13C and 1H NMR analysis of structural defects in PVC: Application to the production of defects at various polymerization stages

High resolution ¹H and ¹³C NMR data were obtained on PVC and PVC reduced with Bu₃SnH. The reduction is never complete and CH₂Cl groups preferentially remain. It causes almost complete formation of cyclopentane structures from both internal and chain end unsaturation. ¹H NMR gives total unsaturation as well as chain end unsaturation except if there are interferences with initiator residues; in that case, its combination with ¹³ C NMR of reduced PVC gives the chain end unsaturation. By the last method short branches and long ends are determined. Residual primary chlorine in all kinds of branches (methyl, ethyl, butyl, long ends) is taken into account. Long end contents are to be corrected (factor around 1.5), due to incomplete relaxation in standard analysis conditions. ¹H NMR of reduced PVC can be used to get the total non-reduced structures, both -CH₂Cl and -CHCl-. PVC was prepared by suspension or solution (trichlorobenzene) polymerization at 55° C, using dicetyl peroxydicarbonate as an initiator. The initiator residue content is higher in suspension PVC at very low conversion, and then levels off at a low value; in solution polymerization, it chiefly depends on the monomer/initiator ratio. At low conversion, more chain end and less short branches are present in suspension polymerization. Otherwise, only the butyl branch content shows a definite trend to increase with conversion. In solution polymerization, the number of defects is chiefly dependent on the initial monomer concentration; it is generally much higher than in suspension, except for the chloromethyl branches where both processes give about the same results.     

Thermodynamics of the dissociation of Bis H+ in seawater from 5 to 40°C

Electromotive-force measurements of cells without transference were used to determine the dissociation constant of the protonated form of the weak base 2-amino-2-methyl-1, 3-propanediol (Bis) in synthetic seawaters corresponding to salinities of 20, 35, and 45. Hydrogen electrodes and silver-silver chloride electrodes were used, together with standard potentials determined in an earlier investigation. The pK increases in linear fashion with the salinity (S) of the medium, for values of S from 0 to 45. The solvent effect is given by 8.802+0.00378S at 25°C with a mean deviation of 0.001. The medium effect of seawater on H° at 25°C is less than 200 cal-mol^–1 and less than 0.2 cal-^oK-mol^–1 on S°.     

Advances in ultra-high load polymer-supported peptide synthesis with phenolic supports: 2. Use of ‘hydrazinolysis-hplc’ to check for racemization on c-terminal amino acid loading and to determine peptide homogeneity during synthesis with selectively labile c-terminal anchoring linkages

2, 4-Dinitrophenyl-L-phenylalanine has been coupled to L-, D-, and DL-amino acid phenyl esters pendant upon a polymer matrix. The esters had been prepared by di-isopropylcarbodiimide-mediated condensation, catalyzed by 4-dimethylaminopyridine. Reverse phase high pressure liquid chromatography (HPLC), using elution solvents consisting of 10 vol.-% trifluoroacetic acid in water/acetonitrile mixtures, has been used to investigate the 2,4-dinitrophenyl L-L and L-D dipeptide mixtures obtained on hydrazinolysis of each of the dipeptide-matrix assemblies. ‘Hydrazinolysis-HPLC’ has been used also to determine intermediate peptide homogeneity in ultra-high load solid (gel) phase synthesis with Boc amino acids. Cross-linked poly(N-[2-(4-hydroxyphenyl)ethyl]acrylamide) and two derived polymers incorporating spacer groups have been used as supports. The spacer groups made possible peptide C-terminal attachment by either HF-labile benzyl ester or HF-labile cyclohexyl ester bonds, while still incorporating the phenolic ester linkage susceptible to rapid hydrazinolytic scission.     

