Thermochemical characteristics of the interaction of L-cysteine with glycerol,ethylene glycol,and 1,2-propylene glycol in aqueous solutions

Integral enthalpies of dissolution Δ_sol H ^m of L-cysteine in mixtures of water with glycerol, ethylene glycol, and 1,2-propylene glycol at concentrations of organic solvents of up to 0.37 mole fraction were measured by calorimetry of dissolution. The standard values of the dissolution enthalpies (Δ_sol H°) and the transfer enthalpies (Δ_tr H°) of amino acid from water to the mixed solvent were calculated. It was shown that the calculated enthalpic coefficients of the pair interactions of L-cysteine with cosolvent molecules have positive values. The obtained data are interpreted from the viewpoint of the prevalence of different types of interactions in the solutions and influence of the cosolvents nature on the thermochemical characteristics of amino acid dissolution.     

Thermochemical investigation of interaction of L-serin with glycerol,ethylene glycol,and 1,2-propylene glycol in aqueous solutions

By the method of dissolution calorimetry integral enthalpies of dissolution Δ_sol H ^m of L-serine are measured in the mixtures of water with glycerol, ethylene glycol, and 1,2-propylene glycol at the concentration of the organic solvent up to 0.42 mole fraction. The standard values of enthalpies of dissolution (Δ_sol H ⁰) and transfer (Δ_tr H ⁰) of amino acids from water to mixed solvents are calculated. The calculated values of the enthalpy coefficients of pair interactions of L-serine with the molecules of co-solvents are positive. The data obtained are interpreted in terms of prevalence of different types of interactions in solutions and the influence of nature of co-solvents on the thermochemical characteristics of the dissolved amino acids.     

Thermochemical characteristics of interactions of DL-alanine in aqueous solutions of glycerol, ethylene glycol, and 1,2-propylene glycol

The method of dissolution calorimetry was used to measure the integral enthalpy of dissolution ??_sol H ^m of DL-alanine in mixtures of water with glycerol, ethylene glycol, and 1,2-propylene glycol at a concentration of organic solvent up to 0.32 mole fraction. The standard dissolution enthalpy (??_sol H ⁰) and transport enthalpy of amino acids from water to mixed solvent (??_tr H ⁰) were calculated. The calculated enthalpy coefficients of pair interactions of the DL-alanine molecules with the polyol molecules are positive and less than these values for L-alanine. The effect of interactions of different types in solution and the structural features of biomolecules and co-solvents on the enthalpy of dissolution characteristics of amino acids were considered.     

Standard enthalpies of dissolution of L-alanine in the water solutions of glycerol, ethylene glycol, and 1,2-propylene glycol at 298.15 K

The integral enthalpies of dissolution Δ_sol H ^m of L-alanine in mixtures of water with glycerol, ethylene glycol, and 1,2-propylene glycol under the concentration of organic solvents up to 0.32 mole fraction were measured by means of calorimetry. The standard values of the dissolution enthalpies (Δ_sol H ^o) and transfer enthalpies (Δ_tr H ^o) of amino acids from water to the mixed solvent were calculated. It was shown that the calculated enthalpic coefficients of pair interactions of L-alanine with cosolvent molecules have positive values. The data obtained are interpreted from the viewpoint of prevalence of different types of interactions in the solutions and influence of the cosolvents nature on the thermo-chemical characteristics of amino acid dissolution.     

Enthalpy of dilution of aqueous mixtures of amides,sugars, urea,ethylene glycol,and pentaerythritol at 25°C: Enthalpy of interaction of the hydrocarbon,amide, and hydroxyl functional groups in dilute aqueous solutions

The enthalpy of dilution of all one-and two-solute aqueous mixtures of a series of compounds were measured from about 0.2 to 2.0 mole-kg^–1 at 25°C. The compounds included in the study wereN-methylformamide,N-methylacetamide,N-methylpropionamide,N-butylacetamide, urea, ethylene glycol, pentaerythritol, glucose, and sucrose. The results of the enthalpy measurements were used to calculate the pairwise enthalpy of interaction for each compound with all the other compounds. A simple additivity principle is used to correlate the data. The principle assumes that each functional group on one molecule interacts with every functional group on the other molecule and that each of these interactions has a characteristic effect on the enthalpy that is independent of the positions of the functional groups in the two molecules. The resulting equation gives a rough but useful correlation of the results. Of the six interactions between the CH₂, CONH, and CHOH functional groups, the CONH–CONH interaction is the strongest, the CHOH–CHOH interaction is the weakest, and the CH₂–CH₂ interaction is about equal in magnitude to the rest of the interactions. Thus, the CH₂–CH₂ and CONH–CONH are not the only interactions making important contributions to the enthalpy of a wide variety of systems.     

