Bond dissociation energies and radical stabilization energies associated with model peptide-backbone radicals

Bond dissociation energies (BDEs) and radical stabilization energies (RSEs) have been calculated for a series of models that represent a glycine-containing peptide-backbone. High-level methods that have been used include W1, CBS-QB3, U-CBS-QB3, and G3X(MP2)-RAD. Simpler methods used include MP2, B3-LYP, BMK, and MPWB1K in association with the 6-311+G(3df,2p) basis set. We find that the high-level methods produce BDEs and RSEs that are in good agreement with one another. Of the simpler methods, RBMK and RMPWB1K achieve good accuracy for BDEs and RSEs for all the species that were examined. For monosubstituted carbon-centered radicals, we find that the stabilizing effect (as measured by RSEs) of carbonyl substituents (CX=O) ranges from 24.7 to 36.9 kJ mol(-1), with the largest stabilization occurring for the CH=O group. Amino groups (NHY) also stabilize a monosubstituted alpha-carbon radical, with the calculated RSEs ranging from 44.5 to 49.5 kJ mol(-1), the largest stabilization occurring for the NH2 group. In combination, NHY and CX=O substituents on a disubstituted carbon-centered radical produce a large stabilizing effect ranging from 82.0 to 125.8 kJ mol(-1). This translates to a captodative (synergistic) stabilization of 12.8 to 39.4 kJ mol(-1). For monosubstituted nitrogen-centered radicals, we find that the stabilizing effect of methyl and related (CH2Z) substituents ranges from 25.9 to 31.7 kJ mol(-1), the largest stabilization occurring for the CH3 group. Carbonyl substituents (CX=O) destabilize a nitrogen-centered radical relative to the corresponding closed-shell molecule, with the calculated RSEs ranging from -30.8 to -22.3 kJ mol(-1), the largest destabilization occurring for the CH=O group. In combination, CH2Z and CX=O substituents at a nitrogen radical center produce a destabilizing effect ranging from -19.0 to -0.2 kJ mol(-1). This translates to an additional destabilization associated with disubstitution of -18.6 to -7.8 kJ mol(-1).     

Sensing the physicochemical nature of he and ne in micropores by adsorption measurements

He and Ne in contact with molecular sieves in the form of crystalline A zeolites and amorphous carbon molecular sieves fibers (CMSF) were studied by adsorption measurements. Classification of the effective enclosure of zeolitic apertures and of graphitic constrictions, as determined by recent temperature-programmed desorption mass spectrometry (TPD-MS) studies of adsorption of He and Ne onto these materials, was utilized in making a prudent choice of samples and experimental conditions. In view of the former TPD information, the behaviors of adsorption and volumetric measurements reported herein are straightforwardly interpreted. The combined TPD, adsorption isotherms, and dead volume data deepen the understanding of the physicochemical nature of adsorbed gas, where gas adsorption in the vicinity of pore constrictions and/or apertures as well as on the inner surface areas of pores and/or cages could be resolved. Previous conclusions that the huge activation energies measured for Ne/CMSF at high temperatures are unlikely to characterize chemical desorption but reflect those required for overcoming the barrier of effectively constricted apertures were confirmed by the volumetric data presented here. At 77 K, considerable He adsorption was observed in the porous solids and found to be responsible for abnormal deduced values of dead volumes. The occurrence of significant adsorption of He onto A zeolites and CMSF at 77 K warrants the realization that in cases concerning porous materials, volumetrically deduced quantities should not be taken for granted, but should be carefully considered and uniquely interpreted in relation to the specific experimental conditions under which they are taken.     

