Molecular modeling study of the differential ligand–receptor interaction at the μ, δ and κ opioid receptors

3D models of the opioid receptors , and were constructed using BUNDLE, an in-house program to build de novo models of G-protein coupled receptors at the atomic level. Once the three opioid receptors were constructed and before any energy refinement, models were assessed for their compatibility with the results available from point-site mutations carried out on these receptors. In a subsequent step, three selective antagonists to each of three receptors (naltrindole, naltrexone and nor-binaltorphamine) were docked onto each of the three receptors and subsequently energy minimized. The nine resulting complexes were checked for their ability to explain known results of structure-activity studies. Once the models were validated, analysis of the distances between different residues of the receptors and the ligands were computed. This analysis permitted us to identify key residues tentatively involved in direct interaction with the ligand.     

Excess enthalpies of aqueous ternary solutions of urea and polyols at 25°C

The heats of dilution of nine ternary solutions of urea and polyols have been determined at 25°C. Excess enthalpies and their virial coefficients h _xy have been evaluated and compared with the data reported in the literature for mono- and polyfunctional alcohols and other oxygenated nonelectrolytes. The group additivity approach of Savage and Wood was applied and the contributions to the enthalpy coefficients, due to the water mediated interactions between urea and the functional groups –CH₂–, –OH, and –O– were determined. On the other hand, by using empirical combination rules among the cross- and self-enthalpic interaction coefficients it is possible to emphasize the large differences in the behavior (even in the presence of urea) of the polyols (and in particular of cyclitols) and of saccharides.     

The ionization of sulfurous acid in Na−Mg−Cl solutions at 25°C

The stoichiometric pK ₁ ^* and pK ₂ ^* for the ionization of sulfurous acid has been determined from emf measurements in NaCl solutions with varying concentrations of added MgCl₂ (m=0.1, 0.2 and 0.3) from I=0.5 to 6.0 molal at 25°C. These experimental results have been treated using both the ion pairing and Pitzer's specific ion-interaction models. The Pitzer parameters for the interaction of Mg²⁺ with SO₂ and HSO ₃ ^– yielded =0.085±0.004, ⁽⁰⁾ = 0.35±0.02, ⁽¹⁾ = 1.2±0.04, and C = –0.072±0.007. The Pitzer parameters ⁽⁰) = –2.8±0.4, ⁽¹⁾ = 12.9±2.9 and ⁽²⁾ = –2071±57 have been determined for the interactions of Mg²⁺ with SO ₃ ^2– . The calculated values of pK ₁ ^* and pK ₂ ^* using Pitzer's equations reproduce the measured values to within ±0.04 pK units. The ion pairing model with log K_MgSO3=2.36±0.02 and log_MgSO3 = 0.1021, reproduces the experimental values of pK ₂ ^* to ±0.01. These results demonstrate that treating the data by considering the formation of MgSO₃ yields a better fit of the experimental measurements with fewer adjustable parameters. With these derived coefficients obtained from the Pitzer equations and the ion pairing model, it is possible to make reliable estimates of the activity coefficients of HSO ₃ ^– and SO ₃ ^2– in seawater, brines and marine aerosols containing Mg²⁺ ions.     

Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

Mechanistic aspects of the Wolff-Kishner reaction. V. The cation effect on the reaction of benzophenone hydrazone in butyl carbitol and decyl alcohol

The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated.     

Surface solid-state interactions in copper-nickel-cement catalysts for hydrogenation of oxygen

The surface phase composition of alumocalcium cement-supported CuO and CuO-NiO catalysts prepared by chemical mixing has been studied using the method of thermo-vacuum curves of electric conductivity. The deactivation of these catalysts due to overheating to 800 °C under conditions of hydrogenation of oxygen is rationalized by the partial extraction of CuO (and NiO) from the stabilizing structure of the support solid solutions and by sintering of the extracted oxides and the reduced metallic phase. Complete regeneration of the CuO-NiO-talum catalysts can be achieved if a considerable amount (20%) of copper hydroxocarbonate is added.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1559–1562, September, 1994.     

Synthesis, crystal structure and magnetic properties of a novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O)

A novel complex [Cu(NIT2Py)(PDA)(H₂O)]·(CH₃OH)(H₂O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H₂O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H₂O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.     

Diffusion current on a nonuniform electrode: Calculation with integral equations

Identity of mathematical problems concerning calculation of the distribution of reactants’ concentrations and the current near the surface of a nonuniform (strip) electrode and distribution of displacements and forces in the case of an elastic layer “antiplane” deformation caused by the punch action. Formulas for calculating the current at a strip electrode are derived for various ratios between the electrode width and the diffusion layer thickness by means of asymptotic methods designed for calculating problems of mechanical contact interactions. It is noted that calculations of the diffusion current for involved activity distributions at the electrode surface may benefit from asymptotic methods of mechanics of contact interactions.     

Intramolecular dimers: a new design strategy for fluorescence-quenched probes

Fluorogenic probes dual-labeled with reporter and quencher dyes use a change in fluorescence to monitor biochemical events (e.g., substrate binding or enzyme digestion). Such events change the reporter-quencher distance, which affects fluorescence. Recently, it is has been shown that static quenching through intramolecular dimers is an important mechanism that can sometimes be more efficient than F?rster resonance energy transfer (FRET).