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Biomedical subjects

H Eyring

Publications and source records attributed to H Eyring.

At least 37 records · Page 2Linked to original sources
PubMed1980

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form.

The rotational strengths of the four longer wavelength transitions, B(2u), B(1u), and the two E(1u), of adenosine derivatives constrained in the syn form have been investigated theoretically and experimentally. The theory combines a complete neglect of differential overlap version S (CNDO/S) description of the base with a generalized bond exciton method by means of a matrix method. Rotational strength wheels for these transitions showing the rotational strength as a function of the glycosidic rotational angles are presented and sector rules discussed. Similar sector rules are predicted for purine nucleoside derivatives containing the 6-amino substituent, regardless of heteroatom content at positions 1 or 3 of the base. The sector rules for the B(2u) rotational strength of purine nucleosides lacking the 6-amino substituent are strongly influenced by aza substitution. The circular dichroism spectra of 3-deazaadenosine, 8-(alpha-hydroxyisopropyl)-adenosine, and other purine nucleosides having a strong preference for the syn conformation are presented and compared with the theoretical results.

Journal Article↗
PubMed1980

Temperature and pressure dependence of viscosity of quantum liquid He according to significant structure theory.

Both solid-like and gas-like flow structures are considered in the calculation of viscosity of liquid (4)He using the significant structure theory of liquids. The predominance of quantum mechanical zero-point motion over that arising from thermal excitation is taken into account for the solid-like motion of molecules. The viscosity of liquid (4)He under its own vapor pressure calculated over its whole temperature range is in reasonably good agreement with experimental data. The pressure dependence of viscosity also was obtained. The calculation does not yield good results at high densities where the free jumping of molecules into the nearest neighboring vacancies through the kinetic zero-point motion is no longer plausible.

Journal Article↗
PubMed1980

A theoretical study of resonance Raman scattering from molecules: High pressure effect.

The main purpose of this paper has been to study the high pressure effect on the resonance Raman scattering (RRS) of molecules in a dense medium. In deriving the RRS cross section under high pressure, a different approach from that presented in the previous papers has been used, and the resulting expression for the RRS cross section can be used to treat both pressure and temperature effects.

Journal Article↗
PubMed1979

Antagonism between high pressure and anesthetics in the thermal phase-transition of dipalmitoyl phosphatidylcholine bilayer.

The antagonizing action of hydrostatic pressure against anesthesia is well known. The present study was undertaken to quantitate the effects of hydrostatic pressure and anesthetics upon the phase-transition temperature of dipalmitoyl phosphatidylcholine vesicles. The drugs used to anesthetize the phospholipid vesicles included an inhalation anesthetic, halothane, a dissociable local anesthetic, lidocaine and an undissociable local anesthetic, benzyl alcohol. All anesthetics decreased the phase-transition temperature dose-dependently. In the case of lidocaine, the depression was pH dependent and only uncharged molecules were effective. The application of hydrostatic pressure increased the phase-transition temperature both in the presence and the absence of anesthetics. The temperature-pressure relationship was linear over the entire pressure range studied up to 340 bars. Through the use of Clapeyron-Clausius equation, the volume change accompanying the phase-transition of the membrane was calculated to be 27.0 cm3/mol. Although the anesthetics decreased the phase-transition temperature, the molar volume change accompanying the phase-transition was not altered. The anesthetics displaced the temperature-pressure lines parallel to each other. The mole fraction of the anesthetics in the liquid crystalline membrane, calculated from the van't Hoff equation, was independent of pressure. This implies that pressure does not displace the anesthetics from the liquid membrane, and the partition of these agents remains constant. The volume change of the anesthetized phospholipid membranes is entirely dependent upon the phase-transition and not on the space occupied by the anesthetics.

Anesthetics↗
PubMed1979

Hydrophilic region of lecithin membranes studied by bromothymol blue and effects of an inhalation anesthetic, enflurane.

