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Free Energy Changes (free + energy_change)
Kinds of Free Energy Changes Selected AbstractsBioenergetics of the formyl-methanofuran dehydrogenase and heterodisulfide reductase reactions in Methanothermobacter thermautotrophicusFEBS JOURNAL, Issue 1 2003Linda M. I. De Poorter The synthesis of formyl-methanofuran and the reduction of the heterodisulfide (CoM-S-S-CoB) of coenzyme M (HS-CoM) and coenzyme B (HS-CoB) are two crucial, H2 -dependent reactions in the energy metabolism of methanogenic archaea. The bioenergetics of the reactions in vivo were studied in chemostat cultures and in cell suspensions of Methanothermobacter thermautotrophicus metabolizing at defined dissolved hydrogen partial pressures (,pH2). Formyl-methanofuran synthesis is an endergonic reaction (,G°, = +16 kJ·mol,1). By analyzing the concentration ratios between formyl-methanofuran and methanofuran in the cells, free energy changes under experimental conditions (,G,) were found to range between +10 and +35 kJ·mol,1 depending on the pH2 applied. The comparison with the sodium motive force indicated that the reaction should be driven by the import of a variable number of two to four sodium ions. Heterodisulfide reduction (,G°, = ,40 kJ·mol,1) was associated with free energy changes as high as ,55 to ,80 kJ·mol,1. The values were determined by analyzing the concentrations of CoM-S-S-CoB, HS-CoM and HS-CoB in methane-forming cells operating under a variety of hydrogen partial pressures. Free energy changes were in equilibrium with the proton motive force to the extent that three to four protons could be translocated out of the cells per reaction. Remarkably, an apparent proton translocation stoichiometry of three held for cells that had been grown at pH2<0.12 bar, whilst the number was four for cells grown above that concentration. The shift occurred within a narrow pH2 span around 0.12 bar. The findings suggest that the methanogens regulate the bioenergetic machinery involved in CoM-S-S-CoB reduction and proton pumping in response to the environmental hydrogen concentrations. [source] Characterization of interaction between doxycycline and human serum albumin by capillary electrophoresis-frontal analysisELECTROPHORESIS, Issue 11 2009Hanwen Sun Abstract The binding of doxycycline to HSA under simulated physiological conditions (pH 7.4, 67,mM phosphate, I=0.17, drug concentration 100,,M, HSA concentration up to 475,,M, 36.5°C) was studied by CE-frontal analysis. The number of primary binding sites, binding constant and physiological protein-binding percentage were 1.9, 1.51×103,M,1 and 59.80%, respectively. In addition, the thermodynamic parameters including enthalpy change (,H), entropy change (,S) and free energy change (,G) of the reaction were obtained in order to characterize the acting forces between doxycycline and HSA. Furthermore, to better understand the nature of doxycycline,HSA binding and to get information about potential interaction with other drugs, displacement experiments were performed. The results showed that doxycycline binds at site II of HSA. [source] Solubilities and surface activities of phthalates investigated by surface tension measurementsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2001Marianne Thomsen Abstract Aueous solutions of DEP (di-ethyl), DnBP (di- n -butyl), DnH(6)P (di- n -hexyl), and DEHP (di-[2-ethyl-hexyl])phthalates have been investigated by use of surface tension measurements at temperatures between 10 and 35°C. A tensiometric approach allows for the determination of unimeric solubilities and ,G°, which is the standard Gibbs free energy change, for the dissolution of phthalates in water. The unimeric solubility of the phthalates increase with decreasing temperature. The ,G° shows a linear increase with increasing phthalate alkyl chain length. The contribution of enthalpy (,H°) and entropy (,S°) to ,G° were calculated from the temperature-dependent solubilities. The contributions of both ,H° and ,S° are negative and increase in magnitude with increasing alkyl chain length, suggesting hydrophobic interactions between phthalates and water. The ability of different phthalates to lower the surface tension decreases with increasing alkyl chain length, whereas the relative affinity for adsorption in the air-water interface increases drastically for long-chain phthalates. Despite the low surface activity of phthalates compared with that of common surfactants, they show significant affinity for adsorption in air-water interfaces of natural surface waters. This property, combined with their low solubilities, may affect the fate of these compounds within the natural environment, because they form emulsions above unimeric saturation in aqueous media. [source] Thermodynamics of the folding of D-glyceraldehyde-3-phosphate dehydrogenase assisted by protein disulfide isomerase studied by microcalorimetryFEBS JOURNAL, Issue 15 