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Stoichiometry
Kinds of Stoichiometry Terms modified by Stoichiometry Selected AbstractsACCLIMATION TO VARYING LIGHT QUALITIES: TOWARD THE FUNCTIONAL RELATIONSHIP OF STATE TRANSITIONS AND ADJUSTMENT OF PHOTOSYSTEM STOICHIOMETRYJOURNAL OF PHYCOLOGY, Issue 4 2005Thomas PfannschmidtArticle first published online: 31 AUG 200 No abstract is available for this article. [source] Stoichiometry of endothermy: shifting the quest from nitrogen to carbonECOLOGY LETTERS, Issue 8 2008Marcel Klaassen Abstract For many animals, notably herbivores, plants are often an inadequate food source given the low content of protein and high content of C-rich material. This conception is mainly based on studies on ectotherms. The validity of this conception for endotherms is unclear given their much higher carbon requirements for maintenance energy metabolism than ectotherms. Applying stoichiometric principles, we hypothesized that endotherms can cope with diets with much higher (metabolizable) carbon to nitrogen ratios than ectotherms. Using empirical data on birds, eutherian mammals, marsupials and reptiles, we compiled and compared measurements and allometric equations for energy metabolism as well as nitrogen requirements. Our analysis supports our hypothesis that plants, and especially their leaves, are generally sufficiently rich in nitrogen to fulfil protein demands in endotherms, at least during maintenance conditions, but less so in ectotherms. This has important implications with respect to community functioning and the evolution of endothermy. [source] Nutrition, ecology and nutritional ecology: toward an integrated frameworkFUNCTIONAL ECOLOGY, Issue 1 2009David Raubenheimer Summary 1The science of nutritional ecology spans a wide range of fields, including ecology, nutrition, behaviour, morphology, physiology, life history and evolutionary biology. But does nutritional ecology have a unique theoretical framework and research program and thus qualify as a field of research in its own right? 2We suggest that the distinctive feature of nutritional ecology is its integrative nature, and that the field would benefit from more attention to formalizing a theoretical and quantitative framework for developing this. 3Such a framework, we propose, should satisfy three minimal requirements: it should be nutritionally explicit, organismally explicit, and ecologically explicit. 4We evaluate against these criteria four existing frameworks (Optimal Foraging Theory, Classical Insect Nutritional Ecology, the Geometric Framework for nutrition, and Ecological Stoichiometry), and conclude that each needs development with respect to at least one criterion. 5We end with an initial attempt at assessing the expansion of our own contribution, the Geometric Framework, to better satisfy the criterion of ecological explicitness. [source] Equilibrium and kinetic investigation of the interaction of model palladium(II) complex with biorelevant ligandsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 10 2010Mohamed M. Shoukry Pd(DME)Cl2 complex was synthesized and characterized, where DME is 2-{[2-(dimethylamino)ethyl]-methylamino}ethanol. Stoichiometry and stability constants of the complexes formed between various biologically relevant ligands (amino acids, peptides, DNA constituents, and dicarboxylic acids) and [Pd(DME)(H2O)2]2+ are investigated at 25°C and at constant 0.1 M ionic strength. The effect of dielectric constant of the medium on the stability constant of Pd(DME)-CBDCA complex, where CBDCA is cyclobutanedicarboxylate, is also reported. The concentration distribution diagrams of the various species formed are evaluated. The kinetics of base hydrolysis of amino acid esters coordinated to Pd(DME)2+ complex is investigated. The effect of the temperature on the kinetics of base hydrolysis of glycine methyl ester complex is studied. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 608,618, 2010 [source] Uncatalyzed and ruthenium(III)-catalyzed reaction of acidic chlorite with methylene violetINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2003S. B. Jonnalagadda The kinetics and mechanism of the uncatalyzed and Ru(III)-catalyzed oxidation of methylene violet (3-amino-7-diethylamino-5-phenyl phenazinium chloride) (MV+) by acidic chlorite is reported. With excess concentrations of other reactants, both uncatalyzed and catalyzed reactions had pseudo-first-order kinetics with respect to MV+. The uncatalyzed reaction had first-order dependence on chlorite and H+ concentrations, but the catalyzed reaction had first-order dependence on both chlorite and catalyst, and a fractional order with respect to [H+]. The rate coefficient of the uncatalyzed reaction is (5.72 ± 0.19) M,2 s,1, while the catalytic constant for the catalyzed reaction is (22.4 ± 0.3) × 103 M,1 s,1. The basic stoichiometric equation is as follows: 2MV+ + 7ClO2, + 2H+ = 2P + CH3COOH + 4ClO2 + 3Cl,, where P+ = 3-amino-7-ethylamino-5-phenyl phenazinium-10-N-oxide. Stoichiometry is dependent on the initial concentration of chlorite present. Consistent with the experimental results, pertinent mechanisms are proposed. The proposed 15-step mechanism is simulated using literature; experimental and estimated rate coefficients and the simulated plots agreed well with the experimental curves. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 294,303, 2003 [source] Kinetics and mechanism of the oxidation of 4-methyl-3-thiosemicarbazide by acidic bromate,INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2002Sreekantha B. Jonnalagadda The oxidation of 4-methyl-3-thiosemicarbazide (MTSC) by bromate and bromine was studied in acidic medium. The stoichiometry of the reaction is extremely complex, and is dependent on the ratio of the initial concentrations of the oxidant to reductant. In excess MTSC and after prolonged standing, the stoichiometry was determined to be H3CN(H)CSN(H)NH2 + 3BrO3, , 2CO2 + NH4+ + SO42, + N2 + 3Br, + H+ (A). An interim stoichiometry is also obtained in which one of the CO2 molecules is replaced by HCOOH with an overall stoichiometry of 3H3CN(H)CSN(H)NH2 + 8BrO3, , CO2 + NH4+ + SO42, + HCOOH + N2 + 3Br, + 3H+ (B). Stoichiometry A and B are not very different, and so mixtures of the two were obtained. Compared to other oxidations of thiourea-based compounds, this reaction is moderately fast and is first order in both bromate and substrate. It is autocatalytic in HOBr. The reaction is characterized by an autocatalytic sigmoidal decay in the consumption of MTSC, while in excess bromate conditions the reaction shows an induction period before autocatalytic formation of bromine. In both cases, oxybromine chemistry, which involves the initial formation of the reactive species HOBr and Br2, is dominant. The reactions of MTSC with both HOBr and Br2 are fast, and so the overall rate of oxidation is dependent upon the rates of formation of these reactive species from bromate. Our proposed mechanism involves the initial cleavage of the CN bond on the azo-side of the molecule to release nitrogen and an activated sulfur species that quickly and rapidly rearranges to give a series of thiourea acids. These thiourea acids are then oxidized to the sulfonic acid before cleavage of the CS bond to give SO42,, CO2, and NH4+. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 237,247, 2002 [source] Stoichiometry of Tyrosine Hydroxylase Phosphorylation in the Nigrostriatal and Mesolimbic Systems In VivoJOURNAL OF NEUROCHEMISTRY, Issue 1 2000Effects of Acute Haloperidol, Related Compounds Abstract ; Electrical stimulation of the medial forebrain bundle increases 32P incorporation into striatal tyrosine hydroxylase (TH) at Ser 19, Ser31, and Ser40. In the present studies, the effects of acute haloperidol and related drugs on sitespecific TH phosphorylation stoichiometry (PS) in the nigrostriatal and mesolimbic systems were determined by quantitative blot immunolabeling using phosphorylation statespecific antibodies. The striatum (Str), substantia nigra (SN), nucleus accumbens (NAc), and ventral tegmental area (VTA) from Sprague-Dawley rats were harvested 30-40 min after a single injection of either vehicle, haloperidol (2 mg/kg), raclopride (2 mg/kg), clozapine (30 mg/kg), or SCH23390 (0.5 mg/kg). In vehicle-injected control rats, Ser19 PS was 1.5- to 2.5-fold lower in Str and NAc than in SN and VTA, Ser31 PS was two-to fourfold higher in Str and NAc than in SN and VTA, and Ser40 PS was similar between the terminal field and cell body regions. After haloperidol, Ser40 PS increased twofold in Str and NAc, whereas a smaller increase in SN and VTA was observed. The effects of haloperidol on Ser19 PS were similar to those on Ser40 in each region ; however, haloperidol treatment increased Ser31 PS at least 1.6-fold in all regions. The effects of raclopride on TH PS were comparable to those of haloperidol, whereas clozapine treatment increased TH PS at all sites in all regions. By contrast, the effects of SCH23390 on TH PS were relatively small and restricted to the