Extraction of ethylene glycol from aqueous salt solutions

A method is proposed for extracting ethylene glycol from aqueous salt solutions by dialysis through ion-exchange membranes, based on the Donnan exclusion of the electrolyte. Dialysis is performed in the continuous and batch modes. It is found that the batch mode of dialysis is more effective for extracting ethylene glycol from its aqueous salt solutions. The effect of the ionic form of the membrane on ethylene glycol fluxes is explained through computer simulation.     

Molar volumes of aqueous and ethylene glycol solutions of tetrahydrofuran

The densities of ethylene glycol solutions of tetrahydrofuran (THF) with 0–20 mol % THF were measured at 20–60°C and atmospheric pressure to an accuracy of 5 × 10⁻⁵ g/cm³. The apparent molar volumes of THF in the solutions were calculated and their concentration and temperature dependences determined. The results were compared with the apparent molar volumes of THF in aqueous systems calculated from the literature data. Minima were found on the concentration dependence of the apparent volume of THF for both aqueous and ethylene glycol solutions and changed differently as the temperature increased. The data obtained were discussed from the standpoint of solvophobic effects in aqueous and ethylene glycol solutions of THF.     

The interaction between triton X series surfactants and poly (ethylene glycol) in aqueous solutions

 A series of Triton X surfactants with different ethylene oxide chain length and poly(ethylene glycols) with different molecular weight were used, to find the effects of polymer chain length and size of the micelles on the cloud point of the surfactants. Two possible models are considered on the basis of cloud point changes of the solutions, to describe the polymer–surfactant interactions. One model considers that intra-chain micelles of polysoap are formed among the surfactant monomers and long polymer chains. The bridging attraction between two intra-chain micelles in such structures can enhance the collisions among the micelles, due to the exchange of amphiphilic monomers among the neighboring micelles. The other model suggests that flocculation depletion for the polymer chains exists between two regular micelles. This provides the driving force for the neighboring micelles to approach each other and destabilize the colloidal system. The flocculation effect is more significant for polymer with a long chain. Polymers with a shorter chain block the approach of the micelles, since there is no typical polymer–surfactant association formed but just simple small molecule associations in which the steric and solvation effects of the polymer chains make the inter-micelle interactions repulsive. Received: 19 August 1997 Accepted: 11 December 1997     

Spectrophotometric method for the determination of 1,2-propylene glycol

A spectrophotometric method is proposed for the determination of 1,2-propylene glycol. It is based on the ADH/ AlDH catalyzed oxidation of propylene glycol by NAD⁺. The NADH formed is measured at 340 nm. Alcohol dehydrogenase from equine liver was found to be much more effective than that of yeast. No enantiomeric selectivity for s(+) propylene glycol was observed. A linear relation was found in the concentration range from 5 to 50 mg/L. The method achieves a correlation coefficient of r = 0.996 and a relative standard deviation of 1.37%. The limit of quantitation was calculated to 9.6 mg/L. Since the total reaction volume was restricted to 800 μL, only 2.8 units of AlDH and 8 units of ADH were sufficient to develop the final absorption within 30 min.     

