Poly(arylene sulfide)s by nucleophilic aromatic substitution polymerization of 2,7‐difluorothianthrene

Poly(thianthrene phenylene sulfide) and poly(thianthrene sulfide) have been prepared by nucleophilic aromatic substitution polymerization of the activated monomer 2,7‐difluorothianthrene with bis thiophenoxide and sulfide nucleophiles, respectively. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) mass spectrometry, UV‐Vis spectroscopy, refractometry, and intrinsic viscosity (IV) measurements. The polymers produced exhibit 5% weight loss values approaching 500 °C in inert and air atmospheres and glass transition temperatures that range from 149 to 210 °C. Poly(thianthrene phenylene sulfide) with a number average molecular weight of 22,100 g/mol has been synthesized with an IV in DMPU of 0.62 dL/g at 30 °C. Creasable films of this polymer have been prepared by solvent casting and melt pressing at 250 °C. Films of poly(thianthrene phenylene sulfide) exhibit transparencies greater than 50% at wavelengths exceeding 400 nm and a high refractive index value of 1.692 at a wavelength of 633 nm, making the polymer interesting for optical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2453–2461, 2009     

Virtual reality in medicine: A personal perspective

This personal perspective is an attempt to look at the role and impact of virtual reality (VR) as related to medicine and medical practice over the past 10–15 years. A similar treatise was recently published (Robb, 2002) in much shorter form. This more complete version is still not intended to be, nor can it be, fully comprehensive and inclusive of all developments or viewpoints. It is primarily based on the author’s experience and opinion. Although such a review begs for many references to published works, that too is eschewed in the interest of preserving, for better or worse, the single view of the author in this article. Only seven references are included which contain copious other references to much of the material touched upon in this essay. To the extent that one can learn from history, this synopsis will also fall short, not so much due to lack of confirming references, but rather because the impact of VR in medicine has been an evolutionary culmination of digression and progression that has resulted in some success and useful contributions but also some wasted time and resources.     

Estimating functions of canonical correlation coefficients

Let ρ²₁,…,ρ²_p be the squares of the population canonical correlation coefficients from a normal distribution. This paper is concerned with the estimation of the parameters δ₁,…,δ_p, where $\text{δ}{}_{\mathrm{i}}\text{=}\text{ρ}{}^2{}_{\mathrm{i}}\text{(1 ? ρ}{}^2{}_{\mathrm{i}}\text{)}$, i = 1,…,p, in a decision theoretic way. The approach taken is to estimate a parameter matrix Δ whose eigenvalues are δ₁,…,δ_p, given a random matrix F whose eigenvalues have the same distribution as $\text{r}{}^2{}_{\mathrm{i}}\text{(1 ? r}{}^2{}_{\mathrm{i}}\text{)}$, i = 1,…,p, where r₁,…,r_p are the sample canonical correlation coefficients.     

Relative timing characteristics of hearing-impaired speakers.

Speech duration characteristics of phrase-level utterances produced by 26 severely and profoundly hearing-impaired adults were examined acoustically using relative timing measures. The measures were then compared to the same utterances produced by 13 normal-hearing adults. Although absolute speech durations of the hearing-impaired subjects were significantly longer than their normal-hearing counterparts, relative timing did not differ between groups. Findings are discussed in relation to the biological constraint hypothesis associated with speech timing, as well as the role of auditory feedback in models of speech production.     

Kinetic and mechanistic study of the reactions of palladium(II) chlorocomplexes with ethylenediamine in aqueous acid medium

The complexes PdCl₄^2?, PdCl₃(H₂O)^?, and PdCl₃(Ac)^2?, in rapid equilibrium with each other under the adopted experimental conditions, react with ethylenediamine according to the experimental rate law A reaction scheme is proposed involving the reaction of enH⁺ with each of the above species, and the specific rate constants are computed. The activation parameters are given.     

On some distribution problems in Manova and discriminant analysis

Asymptotic expansions, valid for large error degrees of freedom, are given for the multivariate noncentral F distribution and for the distribution of latent roots in MANOVA and discriminant analysis. The asymptotic results are expressed in terms of elementary functions which are easy to compute and the results of some numerical work are included. The Bartlett test of the null hypothesis that some of the noncentrality parameters in discriminant analysis are zero is also briefly discussed.     

Efficient photochemical merocyanine-to-spiropyran ring closure mechanism through an extended conical intersection seam. A model CASSCF/CASPT2 study

A mechanism of the thermal and photochemical bleaching of merocyanine to spiropyran is proposed on the basis of CASSCF/CASPT2 calculations on the 6-(2-propenyliden)cyclohexadienone model system. Our results suggest that this photochemical transformation takes place in two steps. First, the initially pumped 1(pi-pi) S2 undergoes radiationless decay to 1(n-pi) S1 via an extended S2/S1 conical intersection seam that runs approximately parallel to the trans-to-cis isomerization coordinate, a few kilocalories per mole higher in energy. Thus, S2 --> S1 internal conversion is possible at all values of the S2 trans-to-cis reaction coordinate. Second, on the S1 potential energy surface, there is a barrierless ring closure reaction path from the S1 cis minimum that leads to a peaked S1/S0 conical intersection where the deactivation to the ground state takes place. The inertia of the moving nuclei then drives the system toward the ground-state minimum of the 2H-chromene product. Thus, the extended seam topology of the S2/S1 conical intersection and the coordinate of the branching space of the S1/S0 conical intersection are essential to explain the efficiency and high speed of this reaction.     

Controlling S1/S0 decay and the balance between photochemistry and photostability in benzene: a direct quantum dynamics study

In this work, we investigate general mechanistic principles that control reaction selectivity following S(1)/S(0) internal conversion in benzene. A systematic relationship is drawn between the varying topology of an extended seam of conical intersection and the balance between two competitive radiationless decay channels: photophysical (benzene reactant regeneration) and photochemical (prefulvene product formation). This is supported by a model quantum dynamics study, using a direct dynamics approach based on variational multiconfiguration Gaussian wavepackets, where initial excitation of specific vibrational modes is designed to generate dynamical pathways that reach selected targets regions of the seam. High-energy regions of the seam are found to be sloped and in favor of the photophysical channel, while lower-energy regions are peaked and give access to the photochemical channel. This changeover could in principle be exploited to define targets for optimal control, by exciting different combinations of specific vibronic levels in S(1), accessing different regions of the seam, and giving different products.     

Excess partial molar enthalpies,entropies, Gibbs energies,and volumes in aqueous dimethylsulfoxide

The excess partial molar enthalpies, the vapor pressures, and the densities of dimethylsulfoxide (DMSO)–H₂O mixtures were measured and the excess partial molar Gibbs energies and the partial molar volumes were calculated for DMSO and for H₂O. The values of the excess partial molar Gibbs energies for both DMSO and H₂O are negative over the entire composition range. The results for the water-rich region indicated that the presence of DMSO enhances the hydrogen bond network of H₂O. Unlike monohydric alcohols, however, the solute-solute interaction is repulsive in terms of the Gibbs energy. This was a result of the fact that the repulsion among solutes in terms of enthalpy surpassed the attraction in terms of entropy. The data in the DMSO-rich region suggest that DMSO molecules form clusters which protect H₂O molecules from exposure to the nonpolar alkyl groups of DMSO.