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Conductivities, densities and ultrasonic speeds measurements of hexadecyltrimethylammonium bromide (HTAB) in aqueous solutions of glycine (Gly) and glycylglycine (Gly-Gly) have been made at various temperatures. The critical micelle concentration (CMC), the degree of ionization (??) of the micelles, standard free energy, enthalpy, and entropy of the micellization process (??G m ° , ??H m ° , and ??S m ° ) for the present systems were estimated at different temperatures. The CMC values of HTAB in aqueous Gly and Gly-Gly were also evaluated by density and ultrasonic speed measurements. Apparent molar volumes, (V ?), apparent molar volumes at infinite dilution, (V ? ° ), apparent molar compressibilities, (K ?), of HTAB in the pre- and post-micellar regions, and volume change on micellization (??V ? m ) were also estimated. Large positive values of T??S m ° and small negative values of ??H m ° suggest that micellization process is driven primarily by entropy increase. The increase in ??V ? m and K ? with rise in temperature is indicative of less compact micellar structure of HTAB in presence of amino acid additives. These data suggest that amino acids are solubilised probably in the palisade layer of the micelle.  相似文献   

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Calorimetric measurements of enthalpies of solution Δsol H m for glycine, L-cysteine, and glycylglycine in aqueous solutions of sodium dodecyl sulfate (SDS) with concentrations of up to 0.05 mol kg–1 are made. Standard enthalpy of solution Δsol H 0 and enthalpy of transfer Δtr H 0 of the dipeptide from water into mixed solvent are calculated. The calculated enthalpy coefficients of paired interactions of amino acids and dipeptide with SDS prove to be positive. Hydrophobic interactions between the biomolecules and SDS are found to have a major impact on the enthalpies of interaction in the three-component systems under study, within the indicated range of concentrations.  相似文献   

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In this work, new results for density, viscosity, and vapour pressure of (triethylene glycol or propylene glycol) in H2O with LiCl or LiBr systems over temperatures ranging from 303.15 K to 343.15 K are presented. For each ternary system, four systems of which (4 to 25) mass% salt mixed with various glycols (50 to 80) mass% were studied. Incorporated with the pseudo-solvent approach, a vapour pressure model based on the mean spherical approximation for aqueous electrolyte solutions was used to represent the measured vapour pressure of the investigated systems. The present density and viscosity results were also correlated as a function of temperature and composition. The correlations yield satisfactory results. Compared to the conventionally used liquid desiccants, the vapour pressures of the systems studied yield smaller values of vapour pressures. The properties presented in this work are, in general, of sufficient accuracy for most engineering-design calculations.  相似文献   

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Isopiestic and viscosity measurements on aqueous sodium cholate-lecithin solutions are reported at high concentrations which include the physiological region as a lower limit. At low cholate concentration, the addition of lecithin increases the activity of water, consistent with earlier studies showing increases of micellar weights. At higher cholate concentrations, the activity of water is independent of lecithin concentrations. Studies of binary solutions of bile acid salts and detergents agree very closely with earlier work.  相似文献   

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Thermodynamic characteristics of aqueous linear diol solutions are calculated. These data are used to identify regularities in the variations of the structural properties of the mixtures being studied. The correlation between the entropy and enthalpy characteristics of water-diol systems with excess packing coefficients is evidence that the structural and energy properties of aqueous linear diol solutions are determined by universal interactions. The form of the concentration dependences of the solvation enthalpies and entropies of noble gases in water-linear diols mixtures is determined by the reorganization component and is attributed to the destruction of the H bond network of water, which results in the formation of the most densely packed solutions in the medium range of compositions.  相似文献   