Spectrophotometric method for the determination of 1,2-propylene glycol

A spectrophotometric method is proposed for the determination of 1,2-propylene glycol. It is based on the ADH/ AlDH catalyzed oxidation of propylene glycol by NAD⁺. The NADH formed is measured at 340 nm. Alcohol dehydrogenase from equine liver was found to be much more effective than that of yeast. No enantiomeric selectivity for s(+) propylene glycol was observed. A linear relation was found in the concentration range from 5 to 50 mg/L. The method achieves a correlation coefficient of r = 0.996 and a relative standard deviation of 1.37%. The limit of quantitation was calculated to 9.6 mg/L. Since the total reaction volume was restricted to 800 μL, only 2.8 units of AlDH and 8 units of ADH were sufficient to develop the final absorption within 30 min. Received: 16 April 1997 / Revised: 19 June 1997 / Accepted: 25 June 1997     

Swelling of polyacrylamide gels in aqueous solutions of ethylene glycol oligomers

Addition of a small amount of ethylene glycol oligomers (OEG), with the number of repeat units y = 2–4, in an aqueous solution leads to the contraction of both linear and cross-linked poly(acrylamide-co-acrylic acid) chains. The results present clear evidence for the screening effect of OEG on the ionic groups of the polymer chains. Measurements indicate that the pre-swollen poly (acrylamide-co-acrylic acid) gels immersed in aqueous OEG solutions are at equilibrium. However, as the molecular weight of OEG increases, these gels cannot attain their equilibrium swelling ratio due to the appearance of non-equilibrium structures. The stability of these structures increases as the initial swelling degree of the gels increases.     

Conductometric studies of hexadecyltrimethylammonium bromide in aqueous solutions of ethanol and ethylene glycol

The effect of cosolvent on micellization of hexadecyltrimethyl ammonium bromide (CTAB) in aqueous solutions was studied. The conductivity of a mixture (cosolvent + water) as function of CTAB concentration was measured at different temperatures. Ethylene glycol and ethanol were used as a cosolvent. The conductivity data were used to determine the critical micelle concentration (CMC) and the effective degree of counterion dissociation of micelle in the temperature range 303.2 to 313.2 K. In all the cases studied, a linear relationship between log([CMC]_mix/mol dm⁻³) and the mass fraction of cosolvent in solvent mixture has been observed. The free energy (ΔG _mic ⁰ ), enthalpy (ΔH _mic ⁰ ), and entropy (ΔS _mic ⁰ ) of micellization were determined using the temperature dependence of CMC. The dependence of these thermodynamic parameters on solvent composition was determined. The standard free energy of micellization was found to be negative in all cases and becomes less negative as the cosolvent content increases. The enthalpy and entropy of micellization are independent of temperature in pure water, while ΔH _mic ⁰ and ΔS _mic ⁰ decrease dramatically with temperature in mixed cosolvents. Furthermore, the entropic contribution is larger than the enthalpic one in pure water, while in the mixed solvents, the enthalpic contribution predominates. The text was submitted by the authors in English.     

Solvation of amides of carboxylic acids in aqueous solutions of ethylene glycol

Enthalpies of solution of amides of formic, acetic, and propionic acids with different degrees of N-substitution in aqueous solutions of ethylene glycol were measured at 298.15 K. The concentration of ethylene glycol did not exceed 4 mol kg^–1. The reasons for increasing endothermic values of the enthalpies characterizing the amide transfer from water to a mixed aqueous-organic solvent on going from primary to tertiary amides and from formamides to the corresponding acetamides are discussed. The enthalpic coefficients of pair interactions between amides and ethylene glycol in water were calculated. The endothermicity of the interaction of the alkyl groups of the amide molecules with ethylene glycol results in positive values of the coefficients. The coefficient values increase with the enhancement of the hydrophobic properties of hydrophilic non-electrolytes (urea, formamide, ethylene glycol) due to an increase in the contribution of the hydrophobic component and a decrease in the contribution from the interaction of the polar groups of amides to the total interaction.     

Densities,refractive indices,and viscosities of N,N-diethylethanol ammonium chloride–glycerol or –ethylene glycol deep eutectic solvents and their aqueous solutions

In this work, we report new experimental data on density, ρ, refractive index, n_D, and viscosity, η, of two deep eutectic solvents, N,N-diethylethanol ammonium chloride–glycerol (DEACG) and N,N-diethylethanol ammonium chloride–ethylene glycol (DEACEG), and their aqueous solutions, over the complete composition range, at temperatures from (298.15 to 343.15) K. Densities and viscosities were measured using the vibrating tube and the falling ball techniques, respectively, while the refractive index at the sodium D line was measured using an automatic refractometer. We aimed to represent the measured properties as a function of temperature and composition, and correlated them using the Redlich–Kister-type equation, for density, a polynomial function, for refractive index, and the Vogel–Fulcher–Tammann (VFT) equation, for viscosity.     

