The Modified Group Expansions for Construction of Solutions to the BBGKY Hierarchy

A solution to the BBGKY hierarchy for nonequilibrium distribution functions is obtained within modified boundary conditions. The boundary conditions take into account explicitly both the nonequilibrium one-particle distribution function as well as local conservation laws. As a result, modified group expansions are proposed. On the basis of these expansions, a generalized kinetic equation for hard spheres and a generalized Bogolubov–Lenard–Balescu kinetic equation for a dense electron gas are derived within the polarization approximation.     

Properties of poly(vinyl alcohol)-graft-polyacrylamide copolymers depending on the graft length. 3. Benzene solubilization by solutions of the copolymer

The peculiarities of poly(vinyl alcohol)-graft-polyacrylamide copolymers (PVA-g-PAA), which are characterized by the equal average number (N=9), but various molecular weight (or length) of graft chains, in comparison with individual PAA and PVA, were investigated in aqueous medium. Sharp rise in benzene solubilization in PVA-g-PAA solutions at M_PAA higher than 4.3·10⁵ has been established. It was shown that such effect is stipulated by the destruction of intramolecular polymer-polymer complex in the copolymer and increasing the benzene binding to separate PVA-g-PAA groups by means of hydrogen bonds. The changes in the PVA-g-PAA solubilizing ability as the function of temperature were also investigated. The obtained results are discussed from the point of view of conformational transitions of intramolecular polymer-polymer complexes (intraPPC), which exist in copolymers, in dependence on the length of graft chains.     

Simple preparation of diamondoid 1,3-dienes via oxetane ring opening

The transformations of apical mono- and bisacetyl diamondoids to the respective oxetanes and subsequent acid-catalyzed ring opening/dehydration lead to diamondoidyl mono- and bis-1,3-dienes in high preparative yields.     

Stable alkanes containing very long carbon-carbon bonds

The metal-induced coupling of tertiary diamondoid bromides gave highly sterically congested hydrocarbon (hetero)dimers with exceptionally long central C-C bonds of up to 1.71 ? in 2-(1-diamantyl)[121]tetramantane. Yet, these dimers are thermally very stable even at temperatures above 200 °C, which is not in line with common C-C bond length versus bond strengths correlations. We suggest that the extraordinary stabilization arises from numerous intramolecular van der Waals attractions between the neighboring H-terminated diamond-like surfaces. The C-C bond rotational dynamics of 1-(1-adamantyl)diamantane, 1-(1-diamantyl)diamantane, 2-(1-adamantyl)triamantane, 2-(1-diamantyl)triamantane, and 2-(1-diamantyl)[121]tetramantane were studied through variable-temperature (1)H- and (13)C NMR spectroscopies. The shapes of the inward (endo) CH surfaces determine the dynamic behavior, changing the central C-C bond rotation barriers from 7 to 33 kcal mol(-1). We probe the ability of popular density functional theory (DFT) approaches (including BLYP, B3LYP, B98, B3LYP-Dn, B97D, B3PW91, BHandHLYP, B3P86, PBE1PBE, wB97XD, and M06-2X) with 6-31G(d,p) and cc-pVDZ basis sets to describe such an unusual bonding situation. Only functionals accounting for dispersion are able to reproduce the experimental geometries, while most DFT functionals are able to reproduce the experimental rotational barriers due to error cancellations. Computations on larger diamondoids reveal that the interplay between the shapes and the sizes of the CH surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers) that are strongly held together exclusively by dispersion forces.     