2001Yi Liang Thermodynamics of the refolding of denatured d -glyceraldehyde 3-phosphate dehydrogenase (GAPDH) assisted by protein disulfide isomerase (PDI), a molecular chaperone, has been studied by isothermal microcalorimetry at different molar ratios of PDI/GAPDH and temperatures using two thermodynamic models proposed for chaperone,substrate binding and chaperone-assisted substrate folding, respectively. The binding of GAPDH folding intermediates to PDI is driven by a large favorable enthalpy decrease with a large unfavorable entropy reduction, and shows strong enthalpy,entropy compensation and weak temperature dependence of Gibbs free energy change. A large negative heat-capacity change of the binding, ,156 kJ·mol,1·K,1, at all temperatures examined indicates that hydrophobic interaction is a major force for the binding. The binding stoichiometry shows one dimeric GAPDH intermediate per PDI monomer. The refolding of GAPDH assisted by PDI is a largely exothermic reaction at 15.0,25.0 °C. With increasing temperature from 15.0 to 37.0 °C, the PDI-assisted reactivation yield of denatured GAPDH upon dilution decreases. At 37.0 °C, the spontaneous reactivation, PDI-assisted reactivation and intrinsic molar enthalpy change during the PDI-assisted refolding of GAPDH are not detected. [source] Synthesis, characterization, and kinetic of thermal degradation of oligo-2-[(4-bromophenylimino)methyl]phenol and oligomer-metal complexesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2009smet Kaya Abstract Oligo-2-[(4-bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2-[(4-bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet,visible spectrophotometer (UV,vis), 1H-NMR, and 13C-NMR analyses. The characterization was made by TG-DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer-metal complexes with Co+2, Ni+2, and Cu+2 ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats-Redfern, MacCallum-Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (Ea), the reaction order (n), preexponential factor (A), the entropy change (,S*), enthalpy change (,H*), and free energy change (,G*) obtained by earlier-mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Kinetic and thermodynamic characterization of HIV-1 protease inhibitorsJOURNAL OF MOLECULAR RECOGNITION, Issue 2 2004Cynthia F. Shuman Abstract Interaction kinetic and thermodynamic analyses provide information beyond that obtained in general inhibition studies, and may contribute to the design of improved inhibitors and increased understanding of molecular interactions. Thus, a biosensor-based method was used to characterize the interactions between HIV-1 protease and seven inhibitors, revealing distinguishing kinetic and thermodynamic characteristics for the inhibitors. Lopinavir had fast association and the highest affinity of the tested compounds, and the interaction kinetics were less temperature-dependent as compared with the other inhibitors. Amprenavir, indinavir and ritonavir showed non-linear temperature dependencies of the kinetics. The free energy, enthalpy and entropy (,G, ,H, ,S) were determined, and the energetics of complex association (,Gon, ,Hon, ,Son) and dissociation (,Goff, ,Hoff, ,Soff) were resolved. In general, the energetics for the studied inhibitors was in the same range, with the negative free energy change (,G,<,0) due primarily to increased entropy (,S,>,0). Thus, the driving force of the interaction was increased degrees of freedom in the system (entropy) rather than the formation of bonds between the enzyme and inhibitor (enthalpy). Although the ,Gon and ,Goff were in the same range for all inhibitors, the enthalpy and entropy terms contributed differently to association and dissociation, distinguishing these phases energetically. Dissociation was accompanied by positive enthalpy (,Hoff,>,0) and negative entropy (,Soff,<,0) changes, whereas association for all inhibitors except lopinavir had positive entropy changes (,Son,>,0), demonstrating unique energetic characteristics for lopinavir. This study indicates that this type of data will be useful for the characterization of target,ligand interactions and the development of new inhibitors of HIV-1 protease. Copyright © 2004 John Wiley & Sons, Ltd. [source] Influence of Grafting on the Solution Properties and the Dissociation Behavior of Ionic/Nonionic Grafted CopolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2007Jens Weber Abstract A new synthetic approach towards grafted terpolymers based on a poly[(methyl vinyl ether)- alt -(maleic anhydride)] backbone and poly(ethylene glycol) monomethyl ether (MPEG) side chains is presented. Resulting comb polymers with controllable grafting degree still have highly reactive anhydride moieties along the polymer backbone, as proved by IR spectroscopy. Grafting degree depends on the anhydride hydroxide stoichiometric ratio. It is not influenced by the molecular weight of MPEG. An increase in the grafting