Polychlorinated polyamides. II. Synthesis and characterization of polyamides derived from 2, 5-dichloroterephthaloyl dichloride and perchloroterephthaloyl dichloride

New thermally stable polyamides were prepared by interfacial polymerization of the title compounds and various aliphatic and aromatic diamines. The polymers were characterized by infrared spectrometry, elemental analysis, and differential scanning calorimetry. The molecular weights of the polymers were estimated by viscosity measurements. The influence of the halogen content on the thermal properties and degree of polymerization of the polymers was studied. One of the polyamides was fractionated to determine the degree of polydispersity.     

Study of CO chemisorption on polycrystalline Pt

The chemisorption of CO on a sputtered and annealed polycrystalline Pt surface has been examined using ion scattering spectroscopy (ISS) and temperature programmed desorption (TPD). Data obtained from an isotopic TPD experiment indicate that adsorption is molecular with no detectable CO dissociation. ISS data demonstrate that the CO bonds to the Pt through the C with the O pointing away from the surface and that about 80% of the Pt surface is covered at saturation based on the relative sizes of the ISS Pt peak heights obtained from the clean and CO-saturated surfaces. Coverage versus exposure plots have been determined from both the ISS and TPD data, and the agreement is generally good. The sticking coefficient is close to 1 up to =0.5 and than falls rapidly with increasing exposure to the saturation exposure of 90 L. The Kisliuk adsorption model, which assumes adsorption at a single type of site, is able to provide a good fit of the ISS uptake data but is not as successful in fitting the TPD uptake data.     

Asymptotic analysis of Daubechies polynomials

To study wavelets and filter banks of high order, we begin with the zeros of . This is the binomial series for , truncated after terms. Its zeros give the zeros of the Daubechies filter inside the unit circle, by . The filter has additional zeros at , and this construction makes it orthogonal and maximally flat. The dilation equation leads to orthogonal wavelets with vanishing moments. Symmetric biorthogonal wavelets (generally better in image compression) come similarly from a subset of the zeros of . We study the asymptotic behavior of these zeros. Matlab shows a remarkable plot for . The zeros approach a limiting curve in the complex plane, which is the circle . All zeros have , and the rightmost zeros approach (corresponding to ) with speed . The curve gives a very accurate approximation for finite . The wide dynamic range in the coefficients of makes the zeros difficult to compute for large . Rescaling by allows us to reach by standard codes.

     

Synthesis, Structural Characterization, and Oxidation-Reduction Behavior of the gamma-Isomer of the Dodecatungstosilicate Anion

The reaction of tungstate ions with the gamma-10-tungstosilicate in mixed water-ethanol (v/v) yields the corresponding isomer of the 12-tungstosilicate isolated as its tetrabutylammonium salt. It was characterized by means of (183)W NMR, infrared, Raman, and UV spectroscopies and was identified with the isomer resulting from the Keggin structure (alpha-isomer) by rotation of two tritungstic groups by pi/3. Cyclic voltammetry shows that the reducibility increases in the sequence alpha-beta-gamma as the number of rotated tritungstic groups. Whereas the gamma-12-tungstosilicate anion is unstable in pure aqueous solution whatever the pH value, it is stable in mixed aqueous-organic or pure organic solvents, even at boiling temperatures. In contrast, the two- and four-electron-reduced blue species are stable in aqueous media but not the one-electron-reduced blue. Study of the (183)W NMR spectrum of the two-electron-reduced species showed that the two spin-paired electrons are delocalized on all the W atoms on the NMR time scale but have a larger residency time on one group of four atoms.     

Approximation by translates of refinable functions

Summary. The functions are refinable if they are combinations of the rescaled and translated functions . This is very common in scientific computing on a regular mesh. The space of approximating functions with meshwidth is a subspace of with meshwidth . These refinable spaces have refinable basis functions. The accuracy of the computations depends on , the order of approximation, which is determined by the degree of polynomials that lie in . Most refinable functions (such as scaling functions in the theory of wavelets) have no simple formulas. The functions are known only through the coefficients in the refinement equation – scalars in the traditional case, matrices for multiwavelets. The scalar "sum rules" that determine are well known. We find the conditions on the matrices that yield approximation of order from . These are equivalent to the Strang–Fix conditions on the Fourier transforms , but for refinable functions they can be explicitly verified from the . Received August 31, 1994 / Revised version received May 2, 1995     

Styrene emulsion polymerization: Particle-size distributions

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.     

Molecular models of lipopeptide detergents: large coiled-coils with hydrocarbon interiors

We have constructed molecular models of octameric micelles formed by a recently developed lipopeptide detergent consisting of a single amphipathic alpha-helix coupled to two acyl chains at either end of the helix. The models explain the experimentally observed aggregation behavior of peptides with different acyl chain lengths. The octameric micelles form a unique coiled-coil structure, with the acyl chains in a nearly frozen conformation inside the cylindrical assemblies. Two extreme models with helices either all parallel or in an alternating orientation suggest that the alternating orientation is energetically more favorable. The models suggest several new directions for further diversifying this new class of detergents for the structural studies of membrane proteins.     

Optically and thermally induced electron transfer pathways in hexakis[4-(N,N-diarylamino)phenyl]benzene derivatives

The optically and thermally induced electron transfer pathways of highly symmetrical (D(3)) hexaarylbenzene systems with six triarylamine redox sites have been investigated. Owing to slightly different local redox potentials, the radical trication could be selectively generated by electrochemical methods. This trication shows a strong intervalence charge-transfer band in the near infrared (NIR) that was measured by spectroelectrochemistry and analysed using multi-dimensional Mulliken-Hush theory. Quantum chemical AM1 CI calculations indicate that there is no optically induced concerted three-electron transfer that transforms the ground state into a state in which all three positively charged triarylamine moieties change place with their neutral neighbours. The potential energy surface of the ground state was constructed by using quadratic potentials. From this potential surface it is apparent that there is also no thermally allowed concerted three-electron transfer pathway. Instead, three consecutive one-electron transfer steps are necessary for this process.     

The preparation of a new "safety catch" ester linker for solid-phase synthesis

A new "safety catch" linker for esters has been synthesized on polystyrene resin. This 2-tert-butoxyphenol resin 10 may be acylated to give a relatively stable ester that will allow nucleophilic chemistry without reaction at the linking ester group. Removal of the tert-butyl group with acid unmasks a highly reactive 2-hydroxyphenyl ester that reacts readily with nucleophiles to cause release of the product from the resin. This sequence has been exemplified by acylating the resin with various bromo acids, carrying out nucleophilic displacements with thiols, phenols, or amines, activating the ester with trifluoroacetic acid and cleaving from the resin with amines to give the (nucleophile) substituted carboxamides in high yield and purity. Kinetic studies with a model ester revealed half-lives for reaction with morpholine of 119 h for the tert-butoxyphenyl ester and 1 min for the corresponding phenol.