Site-site memory equation approach in study of density/pressure dependence of translational diffusion coefficient and rotational relaxation time of polar molecular solutions: acetonitrile in water, methanol in water, and methanol in acetonitrile

We present results of the theoretical study and numerical calculation of the dynamics of molecular liquids based on the combination of the memory equation formalism and the reference interaction site model (RISM). Memory equations for the site-site intermediate scattering functions are studied in the mode-coupling approximation for the first-order memory kernels, while equilibrium properties such as site-site static structure factors are deduced from RISM. The results include the temperature-density (pressure) dependence of translational diffusion coefficients D and orientational relaxation times tau for acetonitrile in water, methanol in water, and methanol in acetonitrile--all in the limit of infinite dilution. Calculations are performed over the range of temperatures and densities employing the extended simple point charge model for water and optimized site-site potentials for acetonitrile and methanol. The theory is able to reproduce qualitatively all main features of temperature and density dependences of D and tau observed in real and computer experiments. In particular, anomalous behavior, i.e, the increase in mobility with density, is observed for D and tau of methanol in water, while acetonitrile in water and methanol in acetonitrile do not show deviations from the ordinary behavior. The variety exhibited by the different solute-solvent systems in the density dependence of the mobility is interpreted in terms of the two competing origins of friction, which interplay with each other as density increases: the collisional and dielectric frictions which, respectively, increase and decrease with increasing density.     

The synthesis of salts and esters of perfluorinated dithio- and thiocarboxylic acids from carbon disulfide and carbonyl sulfide reacting with RFSiMe3/F

Trimethyl(perfluoroalkyl)silanes react with carbonyl sulfide and carbon disulfide in the presence of fluoride ion to give salts and, after alkylation of the latter, esters of the corresponding perfluorinated thio- and dithiocarboxylic acids.     

Quantum stochastic differential equations for boson and fermion systems—method of non-equilibrium thermo field dynamics

A unified canonical operator formalism for quantum stochastic differential equations, including the quantum stochastic Liouville equation and the quantum Langevin equation both of the Itô and the Stratonovich types, is presented within the framework of non-equilibrium thermo field dynamics (NETFD). It is performed by introducing an appropriate martingale operator in the Schrödinger and the Heisenberg representations with fermionic and bosonic Brownian motions. In order to decide the double tilde conjugation rule and the thermal state conditions for fermions, a generalization of the system consisting of a vector field and Faddeev-Popov ghosts to dissipative open situations is carried out within NETFD.     

Spectral Amplitude Measures of Adductor Spasmodic Dysphonic Speech

Spectral amplitude measures are sensitive to varying degrees of vocal fold adduction in normal speakers. This study examined the applicability of harmonic amplitude differences to adductor spasmodic dysphonia (ADSD) in comparison with normal controls. Amplitudes of the first and second harmonics (H1, H2) and of harmonics affiliated with the first, second, and third formants (A1, A2, A3) were obtained from spectra of vowels and /i/ excerpted from connected speech. Results indicated that these measures could be made reliably in ADSD. With the exception of H1(*)-H2(*), harmonic amplitude differences (H1(*)-A1, H1(*)-A2, and H1(*)-A3(*)) exhibited significant negative linear relationships (P < 0.05) with clinical judgments of overall severity. The four harmonic amplitude differences significantly differentiated between pre-BT and post-BT productions (P < 0.05). After treatment, measurements from detected significant differences between ADSD and normal controls (P < 0.05), but measurements from /i/ did not. LTAS analysis of ADSD patients' speech samples proved a good fit with harmonic amplitude difference measures. Harmonic amplitude differences also significantly correlated with perceptual judgments of breathiness and roughness (P < 0.05). These findings demonstrate high clinical applicability for harmonic amplitude differences for characterizing phonation in the speech of persons with ADSD, as well as normal speakers, and they suggest promise for future application to other voice pathologies.     

Functionalized nanodiamonds part 3: thiolation of tertiary/bridgehead alcohols

[reaction: see text] Treatment of acyclic as well as polycyclic tertiary mono- and dihydroxy hydrocarbon derivatives with thiourea in the presence of hydrobromic and acetic acid represents a convenient one-step route to the respective tertiary thiols and dithiols. This procedure was used for the preparation of diamondoid thiols of diamantane, triamantane, [121]tetramantane, and others that are prospective nanoelectronic materials.