A holographic model of deconfinement and chiral symmetry restoration

We analyze the finite temperature behavior of the Sakai-Sugimoto model, which is a holographic dual of a theory which spontaneously breaks a U(N_f)_L × U(N_f)_R chiral flavor symmetry at zero temperature. The theory involved is a 4 + 1 dimensional supersymmetric SU(N_c) gauge theory compactified on a circle of radius R with anti-periodic boundary conditions for fermions, coupled to N_f left-handed quarks and N_f right-handed quarks which are localized at different points on the compact circle (separated by a distance L). In the supergravity limit which we analyze (corresponding in particular to the large N_c limit of the gauge theory), the theory undergoes a deconfinement phase transition at a temperature T_d = 1/2πR. For quark separations obeying L > L_c ? 0.97 ∗ R the chiral symmetry is restored at this temperature, but for L < L_c ? 0.97 ∗ R there is an intermediate phase which is deconfined with broken chiral symmetry, and the chiral symmetry is restored at T_χSB ? 0.154/L. All of these phase transitions are of first order.     

Mechanism of thermal transport in dilute nanocolloids

Thermal conduction modes in a nanocolloid (nanofluid) are quantitatively assessed by combining linear response theory with molecular dynamics simulations. The microscopic heat flux is decomposed into three additive fluctuation modes, namely, kinetic, potential, and collision. For low volume fractions (<1%) of nanosized platinum clusters which interact strongly with xenon host liquid, a significant thermal conductivity enhancement results from the self correlation in the potential flux. Our findings reveal a molecular-level mechanism for enhanced thermal conductivity in nanocolloids with short-ranged attraction and offer predictions that can be experimentally tested.     

Obtaining the bidirectional transmittance distribution function of isotropically scattering materials using an integrating sphere

This paper demonstrates a method to determine the bidirectional transmittance distribution function (BTDF) using an integrating sphere. Information about the sample’s angle-dependent scattering is obtained by making transmittance measurements with the sample at different distances from the integrating sphere. Knowledge about the illuminated area of the sample and the geometry of the sphere port in combination with the measured data combines to a system of equations that includes the angle-dependent transmittance.The resulting system of equations is an ill-posed problem which rarely gives a physical solution. A solvable system is obtained by using Tikhonov regularization on the ill-posed problem. The solution to this system can then be used to obtain the BTDF.Four bulk-scattering samples were characterised using two goniophotometers and the described method to verify the validity of the new method. The agreement shown is excellent for the more diffuse samples. The solution to the low-scattering samples contains unphysical oscillations, but still gives the correct shape of the solution. The origin of the oscillations and why they are more prominent in low-scattering samples are discussed.     

Interpretation of Polarized Absorption and Emission Spectra of Molecules Incorporated in Stretched Polymer Films

Different methods for the interpretation of linear dichroic spectra of molecules incorporated in uniaxial matrices are discussed. A method based on the combination of both polarized absorption and emission measurements is described for the resolution of absorption and emission spectra into their different polarized components, and for the investigation of molecular distributions in the oriented matrix. The distributions of some planar molecules of different shapes incorporated in stretched polyethylene films are presented.     

Self-diffusion in melts of statistical copolymers: The effect of changes in microstructural composition

We have used nuclear reaction analysis to measure diffusion coefficients D in couples consisting of hydrogenated polybutadienes of structure (C₂H₃(C₂H₅))_x(C₄H₈)_1?x and their partly deuterated counterparts. The 1,2- and 1,4-olefinic isomers are randomly distributed along the chains and the mean vinyl fraction x varies between 0.38 and 0.94. We find that the effective monomeric mobility D₀ [defined by D = D₀(N_e/N²) for each copolymer, where N is the backbone length and N_e the entanglement spacing] decreases monotonically with increasing vinyl content x. Over the range of microstructures and temperatures T (?14?40°C) investigated we find log(D₀/T) varies smoothly with (T ? T_g), where T_g is the glass transition temperature of the respective melts. An analysis of our data in terms of a simple activated rate process model suggests that D₀ is controlled by thermally activated hopping of segments whose effective volume is close to that of the respective statistical segment lengths of the copolymeric chains. ©1995 John Wiley & Sons, Inc.     

Meson distributions in photoproduction

Extension of the nova model is applied to γ + p → π + anything. The concept of a photon is motivated from vector dominance, and the parameters describing the production of photon novas are estimated from hadron results. The model is essentially without arbitrary parameters. We compare with inclusive and exclusive data at 9.3 GeV/c, where we find excellent agreement. Predictions for 20 GeV/c are also presented.