Polymerization of α-Methylstyrene in p-Dioxane with Potassium as Initiator. III. Gel-Permeation Chromatographic Analyses of Polymers

Gel-permeation chromatographic studies on poly-α-methyl-styrene initiated with potassium and potassium-naphthalene in p-dioxane as solvent and polymerized at 5, 15, 25, and 40°C, have been carried out. Bimodal and trimodal distributions are observed in these polymers. It has been shown that these multimodal distributions do not arise because of the monofunctional and bifunctional living ends produced by the reaction of solvent dioxane with the living polymer. These, on the other hand, may be related to the presence of different ion-pairs which contribute to the reaction but to different extents. Contrary to the belief that only contact ion-pairs are responsible for propagation in p-dioxane because of its low dielectric constant, the presence of solvent-separated ion-pairs yielding reversible propagation has been speculated. The different components (D + A), B, and C, similar to the ones present in the a-methyl-styrene-potassium tetrahydrofuran system, have been found in the present study also and are attributed to the dead and a dormant polymer, solvent-separated ion-pair polymer, and that due to a contact pair, respectively. The extent of the formation of component (D + A) has been linked directly to the concentration of living ends. In reactions where naphthalene was used along with potassium for initiation purposes, a unique component yielding reversible propagation was observed. This has been attributed to the presence of polymer due to potassium-naphthalene complex which is different in character to a contact ion-pair but may resemble a solvent-separated ion-pair.     

Metal Ion Recognition. Interaction of New Oxygen-Nitrogen Donor Macrocycles with Selected Transition and Post-Transition Metal Ions

As part of an ongoing investigation of the factors influencing metal ionrecognition, we have investigated structure/function relationships involvingthe metal-ion binding by three new N-benzyl-substituted, 15- and 16-membered,macrocyclic ligands incorporating N₂O ₃- and N ₃O ₃-donor sets (withthe N ₃O ₃-system consisting of a N ₂O ₃-macrocyclic ring with an attachedCH ₂CH ₂NCH ₂C ₆H ₅ pendant arm). Selected solid complexes of thelatter ligand were isolated and the X-ray structures of individual Ni(II) and Ag(I) complexeswere obtained.Where solubility permitted, potentiometric titration studies in 95% methanolwere employed to investigate the binding affinities of all three ligand derivativestowards Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Ag(I) and Pb(II). The 15-memberedN ₂O ₃-ring was found to be selective for Ag(I) over the other six metalsinvestigated, including Cu(II). However, the presence of a further nitrogen donorin the form of the pendant benzylamine functionality in the N ₃O ₃-donorsystem results in an increase in its binding affinity for Ag(I) but an even greaterincrease occurs for Cu(II). As a consequence, the latter ion is now more stronglybound than Ag(I). The factors influencing these respective selectivities are discussed.     

Infrared diffuse reflectance instrumentation and standards at NIST

A spectrophotometer system for spectral characterization of materials in the infrared has been built around a bench-top Fourier transform instrument. Its capabilities include the measurement of directional-hemispherical reflectance from 1 to 18 μm. The spectral reflectance measurement is performed with an integrating sphere with an incidence angle of 8°. Both relative and absolute measurements can be made. Several methods can be used to determine the absolute value of the directional-hemispherical reflectance of samples. The primary method used is independent of the integrating sphere theory and the requisite assumptions associated with its use. The calibration of a standard reference material (SRM) is described. This SRM has a reflectance value near 0.9 over the complete calibration range 2–18 μm. As part of the calibration procedure the spatial uniformity of the sphere throughput and the bi-directional reflectance distribution function (BRDF) of the SRM material are evaluated.     

Zur Untersuchung von Zuckersirup

Ohne Zusammenfassung     

An extended Heath–Jarrow–Morton risk-neutral drift

Using a finite dimensional Hilbert space framework, this work proposes a new derivation of the HJM [D. Heath, R. Jarrow, A. Morton, Bond pricing and the term structure of interest rates: A new methodology for contingent claims valuation, Econometrica 60 (1992) 77–105] risk-neutral drift that takes into account nonzero instantaneous correlations between factors. The results obtained generalize the original HJM risk-neutral drift and provide an approach by which interest rate derivatives can be priced using functions of directly observable factors.     

A Computationally Motivated Definition Of Parametric Estimation And Its Applications To The Gaussian Distribution

We introduce a treatment of parametric estimation in which optimality of an estimator is measured in probability rather than in variance (the measure for which the strongest general results are known in statistics). Our motivation is that the quality of an approximation algorithm is measured by the probability that it fails to approximate the desired quantity within a set tolerance. We concentrate on the Gaussian distribution and show that the sample mean is the unique “best” estimator, in probability, for the mean of a Gaussian distribution. We also extend this method to general penalty functions and to multidimensional spherically symmetric Gaussians. The algorithmic significance of studying the Gaussian distribution is established by showing that determining the average matching size in a graph is #P-hard, and moreover approximating it reduces to estimating the mean of a random variable that (under some mild conditions) has a distribution closely approximating a Gaussian. This random variable is (essentially) polynomial time samplable, thereby yielding an FPRAS for the problem.     

Preparation and characterization of copper(II) tetrasulfonated phthalocyanine nanoparticles formed by laser ablation in poor solvents

Laser irradiation of copper(II) tetrasulfonated phthalocyanine (CuTsPc) microcrystals in poor organic solvents such as methanol, 2-methyl-2-propanol, ethanol, tetrahydrofuran, and acetone has produced CuTsPc nanoparticles with 15–112 nm in diameter. Field emission scanning electron microscopy (FESEM) images have shown the formation of CuTsPc nanoparticles in poor organic solvents used in this work. The mean diameters of CuTsPc nanoparticles obtained from transmission electron microscopy (TEM) images in methanol, 2-methyl-2-propanol, ethanol, tetrahydrofuran, and acetone were determined to be 26, 36, 35, 86, and 78 nm, respectively. A correlation between the size of CuTsPc nanoparticles and a solvent polarity could be found in this work.