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Ethambutol (EMB) is a bacteriostatic antimycobacterial drug prescribed to treat tuberculosis. It is bacteriostatic against actively growing TB bacilli. The density and viscosity of aqueous ethambutol hydrochloride solutions have been studied at 298.15, 301.15 and 304.15 K and at different concentrations (0.255, 0.168, 0.128, 0.087, 0.041, and 0.023 mol dm−3). The apparent molar volume of these solutions for different temperatures and concentrations was calculated from the density data. The relative viscosities of drug solutions have been analysed by Jones-Dole equation. The limiting apparent molar volumes have been evaluated for different temperatures. The different properties have been used to study structural properties, structure formation and breaking properties of drug and solute-solvent interactions in solutions.  相似文献   

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Rheological and erosion studies regarding a liposome-containing polymeric blend that is propaedeutic to its use in paving techniques in tubular organs, such as blood vessels, are reported. Attention is focused on an aqueous polymeric blend composed of Pluronic (PF127) and alginate (Protanal LF 10/60) because both polymers, when dissolved in water at a sufficiently high concentration, are subjected to different structural mechanisms, which are driven by temperature increase and addition of bivalent cations, respectively, and both result in marked viscoelastic and plastic properties. After proving the compatibility between PF127 and alginate, we show that the structural transition temperature of the blend, T(ST), can be properly modulated. In particular, we found that T(ST) for an aqueous solution of pure Pluronic 20% w/w is about 21 degrees C and that even slight reductions in polymer concentration result in considerable T(ST) decrease. The addition of salts or alginate (provided as Na-alginate) provokes a substantial decrease of T(ST) and thus the alginate concentration in the blend should not exceed 1% w/w. In addition, liposomes slow down the structural transition but do not substantially affect the rheological properties of the system in the final state at higher temperatures, thus showing that they can be added to the polymeric blend without significant effects. Finally, erosion tests show that after contact with a source of bivalent cations, the polymeric blend containing PF127 and alginate shows an erosion resistance neatly improved with respect to the simple structured Pluronic system having the same polymer concentration. As a whole, all these results constitute the basis for future potential applications of the considered polymeric blend in tubular organs such as blood vessels.  相似文献   

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The mutual diffusion coefficients for two aqueous ternary systems, both containing a protein, human serum albumin (HSA, component 1), were measured. The first system contained a neutral polymer, polyethylene glycol (PEG, component 2), and the second an "organic solvent", 2-methyl-2,4-pentanediol (MPD, component 3). Both PEG and MPD are used as co-precipitants in HSA crystallization protocols. Measurements were performed at constant protein concentration, with increasing precipitant content. The results obtained for the two systems were discussed and compared. In both cases, the two main diffusion coefficients, relative to the motion of the protein and of the precipitant under their own concentration gradient, can be interpreted in terms of non-specific volume interactions between the solutes. Particularly, it was showed that any possible direct HSA-MPD interaction may not have a significant effect on the values of these two diffusion coefficients. Differences arise between the cross precipitant's diffusion coefficients, relative to the motion of the precipitant under the protein concentration gradient, D(i1) with i = 2, 3. In the case of PEG, the D(21) trend vs. c(2) can be simply interpreted in terms of an "exclude volume" effect. In contrast, in the case of MPD, the D(31)vs. c(3) trend seems to indicate a more complex mechanism of transport. Because the cross precipitant's diffusion coefficient plays an important role in the crystallization process, the implication of the observed difference on the crystallization procedure was also discussed.  相似文献   

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Physicochemical properties of aqueous solutions of L-aspartic acid with and without addition of chitosan have been studied by conductometry, potentiometry, refractometry, tensiometry, and viscosimetry. It has been shown that aspartic acid molecules take a cyclic configuration stabilized by hydrogen bonds in aqueous solution at c > 0.04 g/dL (298 K). The interaction of chitosan with aspartic acid results in the formation of the polymeric salt that dissociates in aqueous solution to give chitosan polycation [~(NH3)+] and aspartate counterions. The addition of chitosan to solutions of L-aspartic acid results in progressive increase in the surface tension, absorbance, and refractive index as well as the change in hydrodynamic properties of the macromolecules. The polymeric salt exhibits polyelectrolyte properties in dilute aqueous solutions. The increase in temperature impairs the thermodynamic quality of the solvent for chitosan leading to the shrinkage of the polymer coils and, hence, to the decrease in the intrinsic viscosity of the system.  相似文献   