degree leads to a contraction of the polymer in the solution. Evaluation of potentiometric titration data gave a deeper insight into the dissociation process. The copolymers showed a two-step dissociation behavior. No significant influence of the grafting degree on the acidic strength was observed, whilst there is a strong effect of the grafting degree on the free energy change upon neutralization ,Gel. Grafting leads to a higher change in free energy ,Gel,1 for the first step but to lower ,Gel,2 required for the second step. [source] Photophysics in Motionally constrained Bioenvironment: Interactions of Norharmane with Bovine Serum Albumin,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2005Arabinda Mallick ABSTRACT Steady-state photophysics of norharmane (NHM), a bioactive alkaloid, has been studied in the presence of a model transport protein, bovine serum albumin (BSA). The emission spectrum undergoes a remarkable change upon addition of BSA to the aqueous solution of NHM in buffer. Addition of BSA leads to a marked increase in the fluorescence anisotropy of the neutral species of NHM, although the fluorescence anisotropy for the cationic species is almost invariant to BSA addition, suggesting that the neutral species is located in a motionally restricted environment of BSA, whereas the cationic species remains in the bulk aqueous phase. The binding constant (K) and free energy change (,G) for the probe-protein binding have been calculated from the fluorescence data. Light has been thrown on the action of urea on protein-bound NHM. The denaturation study suggests that the protein, in its native form, binds with NHM. Polarity of the microenvironment around the probe has been determined from a comparison of the fluorescence properties of the two prototropic species of NHM in water-dioxane mixture with varying composition. [source] Hexavalent uranium supports growth of Anaeromyxobacter dehalogenans and Geobacter spp. with lower than predicted biomass yieldsENVIRONMENTAL MICROBIOLOGY, Issue 11 2007Robert A. Sanford Summary The stimulation of bacteria capable of reducing soluble U(VI) to sparingly soluble U(IV) is a promising approach for containing U(VI) plumes. Anaeromyxobacter dehalogenans is capable of mediating this activity; however, its ability to couple U(VI) reduction to growth has not been established. Monitoring the increase in 16S rRNA gene copy numbers using quantitative real-time PCR (qPCR) in cultures provided with U(VI) as an electron acceptor demonstrated growth, and 7.7,8.6 × 106 cells were produced per ,mole of U(VI) reduced. This biomass yield was lower than predicted based on the theoretical free energy changes associated with U(VI)-to-U(IV) reduction. Lower than predicted growth yields with U(VI) as electron acceptor were also determined in cultures of Geobacter lovleyi and Geobacter sulfurreducens suggesting that U(VI) reduction is inefficient or imposes an additional cost to growing cells. These findings have implications for U(VI) bioremediation because Anaeromyxobacter spp. and Geobacter spp. contribute to radionuclide immobilization in contaminated subsurface environments. [source] Bioenergetics of the formyl-methanofuran dehydrogenase and heterodisulfide reductase reactions in Methanothermobacter thermautotrophicusFEBS JOURNAL, Issue 1 2003Linda M. I. De Poorter The synthesis of formyl-methanofuran and the reduction of the heterodisulfide (CoM-S-S-CoB) of coenzyme M (HS-CoM) and coenzyme B (HS-CoB) are two crucial, H2 -dependent reactions in the energy metabolism of methanogenic archaea. The bioenergetics of the reactions in vivo were studied in chemostat cultures and in cell suspensions of Methanothermobacter thermautotrophicus metabolizing at defined dissolved hydrogen partial pressures (,pH2). Formyl-methanofuran synthesis is an endergonic reaction (,G°, = +16 kJ·mol,1). By analyzing the concentration ratios between formyl-methanofuran and methanofuran in the cells, free energy changes under experimental conditions (,G,) were found to range between +10 and +35 kJ·mol,1 depending on the pH2 applied. The comparison with the sodium motive force indicated that the reaction should be driven by the import of a variable number of two to four sodium ions. Heterodisulfide reduction (,G°, = ,40 kJ·mol,1) was associated with free energy changes as high as ,55 to ,80 kJ·mol,1. The values were determined by analyzing the concentrations of CoM-S-S-CoB, HS-CoM and HS-CoB in methane-forming cells operating under a variety of hydrogen partial pressures. Free energy changes were in equilibrium with the proton motive force to the extent that three to four protons could be translocated out of the cells per reaction. Remarkably, an apparent proton translocation stoichiometry of three held for cells that had been grown at pH2<0.12 bar, whilst the number was four for cells grown above that concentration. The shift occurred within a narrow pH2 span around 0.12 