NAc. The stoichiometries of site-specific TH phosphorylation in vivo are presented for the first time. The nigrostriatal and mesolimbic systems have common features of TH PS, distinguished by differences in TH PS between the terminal field and cell body regions and by dissimilar increases in TH PS in the terminal field and cell body regions after acute haloperidol. [source] A Soft Chemistry Route for the Synthesis of Nanostructured Pb2Ru2O6.5 with a Controlled StoichiometryJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2008Vincenzo Esposito A new chemical route to synthesize nanostructured lead ruthenium pyrochlore (Pb2Ru2O6.5) powders was developed. The synthesis was performed starting from a metal nitrate aqueous solution and N, N, N,, N, tetramethylethylendiamine (TMEDA). The amine, which is a mild basic chelating agent, was able to control the simultaneous precipitation of lead and ruthenium oxo/hydroxides. For the sake of comparison, Pb2Ru2O6.5 powders were prepared using the more conventional polymeric precursor method. The new method was effective for the synthesis of nanostructured Pb2Ru2O6.5 powders already stable at 400°C and up to 1000°C. [source] Nickel-Ion-Mediated Control of the Stoichiometry of His-Tagged Protein/Nanoparticle InteractionsMACROMOLECULAR BIOSCIENCE, Issue 2 2009Mrinmoy De Abstract The interaction between synthetic materials and biomolecules plays an important role in biomedical and pathological sciences. An important issue in these interactions is control of stoichiometry. The interaction between NTA ligands and proteins with six consecutive His residues has been widely used for protein purification. Control of stoichiometry is an important issue in applying this recognition strategy to the creation of defined nanoparticle-protein conjugates. In this communication we report the direct control of particle-protein stoichiometry through variation of nickel chloride concentration, as demonstrated through fluorescence and gel electrophoresis. [source] Pharaonis Phoborhodopsin Binds to its Cognate Truncated Transducer Even in the Presence of a Detergent with a 1:1 Stoichiometry,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 3 2001Yuki Sudo ABSTRACT Pharaonis phoborhodopsin (ppR) (also pharaonis sensory rhodopsin II) is a receptor of the negative phototaxis of Natronobacterium pharaonis.ppR forms a complex with its pharaonis halobacterial transducer (pHtrII), and this complex transmits the light signal to the sensory system in the cytoplasm. The expressed C-terminal-His tagged ppR and C-terminal-His tagged truncated pHtrII (t-Htr) in Escherichia coli (His means the 6× histidine tag) form a complex even in the presence of 0.1% of n -dodecyl-,- d -maltoside, and the M-decay of the complex became about twice slower than that of ppR alone. The photocycling rates under varying concentration ratios of ppR to t-Htr in the presence of detergent were measured. The data were analyzed on the following assumptions: (1) the M-decay of both ppR alone and the complex followed a single exponential decay with different time constants; and (2) the M-decay under varying concentration ratios of ppR to t-Htr, therefore, followed a biexponential decay function which combined the decay of the free ppR and that of the complex as photoreactive species. From these analyses we estimated the dissociation constant (15.2 ± 1.8 ,M) and the number of binding sites (1.2 ± 0.08). [source] Nutrient Limitation and Stoichiometry of Carnivorous PlantsPLANT BIOLOGY, Issue 6 2006A. M. Ellison Abstract: The cost-benefit model for the evolution of carnivorous plants posits a trade-off between photosynthetic costs associated with carnivorous structures and photosynthetic benefits accrued through additional nutrient acquisition. The model predicts that carnivory is expected to evolve if its marginal benefits exceed its marginal costs. Further, the model predicts that when nutrients are scarce but neither light nor water is limiting, carnivorous plants should have an energetic advantage in competition with non-carnivorous plants. Since the publication of the cost-benefit model over 20 years ago, marginal photosynthetic costs of carnivory have been demonstrated but marginal photosynthetic benefits have not. A review of published data and results of ongoing research show that nitrogen, phosphorus, and potassium often (co-)limit growth of carnivorous plants and that photosynthetic nutrient use efficiency is 20 - 50 % of that of non-carnivorous plants. Assessments of stoichiometric relationships