennoble the surface of the substrate. © 2004 Wiley Periodicals, Inc. Adv Polym Techn 23: 291,297, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20024 [source] Factor analysis of spectroelectrochemical reduction of FAD reveals the pKa of the reduced state and the reduction pathwayJOURNAL OF CHEMOMETRICS, Issue 12 2007Edmund R. Malinowski Abstract The free flavin adenine dinucleotide (FAD) cofactor is known to exhibit a pH-dependent midpoint potential involving a simultaneous two-electron transfer step (n,=,2). Uv-vis spectroelectrochemical reductions of FAD at constant pH, ranging from 5 to 9, were recorded and analyzed by factor analysis. Principal factor analysis was used to determine the number of species present at each pH. The results indicate that only two composite forms of FAD are present: the oxidized and the reduced forms. Window factor analysis was used to extract the concentration profiles of the controlling species. The oxidized form was found to be a single pH-independent species, whereas the reduced form consists of two species. The pH-dependent spectroscopic changes of reduced FAD were best modeled by a single proton transfer step involving two different ionization states with an apparent pKa,=,6.3. This value compares favorably with those obtained from NMR and from midpoint potential measurements. At pH 6, the reduction of FAD was found to be first order, whereas at pH 9 the reduction is zero order; these observations are explained in terms of the reaction pathway involving xanthine oxidase, its substrate, and the pH. Copyright © 2007 John Wiley & Sons, Ltd. [source] Transglutaminase Catalysis of Modified Whey Protein DispersionsJOURNAL OF FOOD SCIENCE, Issue 4 2010Debra A. Clare ABSTRACT:, Transglutaminase (TGase) cross-linking reactions were accomplished using a heat-modified whey protein concentrate (mWPC) substrate after pH adjustment to 8. Based on earlier reports, the degree of lactosylation with respect to ,-lactoglobulin was lower in mWPC dispersions than measured in commercial whey concentrate (cWPC) protein solutions. In this study, a higher concentration of free sulfhydryl groups was detected in soluble supernatant fractions. Both factors potentially impact the availability of reactive lysine/glutaminyl residues required for TGase reactivity. The addition of 10 mM dithiothreitol (DTT) to the substrate mix, CBZ-glutaminyl glycine and hydroxylamine, revealed a 3.6-fold increase in TGase activity, likely due in part to maintenance of the catalytic cysteine residue in a reduced state. Furthermore, inclusion of DTT to mWPC dispersions significantly raised the apparent viscosity, independently of enzyme modification, while the rate of polymerization increased 2-fold based on OPA assay measurements. Limited cross-linking slightly increased the apparent viscosity, whereas extensive coupling lowered these values compared to equivalent nonenzyme-treated mWPC samples. Carbohydrate-staining revealed formation of glyco-polymers due to covalent linkages between glucosamine and mWPC proteins after TGase processing. Again, the apparent viscosity decreased after extensive enzymatic modification. Larger particles, sized 11.28 ,m, were observed in the structural matrix of TGase-mWPC-fixed samples compared to 8 ,m particles in control mWPC samples as viewed in scanning electron micrographs. Ultimately, the functional characteristics of TGase-mWPC ingredients may be custom-designed to deliver alternative functional attributes by adjusting the experimental reaction conditions under which catalysis is achieved. Practical Application: Taken together, these results suggest that unique TGase-mWPC and/or TGase-mWPC-glucosamine ingredients may be designed to provide novel, value-added, polymeric/glyco-polymeric protein products that afford added benefit for the milk industry. [source] Enhancing electrochromic properties of conducting polymers via copolymerization: Copolymer of 1-(4-fluorophenyl)-2,5-di(thiophen-2-yl)-1H -pyrrole with 3,4-ethylene dioxythiophene,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2007Ozlem Turkarslan Abstract A copolymer of 1-(4-fluorophenyl)-2,5-di(thiophen-2-yl)-1H -pyrrole (FPTP) with 3,4-ethylene dioxythiophene (EDOT) was electrochemically synthesized and characterized. While poly(FPTP) (P(FPTP)) has only two colors in its oxidized and neutral states (blue and yellow), its copolymer with EDOT has five different colors (purple, red, light gray, green, and blue). Electrochromic devices based on P(FPTP- co -EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed and characterized. The oxidized state of the device shows blue color whereas it shows purple for the reduced state. At several potentials the device has good transparency with green and gray colors. Maximum contrast (,%T) and switching time of the device were measured as 23% and 1.1 s at 555 nm. