Thermal and dilute-solution properties of zwitterionic copolymers

We report the synthesis, characterization, thermal and dilute-solution properties of zwitterionic copolymers of the sulfobetaine type, where the proportion of ionic groups is varied over a wide range. Two different structures are considered: poly (2-vinyl pyridine sulfopropyl betaine) and poly (4-vinyl pyridine sulfopropyl betaine). Synthesis is carried out to obtain random copolymers which are further characterized and their ionic content determined. At low proportions of ionic groups, the behavior is similar to that observed in ionomers, with substantial differences between the two structures, Increased interaction among the zwitterionic groups at higher charge densities is evidenced, which leads to the formation of clusters and agglomerates. An increase in the intrinsic viscosity with salt content in aqueous solutions is also observed. This behavior is analogous to that of homopolymers with 100% ionic content, but with particular features of interest.     

Direct versus resonances mediated F+OH collisions on a new 3A" potential energy surface

A theoretical study of the F(2P) + OH(2Pi) --> HF(1Sigma+) + O(3P) reactive collisions is carried out on a new global potential energy surface (PES) of the ground 3A" adiabatic electronic state. The ab initio calculations are based on multireference configuration interaction calculations, using the aug-cc-pVTZ extended basis sets of Dunning et al. A functional representation of the PES shows no nominal barrier to reaction, contrary to previous results by others. Wave packet and quasiclassical trajectory calculations have been performed for this PES to study the F + OH(v = 0,j) reactive collision. The comparison was performed at fixed and constant values of the total angular momentum from 0 to 110 and relative translational energy up to 0.8 eV. The reaction presents a dynamical barrier, essentially due to the zero-point energy for the bending vibration near the saddle point. This determines two different reaction mechanisms. At energies higher than approximately 0.125 eV the reaction is direct, while below that value it is indirect and mediated by heavy-light-heavy resonances. Such resonances, also found in the simulations of the photodetachment spectrum of the triatomic anion, manifest themselves in the quasiclassical simulations, too, where they are associated to periodic orbits.     

Observation of B(+)-->phiphiK(+) and evidence for B(0)-->phiphiK(0) below eta(c) threshold

We report measurements of the decays B(+)-->phiphiK(+) and B(0)-->phiphiK(0) using a sample of 231 x 10(6) BB pairs collected with the BABAR detector at the PEP-II asymmetric-energy B factory at the Stanford Linear Accelerator Center. The branching fractions are measured to be B(B(+)-->phiphiK(+))=(7.5+/-1.0(stat)+/-0.7(syst)) x 10(-6) and B(B(0)-->phiphiK(0))=(4.1(-1.4)(+1.7)(stat)+/-0.4(syst)) x 10(-6) for a phiphi invariant mass below 2.85 GeV/c(2).     

An accelerated closed universe

We study a model in which a closed universe with dust and quintessence matter components may look like an accelerated flat Friedmann–Robertson–Walker (FRW) universe at low redshifts. Several quantities relevant to the model are expressed in terms of observed density parameters, _M and , and of the associated density parameter _Q related to the quintessence scalar field Q.     

Model study on steady heat capacity in driven stochastic systems

We explore two- and three-state Markov models driven out of thermal equilibrium by non-potential forces, to demonstrate basic properties of the steady heat capacity based on the concept of quasistatic excess heat. It is shown that large enough driving forces can make the steady heat capacity negative. For both the low- and high-temperature regimes we propose an approximative thermodynamic scheme in terms of “dynamically renormalized” effective energy levels.     

Scalar-Particle Self-Energy Amplitudes and Confinement in Minkowski Space

We analyze the analytic structure of the Covariant Spectator Theory (CST) contribution to the self-energy amplitude for a scalar particle in a ${\phi^2\chi}$ theory. To this end we derive dispersion relations in 1+1 and in 3+1 dimensional Minkowski space. The divergent loop integrals in 3+1 dimensions are regularized using dimensional regularization. We find that the CST dispersion relations exhibit, in addition to the usual right-hand branch cut, also a left-hand cut. The origin of this “spectator” left-hand cut can be understood in the context of scattering for a scalar ${\phi^2\chi^2}$ -type theory. If the interaction kernel contains a linear confining component, its contribution to the self-energy vanishes exactly.     

Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

Proton conduction in the binary system (1 − x)CsHSeO4–xKHSeO4 studied with a free-energy model

Electrical Impedance Spectroscopy (EIS) was used to study the electrical properties of the (1???x)CsHSeO₄–xKHSeO₄ binary system with concentrations x?=?0.0 and 0.1. The results show a higher proton-conduction phase above 80°C for both concentrations, however, while DC conductivity of CsHSeO₄ shows a gradual change to higher values in the 80–118°C temperature range, the 0.9CsHSeO₄–0.1KHSeO₄ concentration reveals an abrupt change at about 80°C to an intermediate temperature phase. The observed behavior for the doped sample was modeled using a trial free-energy density, based on the concentration of mobile ions, that takes into account the formation of defects, configurational and phonon entropies, and defect-defect interactions. By minimising the free-energy density one obtains two roots for the carrier concentration at a given temperature, which corresponds to a stable and metastable configuration. It is possible to characterise the phase behavior of the system by means of temperature and two model parameters, which depend on the crystalline properties of the system, but not on temperature. One can successfully explain the conductivity behavior of the system by changing the model parameters if it is assumed that its variations are due to the carriers density.