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The densities, heat capacities, heats of dilution, and viscosities of aqueous 1,1-dimethyl-4,4-dipyridinium dichloride were measured below 1 m at 25°C. From the standard partial molal volumes and heat capacities and the B viscosity coefficients, this salt is shown to be a strong structure breaker. The excess enthalpies, entropies, volumes, and heat capacities all show negative deviations from the limiting Debye-Hückel law for 2:1 electrolytes. These excess functions cannot be explained through association or structural interactions and suggest that, at higher concentrations, this rigid bolaform electrolyte may behave more like a 1:1 electrolyte than a 2:1 electrolyte.  相似文献   

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Measurements of ultrasonic speeds, isentropic compressibilities and viscosities were carried out for six ternary mixtures namely dimethylsulphoxide (1) + 1,2-dichlorobenzene (2) + 1-alkanols (3) at 303.15 K. The 1-alkanols include 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and 1-octanol. The ultrasonic speeds of these ternary mixtures were also evaluated on the basis of Jacobson's free length theory and Schaaff's collision factor theory. From the viscosity data, deviations in viscosity and interaction parameters for various models were also calculated. An attempt has also been made to explain the nature of intermolecular interactions in the light of deviation in isentropic compressibilities and interaction parameter.  相似文献   

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《Chemical physics letters》2003,367(1-2):238-244
Molecular dynamics simulation is used to investigate hydration properties of glycine betaine in a large range of solute concentrations. Statistical analyses of the system trajectories evidence microscopic details suggesting an interpretation of experimental results recently obtained for aqueous solutions of trimethylamine-N-oxide, a bioprotectant closely related to glycine betaine.  相似文献   

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刘春丽  马林  林瑞森 《化学学报》2009,67(24):2875-2878
用RD496-Ⅱ型微量热量计测定了298.15 K甘氨酸在N-甲基甲酰胺(NMF),N, N-二甲基甲酰胺(DMF),N-甲基乙酰胺(NMA),N, N-二甲基乙酰胺(DMA)水溶液中的溶解焓,计算了甘氨酸从水到四种酰胺衍生物水溶液中的迁移焓(ΔtrH)。根据结构水合作用模型讨论了酰胺的结构对甘氨酸迁移焓的影响。实验结果表明:甘氨酸在酰胺衍生物水溶液中的迁移焓均为正值,并且随着溶液浓度增大而增大。比较甘氨酸在甲酰胺(FA)和乙酰胺(AD)水溶液中的迁移焓,发现在不同酰胺水溶液中迁移焓大小为:DMA>NMA>DMF>NMF>AD>FA。甘氨酸与甲酰胺之间以亲水-亲水相互作用为主,与其它酰胺之间以亲水-疏水作用为主。  相似文献   

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The viscosities of dilute solutions (0.05, 0.1, and 0.2 g. per 100 ml.) of relatively high nitrogen content nitrocelluloses, weight-average molecular weights ca. 100,000, have been studied using homologous series of methyl ketones, alkyl acetates, and dialkyl phthalates as solvents. The simple form of the Huggins equation, does not appear to hold, plots of ηsp/c against c being generally curved. The results are capable of expression by where A equals [η] and B the initial slope. Values of B and A appear to be related to solvent power as determined by the volume of hexane required to cause initial phase separation from solution, good solvents giving higher values of B and A than poor. The variation of B with solvent is more marked than that of [η] and may reflect differences in degree of coiling of chains in different solvents. Values of B/[η]2 (Huggins k′) do not generally decrease with solvent power increase. The slopes of Martin plots divided by intrinsic viscosities are not generally related to solvent power in the manner observed by Spurlin with solutions of ethyl cellulose.  相似文献   

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