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4496,4503, 2007 [source] Mutational analysis of RsrA, a zinc-binding anti-sigma factor with a thiol,disulphide redox switchMOLECULAR MICROBIOLOGY, Issue 4 2001Mark S. B. Paget In the Gram-positive bacterium, Streptomyces coelicolor A3(2), expression of the thioredoxin system is modulated by a sigma factor called ,R in response to changes in the cytoplasmic thiol,disulphide status, and the activity of ,R is controlled post-translationally by an anti-sigma factor, RsrA. In vitro, the anti-sigma factor activity of RsrA, which contains seven cysteines, correlates with its thiol,disulphide redox status. Here, we investigate the function of RsrA in vivo. A constructed rsrA null mutant had very high constitutive levels of disulphide reductase activity and ,R -dependent transcription, confirming that RsrA is a negative regulator of ,R and a key sensor of thiol,disulphide status. Targeted mutagenesis revealed that three of the seven cysteines in RsrA (C11, C41 and C44) were essential for anti-sigma factor activity and that a mutant RsrA protein containing only these three cysteines was active and still redox sensitive in vivo. We also show that RsrA is a metalloprotein, containing near-stoichiometric amounts of zinc. On the basis of these data, we propose that a thiol,disulphide redox switch is formed between two of C11, C41 and C44, and that all three residues play an essential role in anti-sigma factor activity in their reduced state, perhaps by acting as ligands for zinc. Unexpectedly, rsrA null mutants were blocked in sporulation, probably as a consequence of an increase in the level of free ,R. [source] Fine structure and 18S rDNA phylogeny of a marine araphid pennate diatom Plagiostriata goreensis gen. et sp. nov. (Bacillariophyta)PHYCOLOGICAL RESEARCH, Issue 1 2009Shinya Sato SUMMARY A marine araphid pennate diatom Plagiostriata goreensis is described from the sand grains of Goree Island, Dakar, Republic of Senegal, based on observations of fine structure of its frustule. The most striking feature of the species is its striation, which is angled at approximately 60° across the robust sternum. The other defining features of the species are its one highly reduced rimoportula and apical pores located at both ends of the valve margin. In the 18S rDNA phylogeny, the species appears as a member of a ,small-celled clade' of araphid pennate diatoms that consist of Nanofrustulum, Opephora and Staurosira. The results of the phylogenetic analyses suggest that the distinct characters of the diatom; namely, oblique striae and apical pores, may have been acquired independently. However, it remains unclear whether the rimoportula of P. goreensis is a reduced state or P. goreensis acquired its morphologically curious rimoportula independently after the loss of an ancient rimoportula at the root of the small-celled clade. [source] Prediction of reversibly oxidized protein cysteine thiols using protein structure propertiesPROTEIN SCIENCE, Issue 3 2008Ricardo Sanchez Abstract Protein cysteine thiols can be divided into four groups based on their reactivities: those that form permanent structural disulfide bonds, those that coordinate with metals, those that remain in the reduced state, and those that are susceptible to reversible oxidation. Physicochemical parameters of oxidation-susceptible protein thiols were organized into a database named the Balanced Oxidation Susceptible Cysteine Thiol Database (BALOSCTdb). BALOSCTdb contains 161 cysteine thiols that undergo reversible oxidation and 161 cysteine thiols that are not susceptible to oxidation. Each cysteine was represented by a set of 12 parameters, one of which was a label (1/0) to indicate whether its thiol moiety is susceptible to oxidation. A computer program (the C4.5 decision tree classifier re-implemented as the J48 classifier) segregated cysteines into oxidation-susceptible and oxidation-non-susceptible classes. The classifier selected three parameters critical for prediction of thiol oxidation susceptibility: (1) distance to the nearest cysteine sulfur atom, (2) solvent accessibility, and (3) pKa. The classifier was optimized to correctly predict 136 of the 161 cysteine thiols susceptible to oxidation. Leave-one-out cross-validation analysis showed that the percent of correctly classified cysteines was 80.1% and that 16.1% of the oxidation-susceptible cysteine thiols were incorrectly classified. The algorithm developed from these parameters, named the Cysteine Oxidation Prediction Algorithm (COPA), is presented here. COPA prediction of oxidation-susceptible sites can be utilized to locate protein cysteines susceptible to redox-mediated regulation and identify possible enzyme catalytic sites with reactive cysteine thiols. [source] Cleavage of the iron-methionine bond in c-type cytochromes: Crystal structure of oxidized and reduced cytochrome c2 from Rhodopseudomonas palustris and its ammonia complexPROTEIN SCIENCE, Issue 1 2002Silvano Geremia Abstract The three-dimensional structures of the native cytochrome c2 from Rhodopseudomonas palustris and of its ammonia