among limiting nutrients, scaling of leaf mass with photosynthesis and nutrient content, and photosynthetic nutrient use efficiency all suggest that carnivorous plants are at an energetic disadvantage relative to non-carnivorous plants in similar habitats. Overall, current data support some of the predictions of the cost-benefit model, fail to support others, and still others remain untested and merit future research. Rather than being an optimal solution to an adaptive problem, botanical carnivory may represent a set of limited responses constrained by both phylogenetic history and environmental stress. [source] Stoichiometry of lipid interactions with transmembrane proteins,Deduced from the 3D structuresPROTEIN SCIENCE, Issue 5 2006Tibor Páli Abstract The stoichiometry of the first shell of lipids interacting with a transmembrane protein is defined operationally by the population of spin-labeled lipid chains whose motion is restricted directly by the protein. Interaction stoichiometries have been determined experimentally for a wide range of ,-helical integral membrane proteins by using spin-label ESR spectroscopy. Here, we determine the spatially defined number of first-shell lipids at the hydrophobic perimeter of integral membrane proteins whose 3D structure has been determined by X-ray crystallography and lipid,protein interactions characterized by spin-labeling. Molecular modeling is used to build a single shell of lipids surrounding transmembrane structures derived from the PDB. Constrained energy optimization of the protein,lipid assemblies is performed by molecular mechanics. For relatively small proteins (up to 7,12 transmembrane helices), the geometrical first shell corresponds to that defined experimentally by perturbation of the lipid-chain dynamics. For larger, multi-subunit ,-helical proteins, the lipids perturbed directly by the protein may either exceed or be less in number than those that can be accommodated at the intramembranous perimeter. In these latter cases, the motionally restricted spin-labeled lipids can be augmented by intercalation, or can correspond to a specific subpopulation at the protein interface, respectively. For monomeric ,-barrel proteins, the geometrical lipid stoichiometry corresponds to that determined from lipid mobility for a 22-stranded barrel, but fewer lipids are motionally restricted than can be accommodated around an eight-stranded barrel. Deviations from the geometrical first shell, in the ,-barrel case, are for the smaller protein with a highly curved barrel. [source] Growth Phase and Elemental Stoichiometry of Bacterial Prey Influences Ciliate Grazing SelectivityTHE JOURNAL OF EUKARYOTIC MICROBIOLOGY, Issue 5 2009DAVID F. GRUBER ABSTRACT. Protozoa are known to selectively graze bacteria and can differentiate prey based on size and viability, but less is known about the effects of prey cellular composition on predator selectivity. We measured the effect of growth phase and elemental stoichiometry of Escherichia coli on grazing by two ciliates, Euplotes vannus and Cyclidium glaucoma. Bacterial cells of a single strain were transformed with green and red fluorescent protein and harvested from culture at differing growth stages. Cells in exponential growth phase had low carbon:phosphorus (39) and nitrogen:phosphorus (9) ratios, while cells from stationary phase had high carbon:phosphorus of 104 and nitrogen:phosphorus of 26. When offered an equal mixture of both types of bacteria, Cyclidium grazed stationary phase, high carbon:phosphorus, high nitrogen:phosphorus cells to 22% of initial abundance within 135 min, while Euplotes reduced these cells to 33%. Neither ciliate species decreased the abundance of the exponential phase cells, lower carbon:phosphorus and nitrogen:phosphorus, relative to control treatments. Because protozoa have higher nitrogen:phosphorus and carbon:phosphorus ratios than their prokaryotic prey, this study raises the possibility that it may be advantageous for protozoa to preferentially consume more slowly growing bacteria. [source] Stoichiometry of a pore mutation that abolishes picrotoxin-mediated antagonism of the GABAA receptorTHE JOURNAL OF PHYSIOLOGY, Issue 2 2006Anna Sedelnikova Picrotoxin, a potent antagonist of the inhibitory central nervous system GABAA and glycine receptors, is believed to interact with residues that line the central ion pore. These pore-lining residues are in the second transmembrane domain (TM2) of each of the five constituent subunits. One of these amino acids, a