Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers

The ability to prepare high T_g low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (T_g) for several thiol–norbornene materials. Results indicate that T_gs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high T_g materials. In particular, as much as a 70 °C increase in T_g was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007     

Assessment of the Formant Frequencies in Normal and Laryngectomized Individuals Using Linear Predictive Coding

The objective of this study was to assess the difference in voice quality as defined by acoustical analysis using sustained vowel in laryngectomized patients in comparison with normal volunteers. This was designed as a retrospective single center cohort study. An adult tertiary referral unit formed the setting of this study. Fifty patients (40 males) who underwent total laryngectomy and 31 normal volunteers (18 male) participated. Group comparisons with the first three formant frequencies (F1, F2, and F3) using linear predictive coding (LPC) (Laryngograph Ltd, London, UK) was performed. The existence of any significant difference of F1, F2, and F3 between the two groups using the sustained vowel /i/ and the effects of other factors namely, tumor stage (T), chemoradiotherapy, pharyngectomy, cricothyroid myotomy, closure of pharyngoesophageal segment, and postoperative complication were analyzed. Formant frequencies F1, F2, and F3 were significantly different in male laryngectomees compared to controls: F1 (P<0.001, Mann-Whitney U test), F2 (P<0.001, Student's t test), and F3 (P=0.008, Student's t test). There was no significant difference between females in both groups for all three formant frequencies. Chemoradiotherapy and postoperative complications (pharyngocutaneous fistula) caused a significantly lower formant F1 in men, but showed little effect in F2 and F3. Laryngectomized males produced significantly higher formant frequencies, F1, F2, and F3, compared to normal volunteers, and this is consistent with literature. Chemoradiotherapy and postoperative complications significantly influenced the formant scores in the laryngectomee population. This study shows that robust and reliable data could be obtained using electroglottography and LPC in normal volunteers and laryngectomees using a sustained vowel.     

Muonium adduct radicals from vinyl-aromatic compounds

During irradiation of liquid samples of 1-vinylimidazole, 2-vinylnaphthalene, 2-vinylpyridine, 4-vinylpyridine and 1,1-diphenylethene with positive muons, radicals of the type MuCH₂ĊHAr (Ar=the appropriate aromatic group), and the MuCH₂ĊPh₂ radical were observed by transverse field μSR; the muon hyperfine couplings are considered in the context of the effectiveness of the aryl groups in delocalising the unpaired electron.     

Zero-temperature Kosterlitz-Thouless transition in a two-dimensional quantum system

We construct a local interacting quantum dimer model on the square lattice, whose zero-temperature phase diagram is characterized by a line of critical points separating two ordered phases of the valence bond crystal type. On one side, the line of critical points terminates in a quantum transition inherited from a Kosterlitz-Thouless transition in an associated classical model. We also discuss the effect of a longer-range dimer interaction that can be used to suppress the line of critical points by gradually shrinking it to a single point. Finally, we propose a way to generalize the quantum Hamiltonian to a dilute dimer model in presence of monomers and we qualitatively discuss the phase diagram.     

Oxygen inhibition in thiol–acrylate photopolymerizations

The overall effects of oxygen on thiol–acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6‐hexanediol diacrylate with the alkane‐based thiol (1,6‐hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol–acrylate photopolymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2007–2014, 2006     

Truncation error bounds for modified continued fractions with applications to special functions

Much recent work has been done to investigate convergence of modified continued fractions (MCF's), following the proof by Thron and Waadeland [35] in 1980 that a limit-periodic MCFK(a _n , 1;x ₁), with andnth approximant

The crystal and molecular structure of 1,1,1,3,3,3-hexaphenyl-1,3-disilapropane

Crystals of the title compound H₂C(SiPh₃)₂ are triclinic, space group P$\text{1}$, with a = 9.290(2), b = 12.128(4), c = 16.882(4) Å, α = 62.08(1), β = 106.88(1), γ = 117.28(2)° and Z = 2. The central skeletal angle SiCSi is 128.8(7)°. The structures of the molecules H₂C(SiR₃)₂ (R = H, CH₃, and Ph) are compared and discussed: a simple model for the skeletal geometry of species H₂C(MR₃)₂ is proposed, and tested against experimental data and theoretical calculations.