Search results for "Activity"
showing 10 items of 7178 documents
Macromolecules in ordered media: 5. Poly(4-vinyl pyridine)—liposome association induced by electrostatic interactions
1997
Abstract The association of water-soluble vinyl polymers to dimyristoyl phosphatidic acid unilamellar vesicles as a function of pH, temperature and salt content using steady-state fluorescence and viscometry has been investigated. Poly(4-vinyl pyridine) fluorescence data were converted to association isotherms and discussed in terms of binding and partition models. The results of this report support previous suggestions: (1) in the case of polyions the inclusion of the activity coefficient in both models is essential; (2) the parameters calculated using the two different theoretical approaches can be directly compared by the relating equation proposed for us. Finally, the excellent agreemen…
Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of Diisopropyl Ether, 2-Propyl Alcohol, and n-Butyl Propionate at 101.3 kPa
2009
Consistent vapor−liquid equilibrium data at 101.3 kPa have been determined for the ternary system diisopropyl ether (1) + 2-propyl alcohol (2) + n-butyl propionate (3) and two constituent binary systems: diisopropyl ether (1) + n-butyl propionate (3) and 2-propyl alcohol (2) + n-butyl propionate (3). The diisopropyl ether (1) + n-butyl propionate (3) system does not present deviation from ideal behavior, and the 2-propyl alcohol (2) + n-butyl propionate (3) system shows light positive deviation from Raoult’s law. The activity coefficients of the solutions were correlated with their compositions by the Wilson, NRTL, and UNIQUAC models. Wisniak−Tamir equations were used to correlate the boili…
Thermodynamic properties of some N-alkyl-N-methylpiperidinium chlorides and N-alkylpiperidine hydrochlorides in water
1993
Densities and heat capacities at 25[degrees]C were measured for N-octyl-, N-decyl- and N-dodecyl-N-methylpiperidinium chlorides and for N-octyl- and N-dodecylpiperidine hydrochlorides in water as functions of concentration. Enthalpies of dilution at 25[degrees]C and osmotic coefficients at 37[degrees]C of the N-methyl-N-alkylpiperidinium chlorides were also measured as functions of concentration. The partial molar volumes, heat capacities, relative enthalpies, nonideal Gibbs energies and entropies at 25[degrees]C were derived as functions of the surfactant concentration. By increasing the alkyl chain length of the surfactant, both the apparent molar volume vs. concentration curves are shift…
Application of headspace analysis to the study of aroma compounds-lipids interactions
1998
Taking into account interactions between aroma compounds and food components is necessary to better manage the flavoring of food products. These interactions occur at a molecular level and reflect changes, at a macroscopic level, in thermodynamic equilibria, such as solubility or volatility. The rate of transfer of an aroma compound from the liquid to the vapor phase can be affected as well. The behavior of aroma compounds in water and lipid solutions was studied in two complementary ways, a thermodynamic and a kinetic approach (head-space analysis). The transfer rate of volatiles at the liquid-water interface does not only depend on the hydrophobicity of the aroma compounds. Vapor-liquid p…
ChemInform Abstract: Conjugate Addition of Organolithium Reagents to α,β-Unsaturated Carboxylic Acids.
2010
Abstract Conjugate addition of primary, secondary, tertiary alkyl and phenyl lithium reagents to 2-alkenoic acids affords good yields of branched saturated carboxylic acids. Methyl groups at the α- and β-carbon of the 2-alkenoic acid decrease reactivity as acceptors, and foster deprotonation, respectively. The lithium enediolate resulting from the conjugate addition can react with electrophiles. PM3 calculations are in agreement with the substituent effects.
ChemInform Abstract: The Construction of Quaternary Stereocenters by the Henry Reaction: Circumventing the Usual Reactivity of Substituted Glyoxals.
2011
The enantioselective Henry reaction between alkyl- and arylglyoxal hydrates and nitromethane catalyzed by Cu(II)-iminopyridine complexes takes place regioselectively on the ketone carbonyl group to give chiral tertiary nitroaldols with high functional group density and enantiomeric excesses of up to 96 %. Both aromatic and aliphatic glyoxals are suitable substrates for this reaction.
Evidence for essential primary amino groups in a bacterial coupling factor F1ATPase.
1980
Abstract We have found that the binding of pyridoxal-5′-phosphate to 6 primary amino groups leads to the inactivation of the enzyme. A preferential reaction of pyridoxal-5′-phosphate with the α-subunits of this enzyme can be demonstrated. The reactivity of the amino groups is influenced by various effectors. In the presence of ATP the inhibition of the ATPase activity is noncompetitive.
An analysis of the regioselectivity of 1,3-dipolar cycloaddition reactions of benzonitrile n-oxides based on global and local electrophilicity and nu…
2009
The regioselectivity of the 1,3-dipolar cycloaddition (13DC) reactions of benzonitrile N-oxides (BNOs) with electrophilic and nucleophilic alkenes has been analyzed by using global and local nucleophilicity and electrophilicity reactivity indices defined within the conceptual DFT. The BNOs react with electron-deficient and electron-rich ethylenes, but the regioselectivities of these polar reactions are different. Whereas the reactions with electron-rich ethylenes are completely regioselective, yielding 5-isoxazolines, a change in the regioselectivity is observed in the reactions with electron-deficient ethylenes, which yield a mixture of 4- and 5-isoxazolines. Analysis of the energies, geom…
Photochemical Functionalization of Allyl Benzoates by C-H Insertion
2013
The photoreactivity of allyl benzoates, containing an electron-rich double bond, has been explored by irradiation at 305 nm in different solvents. Solvent addition products arising from an insertion of the alpha H–C bonds of THF, dioxane, and i-PrOH to the allylic double bond was realized. The observed reactivity depended on reaction conditions and substitution pattern of the substrate. A DFT study on this unusual reaction was performed allowing the formulation of two mechanistic pathways.
A DFT study of the mechanism of NHC catalysed annulation reactions involving α,β-unsaturated acyl azoliums and β-naphthol.
2016
The mechanism of NHC catalysed annulation reactions involving an α,β-unsaturated acyl azolium and β-naphthol has been studied using DFT methods at the MPWB1K/6-311G(d,p) level in toluene. For the C-C bond formation step, which corresponds to the rate- and stereo-determining step of this NHC catalysed reaction, the two competitive addition modes, i.e. the 1,2- and the 1,4-additions, have been studied. In toluene, acyl azolium forms an ion pair (IP) with the counterion chloride anion. Interestingly, β-naphthol forms a hydrogen bond with the chloride anion of IP, increasing the nucleophilic character of β-naphthol and the electrophilic character of the acyl azolium moiety. For the first time, …