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101.
Striegel AM 《Journal of chromatography. A》2004,1033(2):241-245
Our understanding of the nature of solute retention in size-exclusion chromatography (SEC) is predicated upon an equilibrium, entropy-controlled, size-exclusion mechanism. The entropic nature of the separation depends, in turn, upon the solute distribution coefficient (K(SEC) being at (or close to) thermodynamic equilibrium. Classic experiments to confirm this assumption were performed over thirty years ago. Here, we combine information obtained from both flow and static mixing SEC experiments to show that the solute distribution in SEC is in thermodynamic equilibrium over a molar mass range extending one order of magnitude higher than previously measured (from 2 x 10(3) to 1.1 x 10(6) Da) using crosslinked polystyrene packing material of identical pore size (10(4) A). The differences between our observations and previous ones conducted over three decades ago are ascribed, principally, to advances in stationary phase synthesis and column technology for SEC in particular and, secondarily, to improvements in the performance of the various instrumental components of liquid chromatographic systems in general. 相似文献
102.
The linear, nonlinear and improved nonlinear thermodynamic models of the voltage-dependent ion channels were proposed to deduce the exact functional form of the rate constants. In this context, we present a comparative analysis of the linear, nonlinear and improved nonlinear thermodynamic models of voltage-dependent channel kinetics based on the sodium activation experimental data of Cav3.1 channel. We also provide some insight on the assumptions used to derive the thermodynamic models of the channels and show that the improved nonlinear thermodynamic model provides a simple and physically plausible approach to describe the behavior of the voltage-dependent ion channels. 相似文献
103.
Ahmadreza F. GhobadiJ. Richard Elliott 《Fluid Phase Equilibria》2011,306(1):57-66
SAFT models are generally written as a perturbation series of the Helmholtz energy with reciprocal temperature as the argument. The perturbation coefficients are then functions of density and molecular size. The variation of the perturbation coefficients with molecular size is given primarily by Wertheim's theory [6], [7], [8] and [9], but there may be additional variations as in the PC-SAFT model. In the present work, we compare the characterization of perturbation coefficients inferred from PC-SAFT to those derived from molecular simulations.The molecular simulations are based on Discontinuous Molecular Dynamics (DMD) and second order Thermodynamic Perturbation Theory (TPT). DMD simulation is applied to the repulsive part of the potential model with molecular details like fused hard spheres for the interaction sites and 110° bond angles. The thermodynamic effects of disperse attractions are treated by rigorous application of TPT. The present work re-examines the related work of Elliott and Gray [35] in the low density and critical regions, focusing on n-alkanes with carbon numbers ranging from 3 to 80.We find that SAFT theory overestimates the repulsive contribution (A0) and underestimates the first order contribution (A1) of Helmholtz energy relative to simulation. Nevertheless, the correlations are qualitatively reasonable. Significant inconsistencies arise when considering the second order contribution (A2). For example, the PC-SAFT characterization of A2 becomes larger than A1 in the low density, long chain limit, raising concerns about the convergence of the series. Furthermore, fluctuations are underestimated in the critical region and overestimated in the liquid region. In each case, we can suggest improved characterizations. Altogether, these results suggest ways to modify the SAFT formalism to achieve greater consistency between atomistic and coarse-grained models. 相似文献
104.
105.
This article is the first in a series dealing with the thermodynamic properties of quantum Coulomb systems.In this first part, we consider a general real-valued function E defined on all bounded open sets of R3. Our aim is to give sufficient conditions such that E has a thermodynamic limit. This means that the limit E(Ωn)|Ωn|−1 exists for all ‘regular enough’ sequence Ωn with growing volume, |Ωn|→∞, and is independent of the considered sequence.The sufficient conditions presented in our work all have a clear physical interpretation. In the next paper, we show that the free energies of many different quantum Coulomb systems satisfy these assumptions, hence have a thermodynamic limit. 相似文献
106.
A. M. Al Sabagh N. Gh. Kandil A. M. Badawi H. El-Sharkawy 《Colloids and surfaces. A, Physicochemical and engineering aspects》2000,170(2-3):127-136
Three nonionic surfactants; p-isooctylphenol ethoxylates p-[i-OPE10], p-[i-OPE15], and p-[i-OPE20], were phosphorylated to produce three anionic phosphate ester surfactants. In addition, N-diethoxylated perfluorooctanamide (N-DEFOA) was also prepared. The surface and thermodynamic properties of the three types of surfactants and mixtures of the fluorocarbon surfactant (FC) with the hydrocarbon surfactants (HC) have been investigated. Surface tension as a function of concentration of the surfactant in aqueous solution was measured at 30, 40, 50 and 60°C, using the spinning drop technique. From these measurements the critical micelle concentration (CMC), the surface tension at the CMC (γCMC), the maximum surface excess concentration (Γmax), the minimum area per molecule at the aqueous solution/air interface (Amin), and the effectiveness of surface tension reduction (πCMC), were calculated. The thermodynamic parameters of micellization (ΔGmic, ΔHmic, ΔSmic) and of adsorption (ΔGad, ΔHad, ΔSad) for these surfactants and their mixtures were also calculated. Structural effects on micellization, adsorption and effectiveness of surface tension reduction are discussed in terms of these parameters. The results show that the FC surfactant and its mixtures with HC surfactants enhance the efficiency in surface tension reduction and adsorption in the mixed monolayer at the aqueous solution/air interface, and also, reduce γCMC and the tendency towards micellization. 相似文献
107.
