Search results for "Gibbs free energy"
showing 10 items of 88 documents
Quasi-RRHO approximation and DFT study for understanding the mechanism and kinetics of nitration reaction of benzonitrile with nitronium ion
2021
Abstract The nitration reaction of benzonitrile with nitronium cation, NO2+, has been studied within the Molecular Electron Density Theory at the MN15-L/aug-cc-pVTZ level of theory. For this electrophilic aromatic substitution (EAS) reaction, three regioisomeric reaction paths have been studied. Quasi-RRHO approximation was applied to consider the vibrational contribution to entropy and correct the Gibbs free energy profile of the reaction in the solvent phase. Benzonitrile is less nucleophilically activated than benzene due to the presence of the electron-withdrawing CN group the meta position is the more favorable reaction path of this EAS reaction. The analysis of ELF and AIM demonstrate…
Stability of a Split Streptomycin Binding Aptamer
2016
Here we investigated the stability of an aptamer, which is formed by two RNA strands and binds the antibiotic streptomycin. Molecular dynamics simulations in aqueous solution confirmed the geometry and the pattern of hydrogen bond interactions that was derived from the crystal structure (1NTB). The result of umbrella sampling simulations indicated a favored streptomycin binding with a free energy of ΔGbind° = −101.7 kJ mol–1. Experimentally, the increase in oligonucleotide stability upon binding of streptomycin was probed by single-molecule force spectroscopy. Rate dependent force spectroscopy measurements revealed a decrease in the natural off-rate (koff-COMPLEX = 0.22 ± 0.16 s–1) for the …
Fractional hereditariness of lipid membranes: Instabilities and linearized evolution
2016
In this work lipid ordering phase changes arising in planar membrane bilayers is investigated both accounting for elas- ticity alone and for effective viscoelastic response of such assemblies. The mechanical response of such membranes is studied by minimizing the Gibbs free energy which penalizes perturbations of the changes of areal stretch and their gradients only [1]. As material instabilities arise whenever areal stretches characterizing homogeneous configurations lie inside the spinoidal zone of the free energy density, bifurcations from such configurations are shown to occur as oscillatory perturbations of the in-plane displacement. Experimental observations [2] show a power-law in-pl…
Thermodynamic Behavior of Non-Ionic Tri-block Copolymers in Water at Three Temperatures
2006
Apparent molar volumes (V Φ) of aqueous solutions of some copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, were determined as functions of concentration at three temperatures. Viscosity measurements were also carried out on some of these systems. The effects studied include how the molecular architecture and the molecular weight affect the aggregation of the copolymer, keeping constant the EO/PO ratio. Modeling of the volumetric data yielded the partial molar volume of the copolymer in the standard (V°) and the aggregated (V M) states, as well as the equilibrium constant for micellization and the aggregation number. Analysis of the viscosity data supported the insigh…
Enthalpies of transfer of pentanol from water to sodium dodecylsulfate-dodecyl-dimethylamine oxide-water mixtures
1994
At a given surfactant-surfactant ratio, the enthalpies of transfer ΔH (W→W+S) of pentanol 0.03m from water to sodium dodecylsulfate (NaDS)-dodecyldimethylamine oxide-water mixtures as functions of the surfactants mixture concentration (m t) were determined. ForX NaDS=0.9, ΔH (W→W+S) increases monotonically withm t such as observed for pure surfactants. ForX NaDS=0.12 and 0.3, ΔH (W→W+S) increases withm t up to 0.12m beyond which it decreases withm t. AtX NaDS=0.6, two monotonic curves can be distinguished in the ΔH (W→W+S)vs. m t trend. Experimental data were fitted through an equation previously reported for additives in pure surfactants derived by assuming the pseudo-phase transition mode…
Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solu…
1996
Density measurements of pentanol (PentOH)−dodecyltrimethylammonium bromide (DTAB)−water mixtures as functions of both alcohol and surfactant (mS) concentrations were carried out at 0.1 MPa from 45 to 75 °C and at 19 MPa from 25 to 130 °C. The standard (infinite dilution) partial molar volumes and expansibilities of DTAB in water and the corresponding properties in the micellar phase were calculated from the experimental data. As far as PentOH in DTAB micellar solutions is concerned, with the exception of the standard partial molar volume (V°R) data at 130 °C and 19 MPa, all the V°R vs mS trends are monotonic curves with mS. The data of V°R as a function of mS were treated by means of an equ…
A thermodynamic study to evidence the alpha,omega-dichloroalkane/ block copolymer mixed aggregates formation: effect of the copolymer architecture.