threonine at the 6, location, when mutated to phenylalanine, abolishes picrotoxin sensitivity. It has been suggested that this threonine, via hydrogen bonding, directly interacts with the picrotoxin molecule. We previously demonstrated that this mutation, in the ,, , or , subunit, can impart picrotoxin resistance to the GABA receptor. Since the functional pentameric GABA receptor contains two , subunits, two , subunits and one , subunit, it is not clear how many , and , subunits must carry this mutation to impart the resistant phenotype. In this study, by coexpression of mutant , or , subunits with their wild-type counterparts in various defined ratios, we demonstrate that any single subunit carrying the 6, mutation imparts picrotoxin resistance. Implications of this finding in terms of the mechanism of antagonism are considered. [source] A DNA Nanostructure for the Functional Assembly of Chemical Groups with Tunable Stoichiometry and Defined Nanoscale GeometryANGEWANDTE CHEMIE, Issue 48 2009Nick Mitchell No abstract is available for this article. [source] Variable Stoichiometry during the Laccase-Catalyzed Oxidation of Aqueous PhenolBIOTECHNOLOGY PROGRESS, Issue 2 2007Selvia Kurniawati The oxidation of aqueous phenol through the catalytic action of laccase from Trametes versicolor was studied over a wide range of phenol concentrations and enzyme activities. The stoichiometric ratio, which is defined as the molar ratio of phenol transformed to oxygen consumed in the catalytic reaction, was found to increase with phenol concentration in the reaction mixture from a theoretical lower limit of 1 and to approach a theoretical upper limit of 4. A logistic equation was proposed to relate reaction stoichiometry to substrate concentration and was successfully used to relate these parameters over a range of phenol concentrations extending from approximately 0.15 to 8 mM. This expression was incorporated into two kinetic models in order to account for variations in reaction stoichiometry during the reaction and to extend the range over which the models may be accurately applied. The new models demonstrated an improved ability to predict concentrations of phenol and oxygen over time in a closed batch reaction system. [source] ChemInform Abstract: Direct Synthesis of Powdery Inorganic Electride [Ca24Al28O64] 4+(e - )4 and Determination of Oxygen Stoichiometry.CHEMINFORM, Issue 39 2009Satoru Matsuishi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 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] ChemInform Abstract: Stoichiometry and Structure of Uranyl(VI) Hydroxo Dimer and Trimer Complexes in Aqueous Solution.CHEMINFORM, Issue 10 2008Satoru Tsushima Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 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] Tuning the Oxidation Properties of Vanadium(V) Through Ligand Stoichiometry.CHEMINFORM, Issue 47 2006Wei Zeng Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Stereoselective Synthesis of Functionalized Triol Units by SnCl4 Promoted Allylation of ,-Benzyloxyaldehydes: Crucial Role of the Stoichiometry of the Lewis Acid.CHEMINFORM, Issue 49 2004Christophe Dubost Abstract For Abstract see ChemInform Abstract in Full Text. [source] Influence of the Base Stoichiometry on Cyclocondensation of N-(2-Bromoethyl)phthalimide with Lithium Ester Enolates.CHEMINFORM, Issue 2 2003M. Calmes Abstract For Abstract see ChemInform Abstract in Full Text. [source] Study of binding stoichiometries of the human immunodeficiency virus type,1 reverse transcriptase by capillary electrophoresis and laser-induced fluorescence polarization using aptamers as probesELECTROPHORESIS, Issue 2 2006Hao Fu Abstract Binding stoichiometries between four DNA aptamers (RT12, RT26, RTlt49, and ODN93) and the reverse transcriptase (RT) of the type,1 human immunodeficiency virus (HIV-1) were studied using affinity CE (ACE) coupled with LIF polarization and fluorescence polarization (FP). The ACE/LIF study showed evidence of two binding stoichiometries between the HIV-1,RT protein and aptamers RT12, RT26, and ODN93, suggesting that these aptamers can bind to both the p66 and p51 subunits of the HIV-1,RT. Only one binding stoichiometry for aptamer RTlt49 was found. The affinity complexes were easily separated from the unbound aptamers; however, the different stoichiometries were not well resolved. A complementary technique, FP, was able to provide additional information about the binding and supporting evidence for the ACE/LIF results. The ACE/LIFP study also revealed