A pH-indicator dye, bromothymol blue, was used to probe the hydrophilic surface of dimyristoyl-, dipalmitoyl-, and distearoylphosphatidylcholine bilayer vesicles. The apparent pK of the surface-adsorbed dye was larger than the bulk pK value. The contribution of the choline positive charge on the dissociation constant of the dye adsorbed on the vesicle surface was estimated by screening the charge interaction with 2 M KCl. The effective surface potentials interacting with the dye were thus estimated to be 33.2, 45.6, and 46.8 mV, respectively, for the dimyristoyl-, dipalmitoyl-, and distearoylphosphatidylcholine vesicles. From the differences between the obtained effective potentials and the calculated surface potentials of the charge-determining plane of the choline head, the distances between the prototropic part of the dye and the choline charge-determining plane were estimated to be 10.5, 8.0, and 7.8 A, respectively. These values were obtained at 25 degrees C; the dimyristoylphosphatidylcholine membrane was in the liquid-crystalline phase and the other two were in the solid gel phase. Addition of an inhalation anesthetic, enflurane, decreased the distance in the dimyristoylphosphatidylcholine vesicles and increased the distance in the dipalmitoyl- and distearoylphosphatidylcholine vesicles. The increase of precessional motion of choline head by the inhalation anesthetic is apparently responsible for the changes.

Bromthymol Blue↗
PubMed1979

Significant structure theory applied to electrolyte solution.

The significant structure theory has been successfully applied to an aqueous NaCl solution. Liquid water is assumed to have a domain structure and the ions are hydrated by water molecules. The partition function is composed of the partition function for the water and that for the salt, and the excess free energy term from the Debye-Hückel theory is also added. The thermodynamic properties, such as molar volume, vapor pressure, entropy of vaporization, and heat capacity, as well as the dielectric constant are calculated over the whole concentration ranges and wide temperature ranges. The agreement between theory and experiment is satisfactory.

Journal Article↗
PubMed1979

Conformation of nucleosides: circular dichroism study on the syn-anti conformational equilibrium of 2-substituted benzimidazole nucleosides.

The solution conformations of 2-substituted derivatives of 1-(beta-D-ribofuranosyl)benzimidazole have been determined by circular dichroism spectroscopy in aqueous solutions. It is shown that analogs with methyl, amino, or methylamino substituents at position 2 of the benzimidazole ring (position 8 of the purine ring) have predominantly anti conformations, whereas analogs with chloro, aza, methoxy, or methylmercapto substituents have predominantly syn conformations. The preferred solution conformations of the benzimidazole nucleosides and analogous purine nucleosides are compared. The results demonstrate that the replacement of nitrogen by carbon at position 3 of the purine ring of purine (beta) nucleosides leads to important conformational consequences, which are strengthened or neutralized by substituents at position 8 of the purine ring.

Benzimidazoles↗
PubMed1979

Interferon induction: a conformational hypothesis.

The ability of polynucleotides or polynucleotide duplexes such as poly(I).poly(C) to induce interferon production is proposed to depend on the existence of certain stable glycosidic orientations. It appears that a slight increase in instability of 1--3 kcal/mole (1 cal = 4.184 J) in the conformational regions near 20 degrees, 80 degrees, and 160 degrees leads to a loss of potency with respect to interferon induction. Thus, it is proposed that, for a polynucleotide to exist in the overall conformation necessary for interferon induction, stability of glycosidic orientations near 20 degrees, 80 degrees, and 160 degrees may be necessary to confer flexibility and activity on polynucleotide structures. This proposed conformational triad of stable conformational regions essential to interferon induction is based on the results of conformational energy calculations of the glycoside rotational profiles of adenosine, 7-deazaadenosine, inosine, and 7-deazainosine, as well as the conformational properties of other purine nucleoside analogs, and on inferences derived from calculations about the conformational effect in polynucleotides of removing the 2'-OH group.

Adenosine↗
PubMed1979

Thermodynamic properties of solid CH(4).

The significant structures procedure of liquids has been used to calculate the thermodynamic properties of solid C(2)H(4). Two degeneracy terms were used to describe the behavior in the vicinities of the two phase transitions. The calculated entropy and specific heat agree well with experimental results from a few kelvins to the melting point. Less satisfactory agreement is obtained for compressibility and thermal expansion coefficients. This simple model represents surprisingly well the phase transitions in the solid state.

Journal Article↗
PubMed1979

Density matrix method for orbital localization.

A method is presented for localizing molecular orbitals, based on diagonalizing subunits of the density matrix. First, nonbonding orbitals are found by diagonalizing the monatomic subunits; then, diatomic sigma or pi bonding and antibonding orbitals are obtained from the diatomic subunits for all bonded pairs of atoms; finally, the delocalized pi-orbitals for particular chromophores are found by projecting the first set out of the self-consistent field (SCF) Hamiltonian. The results show good general agreement with other localization methods, with advantages in the ability to display group orbitals in complex molecules which most closely resemble the SCF orbitals for simple prototypes.