2006
Abstract The thermodynamics of α , ω -dichloroalkanes in aqueous solutions of (ethylene oxide)11(propylene oxide)16(ethylene oxide)11 (L35) and (propylene oxide)8(ethylene oxide)23(propylene oxide)8 (10R5) was determined at 298 and 305 K. Modeling the experimental data allowed to calculate the standard free energy ( Δ G D o / w ) and the volume ( Δ V D / w ) for the additive–copolymer mixed aggregates formation per additive molecule. Δ G D o / w for Cl2CH2 and Cl2(CH2)2 evidenced that the process is controlled by the forces exercising between the chlorine atoms and the OH groups of the copolymer micelles protruded into the aqueous phase. Cl2(CH2)3 experiences both the hydrophilic and hydrop…
Heat Capacity of Transfer of (Ethylene oxide)13-(propylene oxide)30-(ethylene oxide)13 from Water to the Aqueous Anionic Surfactant Solutions at 298 …
2004
Heat capacities of transfer (ACpt) of unimeric (ethylene oxide)(13)-(propylene oxide)(30)-(ethylene oxide)(13) from water to the aqueous surfactant solutions as functions of the surfactant concentrations (m(S)) were determined at 298 K. The surfactants investigated are sodium hexanoate, sodium heptanoate, sodium octanoate, sodium undecanoate, and sodium dodecanoate. For short alkyl chain surfactants, the profiles of the DeltaCp(t) versus ms curves show maxima and minima; for long alkyl chain surfactants, the maximum becomes sharper and moved to lower ms values whereas the minimum tends to disappear. These experimental trends are different from those of the enthalpy in agreement with the fac…
Thermodynamics of Solubilization of Pentanol in Sodium Dodecyl Sulfate-Dodecyldimethylamine Oxide Mixed Micelles
1994
Abstract Heat capacity and density measurements of pentanol (PeOH)-sodium dodecyl sulfate (NaDS)-dodecyldimethylamine oxide-water mixtures were carried out at 0.03 m PeOH as a function of the total surfactants concentration (mc) at different ratios (XNaDS). From experimental data, the apparent molar volumes (VΦ,R) and heat capacities (CΦ,R) of PeOH in the surfactants mixture solutions were calculated. As a general feature, at a given mixture composition, VΦ,R increases monotonically with mt as observed in pure surfactants. In the cases of XNaDS = 0.1 and 0.3, VΦ,R drops at about 0.1 and 0.15 mt respectively. The decreasing CΦ,R VS mt curve shows peculiarities which were ascribed to the pres…
Viscosity and density of binary mixtures of alcohols and polyols with three carbon atoms and water: equation for the correlation of viscosities of bi…
2009
Measurements have been made of the viscosity and density of binary mixtures of alcohols and polyols with three carbon atoms and water at 298.15 K and at atmospheric pressure, as a function of the mole fraction. Fits have been made of the experimental values corresponding to the excesses of molar volume (V E), the deviations of viscosity (Δη), and the excesses of Gibbs free energy of activation (G* E), by means of the Redlich–Kister equation. A new correlation equation is presented for studying the viscosity of such mixtures, and comparisons are made of the experimental values of viscosity versus the values obtained by means of the mentioned equation and the models of Heric and McAllister. L…