that the FP values of the 1:1 complexes of the HIV-1,RT protein with aptamers RT12, RT26, and ODN93 were always much greater than those of the 1:2 complexes. This was initially surprising because the larger molecular size of the 1:2 complexes was expected to result in higher FP values than the corresponding 1:1 complexes. This phenomenon was probably a result of fluorescence resonance energy transfer between the two fluorescent molecules bound to the HIV-1,RT protein. [source] The Role of Functionalisation, Asymmetry and Shape of a New Macrocyclic Compartmental Ligand in the Formation of Mononuclear, Homo- and Heterodinuclear Lanthanide(III) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2009Sergio Tamburini Abstract The compartmental [1+1] macrocycle H3L, obtained by self-condensation of the formyl precursor 3,3,-(3,6-dioxaoctane-1,8-diyldioxy)bis(2-hydroxybenzaldehyde) with the amine precursor N,N -bis(2-aminoethyl)-2-hydroxybenzylamine, contains one inner ON3O2 Schiff base and one outer O2O4 crown-like chamber. According to the experimental conditions it forms, by a template process, the stable mononuclear complexes Ln(H3L)(Cl)2(CH3COO)·nS·mHCl or [Ln(L)]·nS (Ln = La, Lu, Y, Yb, Er, Dy, Tb, Gd, Eu, Ce) with the lanthanide(III) ion encapsulated in the crown-ether-like and in the Schiff base site. The mononuclear complexes Ln(H3L)(Cl)2(CH3COO)·nS·mHCl, by further complexation with a different lanthanide(III) ion, give rise to the related heterodinuclear complexes [LnLn,(L)(Cl)2(CH3COO)]·nS while the homodinuclear and the heterodinuclear complexes [Ln2(L)](Cl)3·nH2O and [LnLn,(L)](Cl)3·nS could be prepared by a template reaction using the appropriate molar ratio of reactants. Their properties have been studied by using SEM-EDS microscopy, IR and NMR spectroscopy and their compositions confirmed by thermal and ESI-Mass spectrometric analyses. In the heterodinuclear complexes, the site occupancy of the different lanthanide(III) ions was determined by 1H and 13C NMR spectroscopy in CD3OD or (CD3)2SO , it was found that heterodinuclear complexation occurs in methanol with the smaller lanthanide(III) ion mainly coordinating to the Schiff base site and the larger lanthanide(III) ion to the crown site whereas, in dimethyl sulfoxide, demetalation of the weaker coordinated lanthanide(III) ion into the crown ether chamber occurs with the subsequent formation of mononuclear species in solution. The thermal decomposition of the heterodinuclear complexes forms the related mixed oxides, the stoichiometries and properties of which were determined by SEM-EDS microscopy and X-ray powder diffraction studies (XRD). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Structural evidence for a constant c11 ring stoichiometry in the sodium F-ATP synthaseFEBS JOURNAL, Issue 21 2005Thomas Meier The Na+ -dependent F-ATP synthases of Ilyobacter tartaricus and Propionigenium modestum contain membrane-embedded ring-shaped c subunit assemblies with a stoichiometry of 11. Subunit c from either organism was overexpressed in Escherichia coli using a plasmid containing the corresponding gene, extracted from the membrane using detergent and then purified. Subsequent analyses by SDS/PAGE revealed that only a minor portion of the c subunits had assembled into stable rings, while the majority migrated as monomers. The population of rings consisted mainly of c11, but more slowly migrating assemblies were also found, which might reflect other c ring stoichiometries. We show that they consisted of higher aggregates of homogeneous c11 rings and/or assemblies of c11 rings and single c monomers. Atomic force microscopy topographs of c rings reconstituted into lipid bilayers showed that the c ring assemblies had identical diameters and that stoichiometries throughout all rings resolved at high resolution. This finding did not depend on whether the rings were assembled into crystalline or densely packed assemblies. Most of these rings represented completely assembled undecameric complexes. Occasionally, rings lacking a few subunits or hosting additional subunits in their cavity were observed. The latter rings may represent the aggregates between c11 and c1, as observed by SDS/PAGE. Our results are congruent with a stable c11 ring stoichiometry that seems to not be influenced by the expression level of subunit c in the bacteria. [source] The effects of physiologically important nonmetallic ligands in the reactivity of metallothionein towards 5,5,-dithiobis(2-nitrobenzoic acid)FEBS JOURNAL, Issue 18 2001A new method