Journal Article↗
PubMed1979

Effect of molecular rotation on the vibration-vibration energy transfer in condensed media.

The purpose of the present communication has been to present the derivation of the vibrational relaxation rate constant for the case in which both phonons and the molecular rotation (three-dimensional) participate in the vibrational relaxation and to study the effect of molecular rotation on the vibration-vibration energy transfer in the condensed phase. The experimental results of vibration-vibration energy transfer between donors, NH and ND, and acceptors, CO and (13)CO, have been analyzed.

Journal Article↗
PubMed1979

A theory of light-induced explosion.

This paper presents a theoretical analysis, based on a simplified one-dimensional model, of the response of an explosive to a wide range of light intensities. A primary result has been the identification and development of a relationship among the important critical parameters. Numerical results illustrating the relationship among the critical light intensity, sample dimension, and ambient temperature have been obtained, with lead azide as the example.

Journal Article↗
PubMed1978

A conformational basis for the antiviral inactivity of tetrazole ribonucleosides.

The antiviral activity of ribavirin has been associated with its inhibition of the enzyme, IMP dehydrogenase. The ability of ribavirin to inhibit this enzyme has previously been shown to be related to its stability in the high anti glycosidic conformation. The antiviral effectiveness of several analogs of ribavirin have been investigated recently. The evidence indicates their antiviral effectiveness is related to their stability in the high anti conformation. Recently the disposition of purine analogs that pass through the inosine monophosphate branch point has been investigated. The results of these studies are consistent with the concept that the conversion of IMP to XMP requires the high anti conformation and that the conversion of IMP to adenylosuccinate requires some other conformation, possibly the anti conformation.

Azoles↗
PubMed1978

Hysteresis effects of CH(4) and CH(4) in the regions of the solid-phase transitions.

The thermodynamic model of hysteresis in phase transitions based on the regular solution theory, previously developed, was applied to the solid phases of C(1)H(4) and C(2)H(4). The width and height of the hysteresis loops for these systems were calculated and compared with the experimental data; agreement was satisfactory.

Journal Article↗
PubMed1978

Ion flow through a membrane: concentration and current responses to a step potential change.

Solutions of the simplified time-dependent Nernst-Planck electrodiffusion equations for various membrane models under the influence of a step voltage change are presented. Comparison of the results for a membrane with continuous sites to those for membranes with two, three or five intermediate sites shows little difference either qualitatively or quantitatively in the concentration of the diffusible ion inside the membrane, although some quantitative differences are evident in the calculated currents.

Electric Conductivity↗
PubMed1978

Ion flow through a membrane: effect of chemical reaction on time dependence.

The membrane model previously described [Hays, T.R., Buckwalter, C.Q., Lin S.H. & Eyring, H. (1978) Proc. Natl. Acad. Sci. USA 75, 1612-1615] for ion flow through a membrane is expanded to include the effect of binding of the mobile ion at the occupiable sites in the membrane. Two different effects were investigated: alteration of the association-dissociation rates at constant equilibrium constant and alteration of the equilibrium constant at constant dissociation constant. Increasing the rates of association and dissociation initially causes an increased slowing of the relaxation to the final steady state, though ultimately the curves for the faster rates cross those for the slower states. Increasing the equilibrium constant causes a greater delay in the relaxation curve, with the curves for different equilibrium constants not crossing. Overall, the effect of binding is not very great unless the equilibrium constant for binding is quite large.

Binding Sites↗
PubMed1978

Electric double layer dynamics by high-field electroluminescence in aqueous solution (Destriau effect).

Transient luminescence induced by high electric fields (>2.5 x 10(4) V/cm) was observed in aqueous solutions of 6,8-dihydroxypyrene-1,3-disulfonic acid. The light emission takes place both at the leading and the trailing edges of the perturbing electric square pulse. It occurs only during the variation of the applied field and disappears with a time constant of 0.5 musec at constant field. In solid state phosphors, where this phenomenon has been reported previously, it is known as the Destriau effect. The mechanisms of excitation and emission can be explained by the electron injection model, in which the time constant of the luminescence decay is associated with the rate of formation of the space charge. This space charge appears as a separation of positive and negative charges into a double layer stabilized by the applied potential.

Journal Article↗