Solubility of amino acids in aqueous poly (ethylene glycol) solutions

The solubilities of amino acids have been measured in water and aqueous poly(ethylene glycol) (PEG) solutions as a function of temperature and PEG concentration. The free energies of transfer from water to aqueous PEG solutions forl-alanine,l-valine,l-isoleucine andl-leucine were positive, while those forl-phenylalanine andl-tryptophan were negative. The corresponding enthalpies of transfer were almost zero for all amino acids. The equilibrium constants of the binding of amino acids to PEG chain were estimated from the solubility data. Amino acids with larger hydrophobicity are bound more strongly to the PEG chain due to the hydrophobic interaction between the methylene groups of PEG and the side chain of amino acid. The equilibrium constants showed a correlation with the dynamic hydration number (n _DHN) which expresses the hydration properties of amino acids in aqueous solution.     

Thermochemical study of acid-base interactions in L-asparagine aqueous solutions

The heats of reactions between an L-asparagine solution and HNO₃ solutions were measured calorimetrically within different pH ranges at 298.15, 308.15, and 318.15 K and an ionic strength of 0.5, 1.0, and 1.5 (KNO₃ and LiNO₃). The heats of stepwise dissociation of L-asparagine were determined. The standard thermodynamic characteristics (Δ _r H ^o, Δ _r G ^o, δ _r S ^o, and ΔC _p ^⪧) of the acid-base interactions in aqueous solutions of the amino acid were calculated. A relationship between the thermodynamic characteristics of the dissociation of L-asparagine and its structure was considered.     

Selective detector of 1,2-propylene glycol dinitrate, 1, propylene glycol mononitrate,and 2-propylene glycol mononitrate using gas chromatography/ thermal energy analyzer or liquid chromatography/ electrochemical detection

Mono- and di-nitrated propylene glycols can be separated and detected using either a gas chromatogph equipped with a nitro-specific thermal energy analyzer (g.c./t.e.a.) or a high-performance liquid chromatograph equipped with an electrochemical detector in the reductive mode (l.c./e.c.). The g.c./t.e.a. exhibits a linear range of three orders of magnitude and provides detection limits in the μg ml^?1 range or lower for these three compounds. The l.c./e.c. provides a linear response over two orders of magnitude and is best suited for the determination of propylene glycol dinitrate. Trapping of these glycols on Amberlite XAD-2 resin is discussed.     

Surface interaction of ethylene glycol with silver

Interaction of ethylene glycol with clean and oxidized surfaces of an Ag catalyst has been studied under pre-catalysis conditions. On a clean surface, ethylene glycol was reversibly adsorbed with the formation of a multilayer coverage. Adsorbed ethylene glycol weakly bonded to the oxidized silver surface leads to the selective formation of glyoxalvia two parallel routes: dehydrogenation and oxidation. Dissociative interaction of ethylene glycol with Ag led to the appearance of formaldehyde and carbon dioxide by-products.     

Enthalpy characteristics of solution of L-cysteine and L-asparagine in water-alcohol mixtures at 298.15 K

The integral enthalpies of solution Δ_sol H ^m of L-cysteine and L-asparagine in mixtures of water with ethanol, n-propanol, and isopropanol at a mole fraction of alcohol of up to 0.32 were determined by calorimetry of solution. The standard enthalpies of solution (Δ_sol H ⁰) of L-serine and of its transfer (Δ_tr H ⁰) from water to a mixed solvent were calculated. The dependences of Δ_sol H ⁰ and Δ_tr H ⁰ on the composition of water-alcohol mixtures pass through a maximum. The calculated enthalpy coefficients of pair interaction of amino acids with alcohol molecules are positive and increase in the order ethanol, n-propanol, isopropanol. The data obtained were interpreted from the viewpoint of various types of interaction in solution and effect of the amino acid residue on the thermochemical characteristics of solution.