for the determination of ligand interactions with metallothionein The reaction of Cd5Zn2 -metallothionein (MT) with 5,5,-dithiobis(2-nitrobenzoic acid) (Nbs2) has been studied at different reagent stoichiometries, pH and temperature conditions and in the presence of several ligands. At stoichiometries of Nbs2 to MT from 0.5 to 5, the reaction followed first order kinetics. The first order rate constants obtained were independent from the concentration of Nbs2 but were linearly dependent on the concentration of MT. At higher Nbs2/MT stoichiometries, the reaction deviates from first order kinetics and the observed rate constant increases. The reactivity of MT towards Nbs2 has been probed at 4 µm concentration of both reagents where the reaction is monophasic and is characterized by a linear Arrhenius plot (Ea = 45.8 ± 2.7 kJ·mol,1). It has been demonstrated that metal release at low pH or subtraction from MT by EDTA substantially increases the reactivity of MT towards Nbs2. At the same time, a number of nonmetallic ligands moderately accelerate the reaction of MT with Nbs2 and hyperbolic dose,response curves were obtained. The data have been interpreted with the binding of ligands to MT and following MT. Ligand binding constants were calculated as follows: ATP, K = 0.31 ± 0.06 mm; ADP, K = 0.26 ± 0.07 mm. Several compounds such as AMP, S -methylglutathione, and phosphate had no effect on the reaction, but Zn2+ ions showed an inhibitory effect at micromolar concentrations. [source] Experimental measurements and kinetic modeling of CH4/O2 and CH4/C2H6/O2 conversion at high pressure,INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2008Christian Lund Rasmussen A detailed chemical kinetic model for homogeneous combustion of the light hydrocarbon fuels CH4 and C2H6 in the intermediate temperature range roughly 500,1100 K, and pressures up to 100 bar has been developed and validated experimentally. Rate constants have been obtained from critical evaluation of data for individual elementary reactions reported in the literature with particular emphasis on the conditions relevant to the present work. The experiments, involving CH4/O2 and CH4/C2H6/O2 mixtures diluted in N2, have been carried out in a high-pressure flow reactor at 600,900 K, 50,100 bar, and reaction stoichiometries ranging from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Finally, the mechanism was extended with a number of reactions important at high temperature and tested against data from shock tubes, laminar flames, and flow reactors. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 778,807, 2008 [source] Multiple Kv1.5 targeting to membrane surface microdomains,JOURNAL OF CELLULAR PHYSIOLOGY, Issue 3 2008Ramón Martínez-Mármol Surface expression of voltage-dependent K+ channels (Kv) has a pivotal role in leukocyte physiology. Although little is known about the physiological role of lipid rafts, these microdomains concentrate signaling molecules and their ion channel substrates. Kv1.3 associates with Kv1.5 to form functional channels in macrophages. Different isoform stoichiometries lead to distinct heteromeric channels which may be further modulated by targeting the complex to different membrane surface microdomains. Kv1.3 targets to lipid rafts, whereas Kv1.5 localization is under debate. With this in mind, we wanted to study whether heterotetrameric Kv1.5-containing channels target to lipid rafts. While in transfected HEK-293 cells, homo- and heterotetrameric channels targeted to rafts, Kv1.5 did not target to rafts in macrophages. Therefore, Kv1.3/Kv1.5 hybrid channels are mostly concentrated in non-raft microdomains. However, LPS-induced activation, which increases the Kv1.3/Kv1.5 ratio and caveolin, targeted Kv1.5 back to lipid rafts. Moreover, Kv1.5 did not localize to low-buoyancy fractions in L6E9 skeletal myoblasts, which also coexpress both channels, heart membranes or cardiomyocyes. Coexpression of a Cav3DGV -mutant confined Kv1.5 to Cav3DGV -vesicles of HEK cells. Contrarily, coexpression of Kv,2.1 impaired the Kv1.5 targeting to raft microdomains in HEK cells. Our results indicate that Kv1.5 partnership interactions are underlying mechanisms governing channel targeting to lipid rafts. J. Cell. Physiol. 