U. S. Mote S. L. Bhattar S. R. Patil G. B. Kolekar 《Journal of solution chemistry》2009,38(5):619-628
The interaction between fluorescein and felodipine (FLD) was investigated by the spectrofluorometric method. The fluorescence
of FLD was quenched by fluorescein and quenching is in accordance with the Stern-Volmer relation. The binding constants of
fluorescein with FLD were obtained at different temperatures. The binding constant and number of binding sites at different
temperatures were calculated yielding the corresponding thermodynamic parameters ΔS, ΔH and ΔG. The distance r between the donor (FLD) and acceptor (fluorescein) molecules was obtained according to the fluorescence resonance energy
transfer. The optimum conditions for the fluorometric determination of fluorescein were studied and the quenching method was
successfully applied to estimate the fluorescein concentration of the pharmaceutical sample directly. 相似文献
108.
Summary A new graphitized carbon black, Carbograph 4, with a specific surface area of 240 m2 g−1 was studied in terms of enthalpy, entropy and free energy of adsorption, determined by gas chromatographic method on a series
of alkanes (C2−C6) and on benzene. The changes in the isosteric heat and entropy of adsorption when a non-polar stationary phase (squalane)
was added to the adsorbent were also investigated. The data obtained are discussed and compared to those present in the literature
for other graphitized carbon blacks. Some examples of separations obtained with Carbograph 4 are reported. 相似文献
109.
S. Sanjabi A. Faramarzi Z.H. Barber 《Journal of Physics and Chemistry of Solids》2008,69(8):1940-1944
Size-dependent thermodynamic parameters, such as Gibbs free energy, enthalpy and entropy, for the transition of a Ni nanofilm to catalyst particles for subsequent carbon nanotube growth have been explored. In this investigation, we consider the derived equations of the size-dependent melting temperature of nanosolids based on our previous works. Using this thermodynamic approach, it is found that the diameter of Ni particles is 3 times greater than the thickness of the original film. From the critical and stable sizes of transformed Ni nanoparticles, a minimum film thickness for transformation of film to nanoparticles was obtained. Our predictions are in good agreement with experimental results. 相似文献
110.
Sarah R. Dennison Leslie H.G. Morton Andrea J. Shorrocks Frederick Harris David A. Phoenix 《Colloids and surfaces. B, Biointerfaces》2009,68(2):225-230
Aurein 2.5 (GLFDIVKKVVGAFGSL-NH2) is an uncharacterised antimicrobial peptide. At an air/water interface, it exhibited strong surface activity (maximal surface pressure 25 mN m−1) and molecular areas consistent with the adoption of α-helical structure orientated either perpendicular (1.72 nm2 molecule−1) or parallel (3.6 nm2 molecule−1) to the interface. Aurein 2.5 was strongly antibacterial, exhibiting a minimum inhibitory concentration (MIC) of 30 μM against Bacillus subtilis and Escherichia coli. The peptide induced maximal surface pressure changes of 9 mN m−1 and 5 mN m−1, respectively, in monolayers mimicking membranes of these organisms whilst compression isotherm analysis of these monolayers showed ΔGMix > 0, indicating destabilisation by Aurein 2.5. These combined data suggested that toxicity of the peptide to these organisms may involve membrane invasion via the use of oblique orientated α-helical structure. The peptide induced strong, comparable maximal surface changes in monolayers of DOPG (7.5 mN m−1) and DOPE monolayers (6 mN m−1) suggesting that the membrane interactions of Aurein 2.5 were driven by amphiphilicity rather than electrostatic interaction. Based on these data, it was suggested that the differing ability of Aurein 2.5 to insert into membranes of B. subtilis and E. coli was probably related to membrane-based factors such as differences in lipid packing characteristics. The peptide was active against both sessile E. coli and Staphylococcus aureus with an MIC of 125 μM. The broad-spectrum antibacterial activity and non-specific modes of membrane action used by Aurein 2.5 suggested use as an anti-biofilm agent such as in the decontamination of medical devices. 相似文献