bar. The findings suggest that the methanogens regulate the bioenergetic machinery involved in CoM-S-S-CoB reduction and proton pumping in response to the environmental hydrogen concentrations. [source] Thermodynamic study of capillary pressure curves based on free energy minimizationGEOFLUIDS (ELECTRONIC), Issue 3 2001Y. Deng Abstract This paper presents a new method for pore level network simulation of the distribution of two immiscible phases in a permeable medium. The method requires that the Helmholtz free energy of the system , the medium and the two phases contained within the pore space , be a minimum at all saturation states. We describe the method here and show some typical results from a computer algorithm that implements it. The results include (i) an explanation of the ,scanning' behaviour of capillary pressure curves based wholly on the free energy minimization, (ii) predictions of capillary pressure at arbitrary wetting states, including negative capillary pressures, and (iii) illustrations of how the minimized free energy changes along the scanning curves. The method also predicts the known dependency of the capillary pressure on the pore size distribution and interfacial tension. The current work is restricted to two-dimensional networks, but the free energy minimization appears to be generalizable to three dimensions and to more than two fluid phases. Moreover, functions generated through the minimization, specifically contact areas between the medium surface and the phases, appear to have applications predicting other multiphase petrophysical properties. [source] Reactive Processing in Ceramic-Based SystemsINTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY, Issue 1 2006William G. Fahrenholtz Reactive hot pressing is discussed as a processing method to form ceramic-based materials. Fundamental aspects of thermodynamics such as favorable Gibbs'-free energy changes, phase equilibria, and adiabatic temperature are presented as criteria for determining whether the desired reactions can be used to form dense materials. Two case studies are presented as examples to describe control of microstructure and properties. The fabrication of Al2O3,Nb and ZrB2 are discussed with respect to the three thermodynamic criteria as well as the microstructure and properties of the materials that are produced. [source] Thermodynamics and micellar properties of some surface active cobalt(III) metallosurfactants in nonaqueous mediumINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2007K. Santhakumar The critical micelle concentration (CMC) of four kinds of metallosurfactants of the type halogeno(dodecyl/cetylamine)-bis(ethylenediamine)cobalt(III) has been studied in n -alcohol and in formamide at different temperatures by electrical conductivity method. Specific conductivity data (at 293,313 K) served for the evaluation of temperature-dependent CMC and the thermodynamic parameters such as standard Gibbs free energy changes (,G), enthalpies (,H), and entropies (,S) of micelle formation. CMCs have also been measured as a function of percentage concentration of alcohol added. It is suggested that alcohol addition leads to increase in formamide penetration into micellar interface that depends on the alcohol chain length. The results have been discussed in terms of increased hydrophobic effect (solvophobic interaction), dielectric constant of the medium, and the chain length of the alcohols, the surfactant in the solvent mixture. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 22,31, 2007 [source] Adsorption of fulvic acids from aqueous solutions by carbon nanotubesJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 8 2007Shu-Guang Wang Abstract Carbon nanotubes (CNTs) were used as adsorbent to remove fulvic acids (FA) from aqueous solutions. The adsorption capacity of CNTs for FA can reach 24 mg g,1 at 5 °C and equilibrium concentration of 18 mg dm,3. The kinetic and thermodynamic parameters, such as rate of adsorption, standard free energy changes (,G0), standard enthalpy change (,H0) and standard entropy change (,S0), have been obtained. Acidic conditions (pH = 2,5) favor FA removal. An increase in the ionic strength or the addition of divalent cations increase the adsorption of FA dramatically (FA = 60 mg dm,3). An increase in the maximum adsorbed amount of FA was observed when treating FA in synthetic seawater. Desorption studies reveal that FA can be easily and quickly removed from CNTs by altering the pH values of the solution. Good adsorption capacity and quick desorption indicate that CNTs are a promising adsorbent to remove FA from aqueous solutions. Copyright © 2007 Society of Chemical Industry [source] Stability of carbon-centered radicals: Effect of functional groups on the energetics of addition of molecular oxygenJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2009James S. Wright Abstract In this paper we examine a series of hydrocarbons with structural