217: 667,673, 2008. © 2008 Wiley-Liss, Inc. [source] Solvent extraction studies of Sm(III) from nitrate medium and separation factors of rare earth elements with mixtures of sec -octylphenoxyacetic acid and 1,10-phenthrolineJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2010Shujuan Fan Abstract BACKGROUND: Liquid,liquid extraction is widely used for the separation of rare earths, among which synergistic extraction has attracted more and more attention. Numerous types of synergistic extraction systems have been applied to rare earths with high extraction efficiency and selectivities. In the present study, mixtures of sec -octylphenoxyacetic acid (CA12, H2A2) and 1,10-phenanthroline (phen, B) have been used for the extraction of rare earths from nitrate medium. The stoichiometry of samarium(III) extraction has been studied using the methods of slope analysis and constant molar ratio. The possibility of using synergistic extraction effects to separate rare earths has also been studied. RESULTS: Mixtures of CA12 and phen display synergistic effects in the extraction of rare earth elements giving maximum enhancement coefficients of 5.5 (La); 13.7 (Nd); 15.9 (Sm); 24.5 (Tb); 45.4 (Yb) and 12.3 (Y). Samarium(III) is extracted as SmHA4B3 with mixtures of CA12 and phen instead of SmHA4 when extracted with CA12 alone. The calculated logarithm of the equilibrium constant is 6.0 and the thermodynamic functions, ,H, ,G, and ,S, have been calculated as 4.3 kJ mol,1, , 33.7 kJ mol,1 and 129.7 J mol,1 K,1, respectively. CONCLUSION: Mixtures of CA12 and phen exhibit synergistic effects on rare earth elements. Graphical and numerical methods have been successfully used to determine their stoichiometries. The different synergistic effects may provide the possibility of separating yttrium from heavy lanthanoids at an appropriate ratio of CA12 and phen. Copyright © 2010 Society of Chemical Industry [source] Extraction equilibria and separation of phenylalanine and aspartic acid from water with di(2-ethylhexyl)phosphoric acidJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 3 2006Su-Hsia Lin Abstract The distribution equilibria of single and binary L -phenylalanine and L -aspartic acid between water and a kerosene solution of di(2-ethylhexyl)phosphoric acid (D2EHPA) were studied. It was shown that the distribution ratios of phenylalanine generally increased with increasing aqueous pH (2,5) in the D2EHPA concentration range 0.1,0.5 mol dm,3, but those of aspartic acid decreased with increasing solution pH. Different reaction stoichiometries were proposed for the extraction of phenylalanine and aspartic acid under the conditions studied. The extraction equilibrium constants were obtained. Competitive extraction in binary systems was more apparent in the pH range where the cationic form of amino acids was not predominant. The present results indicated that selective separation of phenylalanine to aspartic acid was possible with this cationic extractant when they were extracted at higher pH and stripped using higher acidity of HCl solution. Copyright © 2006 Society of Chemical Industry [source] Modeling l-dopa purification by chiral ligand-exchange chromatographyAICHE JOURNAL, Issue 3 2007Nooshafarin Sanaie Abstract A model describing elution-band profiles that combines multiple chemical equilibria theory with the nonideal equilibrium,dispersion equation for solute transport is used to predict and characterize the separation of l,d-dopa by chiral ligand-exchange chromatography (CLEC). Formation constants and stoichiometries for all equilibrium complexes formed in the interstitial volume and pore liquid are taken from standard thermodynamic databases and independent potentiometric titration experiments. Formation constants for complexes formed with the stationary phase ligand (N-octyl-3-octylthio-d-valine) are determined from potentiometric titration data for a water-soluble analogue of the ligand. This set of pure thermodynamic parameters is used to calculate the spatially discretized composition of each column volume element as a function of time. The model includes a temperature-dependent pure-component parameter, determined by regression to a single elution band for the pure component, that corrects for subtle effects associated with immobilizing the N-octyl-3-octylthio-d-valine ligand onto the stationary phase. The model is shown to accurately predict elution chromatograms and separation performance as a function of key column operating variables. The model is then used to better understand the connection between chemical equilibria within the system and changes in band profiles and band separation resulting from changes in column operating conditions. © 2007 American Institute of Chemical Engineers AIChE J, 2007 [source] | ||||||||||||||||||||||||||||||||||||||||||||||