Dependence of phonation threshold pressure on vocal tract acoustics and vocal fold tissue mechanics

Analytical and computer simulation studies have shown that the acoustic impedance of the vocal tract as well as the viscoelastic properties of vocal fold tissues are critical for determining the dynamics and the energy transfer mechanism of vocal fold oscillation. In the present study, a linear, small-amplitude oscillation theory was revised by taking into account the propagation of a mucosal wave and the inertive reactance (inertance) of the supraglottal vocal tract as the major energy transfer mechanisms for flow-induced self-oscillation of the vocal fold. Specifically, analytical results predicted that phonation threshold pressure (Pth) increases with the viscous shear properties of the vocal fold, but decreases with vocal tract inertance. This theory was empirically tested using a physical model of the larynx, where biological materials (fat, hyaluronic acid, and fibronectin) were implanted into the vocal fold cover to investigate the effect of vocal fold tissue viscoelasticity on Pth. A uniform-tube supraglottal vocal tract was also introduced to examine the effect of vocal tract inertance on Pth. Results showed that Pth decreased with the inertive impedance of the vocal tract and increased with the viscous shear modulus (G") or dynamic viscosity (eta') of the vocal fold cover, consistent with theoretical predictions. These findings supported the potential biomechanical benefits of hyaluronic acid as a surgical bioimplant for repairing voice disorders involving the superficial layer of the lamina propria, such as scarring, sulcus vocalis, atrophy, and Reinke's edema.     

Hearing loss from interrupted, intermittent, and time varying non-Gaussian noise exposure: The applicability of the equal energy hypothesis

Sixteen groups of chinchillas (N=140) were exposed to various equivalent energy noise paradigms at 100 dB(A) or 103 dB(A) SPL. Eleven groups received an interrupted, intermittent, and time varying (IITV) non-Gaussian exposure quantified by the kurtosis statistic. The IITV exposures, which lasted for 8 hday, 5 daysweek for 3 weeks, were designed to model some of the essential features of an industrial workweek. Five equivalent energy reference groups were exposed to either a Gaussian or non-Gaussian 5 days, 24 hday continuous noise. Evoked potentials were used to estimate hearing thresholds and surface preparations of the organ of Corti quantified the sensory cell population. For IITV exposures at an equivalent energy and kurtosis, the temporal variations in level did not alter trauma and in some cases the IITV exposures produced results similar to those found for the 5 day continuous exposures. Any increase in kurtosis at a fixed energy was accompanied by an increase in noise-induced trauma. These results suggest that the equal energy hypothesis is an acceptable approach to evaluating noise exposures for hearing conservation purposes provided that the kurtosis of the amplitude distribution is taken into consideration. Temporal variations in noise levels seem to have little effect on trauma.     

Runge–Kutta Lawson schemes for stochastic differential equations

In this paper, we present a framework to construct general stochastic Runge–Kutta Lawson schemes. We prove that the schemes inherit the consistency and convergence properties of the underlying Runge–Kutta scheme, and confirm this in some numerical experiments. We also investigate the stability properties of the methods and show for some examples, that the new schemes have improved stability properties compared to the underlying schemes.

     

Examining the didactic contract when handheld technology is permitted in the mathematics classroom

The use of mathematics analysis software (MAS) including handheld scientific and graphics calculators offers a range of pedagogical opportunities. Its use can support change in the didactic contract. MAS may become an alternative source of authority in the classroom empowering students to explore variation and regularity, manipulate simulations and link representations. Strategic use may support students to direct their own learning and explore mathematics, equipping them to share their findings with the teacher and the class with more confidence. This paper offers a framework for examining the impact of the use of MAS on the didactic contract. Lessons were observed in 12 grade 10 classes, with 12 different teachers new to MAS. MAS technology was used with a variety of didactic contracts, mostly traditional. The framework drew attention to many ways in which the teaching differed. Analysis of the didactic contract must consider both the teaching of mathematics and of technology skills, because these have different characteristics. In all classes, both teachers and students saw the teacher as having a responsibility to teach technology skills. Students saw technology skills as the main point of the lesson, but the teachers saw the lesson as primarily teaching mathematics—one of the mismatches which may need negotiation to adapt didactic contracts to teaching with MAS.     

Information about group matrices

Each ordering for the elements of a finite group G of order n defines a corresponding class of group matrices for G. First, this paper proves that the number of distinct classes of group matrices for G equals (n ? 1)!/m, where m is the number of automorphisms of G. Then, a study is made of a block-diagonal reduction for the group matrices of any particular class.