features which cause a weakening of the CH bond. We use theoretical calculations to explore whether the carbon-centered radicals R, which are created after breaking the bond can be stabilized enough so that they resist the addition of molecular oxygen, i.e. where the reaction R, + O2 , ROO, becomes energetically unfavorable. Calculations using a B3LYP-based method provide accurate bond dissociation enthalpies (BDEs) for RH and ROO, bonds, as well as Gibbs free energy changes for the addition reaction. The data show strong correlations between ROO, and RH BDEs for a wide variety of structures. They also show an equally strong correlation between the ROO, BDE and the unpaired spin density at the site of addition. Using these data we examine the major functional group categories proposed in several experimental studies, and assess their relative importance. Finally, we combine effects to try to optimize resistance to the addition of molecular oxygen, an important factor in designing carbon-based antioxidants. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] Step-Energy Barriers and Particle Shape Changes during CoarseningJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 3 2002Brian W. Sheldon Models of particle shape changes usually do not account for the step-energy barrier associated with adding or removing additional atomic planes from a faceted surface. However, the step-energy barrier can be a substantial limitation when the free energy changes that drive particle shape changes are relatively low. A good example of this is particle coarsening. The analysis presented in this article describes dislocation-free particles with surfaces that have faceted and nonfaceted regions. When the chemical potential differences responsible for shape changes are too small to overcome the step-energy barrier, atomic layers cannot be added or removed from the facets. Even with this constraint, it is possible to add or remove atoms from the particle surface; however, this can cause the particle shape to differ substantially from the traditional equilibrium shape. [source] Aggregation characteristics of ovalbumin in ,-sheet conformation determined by spectroscopyBIOPOLYMERS, Issue 2 2002Raimon Sabaté Abstract Protein misfolding and aggregation are involved in a number of the so-called "conformational" diseases (e.g., transmissible spongiform encephalopathies and Alzheimer disease). The development of rational strategies to interfere with aggregation is a potential therapeutic approach that requires complete knowledge of the aggregation process. We studied the aggregation of ovalbumin in ,-sheet conformation using mainly the spectral changes in the spectra of two dyes (Congo Red and pinacyanol) caused by the aggregates. We assumed a linear model of polymerization that fit to the experimental data. The critical aggregation constant, concentration of half-aggregation, nucleation parameter, growth parameter, and number of aggregation and free energy changes (total and per residue) were determined as aggregation-related parameters. ,-Ovalbumin aggregates in a cooperative way. Moreover, the differences between such parameters obtained with Congo Red and pinacyanol suggest that each dye interacts with the protein in its own way. © 2002 John Wiley & Sons, Inc. Biopolymers (Biospectroscopy) 67: 113,120, 2002 [source] Photoinduced Electron Transfer Reactions by SmI2 in THF: Luminescence Quenching Studies and Mechanistic InvestigationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2005Edamana Prasad Dr. Abstract Photoluminescence quenching studies of SmI2 in dry THF were carried out in the presence of five different classes of compounds: ketone, alkyl chloride, nitrile, alkene and imine. The free energy change (,G,0) of the photoinduced electron transfer (PET) reactions was calculated from the redox potentials of the donor (SmI2) and acceptors. The bimolecular quenching constants (kq) derived from the Stern,Volmer experiments parallel the free energy changes of the PET processes. The observed quenching constants were compared with the theoretically derived electron transfer rate constants (ket) from Marcus theory and found to be in good agreement when a value of ,=167 kJ,mol,1 (40 kcal,mol,1) was used for the reorganization energy of the system. A careful comparison of the excited state dynamics of SmII in the solid state to the results obtained in solution (THF) provides new insight in to the excited states of SmII in THF. The activation parameters determined for the PET reactions in SmI2/1-chlorobutane system are consistent with a less ordered transition state and high degree of bond reorganization in the activated complex compared to similar ground state reactions. Irradiation studies clearly show that SmI2 acts as a better reductant in the excited state and provides an alternative pathway for rate enhancement in known and novel functional group reductions. [source] | ||||||||||||||||