complex have been obtained at pH 4.4 and pH 8.5, respectively. The structure of the native form has been refined in the oxidized state at 1.70 Å and in the reduced state at 1.95 Å resolution. These are the first high-resolution crystal structures in both oxidation states of a cytochrome c2 with relatively high redox potential (+350 mV). The differences between the two oxidation states of the native form, including the position of internal water molecules, are small. The unusual six-residue insertion Gly82-Ala87, which precedes the heme binding Met93, forms an isolated 310 -helix secondary structural element not previously observed in other c-type cytochromes. Furthermore, this cytochrome shows an external methionine residue involved in a strained folding near the exposed edge of the heme. The structural comparison of the present cytochrome c2 with other c-type cytochromes has revealed that the presence of such a residue, with torsion angles , and , of approximately ,140 and ,130°, respectively, is a typical feature of this family of proteins. The refined crystal structure of the ammonia complex, obtained at 1.15 Å resolution, shows that the sulphur atom of the Met93 axial ligand does not coordinate the heme iron atom, but is replaced by an exogenous ammonia molecule. This is the only example so far reported of an X-ray structure with the heme iron coordinated by an ammonia molecule. The detachment of Met93 is accompanied by a very localized change in backbone conformation, involving mainly the residues Lys92, Met93, and Thr94. Previous studies under typical denaturing conditions, including high-pH values and the presence of exogenous ligands, have shown that the detachment of the Met axial ligand is a basic step in the folding/unfolding process of c-type cytochromes. The ammonia adduct represents a structural model for this important step of the unfolding pathway. Factors proposed to be important for the methionine dissociation are the strength of the H-bond between the Met93 and Tyr66 residues that stabilizes the native form, and the presence in this bacterial cytochrome c2 of the rare six-residue insertion in the helix 310 conformation that increases Met loop flexibility. [source] Redox signalling in cardiovascular diseasePROTEOMICS - CLINICAL APPLICATIONS, Issue 6 2008Rebecca 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] Nitrite reduction: a ubiquitous function from a pre-aerobic pastBIOESSAYS, Issue 8 2009Francesca Cutruzzolà Abstract In eukaryotes, small amounts of nitrite confer cytoprotection against ischemia/reperfusion-related tissue damage in vivo, possibly via reduction to nitric oxide (NO) and inhibition of mitochondrial function. Several hemeproteins are involved in this protective mechanism, starting with deoxyhemoglobin, which is capable of reducing nitrite. In facultative aerobic bacteria, such as Pseudomonas aeruginosa, nitrite is reduced to NO by specialized heme-containing enzymes called cd1 nitrite reductases. The details of their catalytic mechanism are summarized below, together with a hypothesis on the biological role of the unusual d1 -heme, which, in the reduced state, shows unique properties (very high affinity for nitrite and exceptionally fast dissociation of NO). Our results support the idea that the nitrite-based reactions of contemporary eukaryotes are a vestige of earlier bacterial biochemical pathways. The evidence that nitrite reductase activities of enzymes with different cellular roles and biochemical features still exist today highlights the importance of nitrite in cellular homeostasis. [source] Titanium-Based Molecular Squares and Rectangles: Syntheses by Self-Assembly Reactions of Titanocene Fragments and Aromatic N-HeterocyclesCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2005Susanne Kraft Dr. Abstract This paper reports on the potential of titanium compounds as building blocks for supramolecular polygons. Self-assembly reactions of low-valent titanocene units and N-heterocyclic bridging ligands lead to novel titanium-based supramolecular squares. Pyrazine (3), 4,4,-bipyridine (4), and tetrazine (5) were used as bridging ligands, and the acetylene complexes [Cp2Ti{,2 -C2(SiMe3)2}] (1) and [(tBuCp)2Ti{,2 -C2(SiMe3)2}] (2) as sources of titanocene fragments. Molecular rectangles can be synthesized by stepwise reduction of the titanocene dichlorides [Cp2TiCl2] and [(tBuCp)2TiCl2] and consecutive coordination of two different bridging ligands. The resulting complexes are the first examples of molecular rectangles containing bent metallocene corner units. Single-crystal X-ray analyses of the tetranuclear compounds revealed the geometric properties of the molecular polygons in the solid state. Comparison of bond lengths and angles in coordinated and free ligands reveals the reduced state of the bridging ligand in the low-valent titanium compounds. The syntheses and properties of these novel, highly air- and moisture-sensitive compounds are discussed. [source] | |||||||||||||