Epoxidation of Alkyllithium Polybutadienes

Epoxidations with peracetic acid were effected on a series of alkyllithium and sodium polybutadienes, and the properties of the epoxy resins were compared. The alkyllithium and sodium polybutadienes differed in micro-structure and molecular weight distribution. The alkyllithium polybutadienes were more readily epoxidized, and epoxidation resulted in dramatically lower viscosity increases with increasing epoxy contents. Epoxidized alkyllithium polybutadienes varying in molecular weight and epoxy content were shown to be compatible, efficient, and permanent plasticizer-stabilizers for polyvinyl chloride.     

Design and development of original WSN sensor for suspended particulate matter measurements

This paper comprehensively presents key issues in design of an original optoelectronic measurement device built to assess amount of suspended particulate matter. The paper is introduced with a short explanation of concerns with a suspended particulate matter, what role it has in the air quality and how it affects health of human population. Then, problems of construction of the measurement device supported by a theoretical explanation on the basis of Mie theory are discussed. Subsequently, it is followed by an analysis of the device operation both in laboratory and in real conditions. Results obtained with the presented device are compared with the professional measurement equipment and an expensive, outdoor measurement station. Paper is concluded with observations of differences in spatio-temporal PM change at very close but significantly different city locations.     

Spectroscopic and Theoretical Studies of Fluorescence Effects in 2-Methylamino-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazole Induced by Molecular Aggregation

The article presents the results of fluorescence analyses of 2-methylamino-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazole (MDFT) in an aqueous environment. MDFT dissolved in aqueous solutions with a pH value in the range from 1 to 4.5 yielded an interesting effect of two clearly separated fluorescence emissions. In turn, a single fluorescence was observed in MDFT dissolved in water solutions with a pH value from 4.5 to 12. As it was suggested in the previous investigations of other 1,3,4-thiadiazole compounds, these effects may be associated with conformational changes in the structure of the analysed molecule accompanied by aggregation effects. Crystallographic data showed that the effect of the two separated fluorescence emissions occurred in a conformation with the –OH group in the resorcyl ring bound on the side of the sulphur atom from the 1,3,4-thiadiazole ring. The hypothesis of aggregation as the mechanism involved in the change in the spectral properties at low pH is supported by the results of (Time-Dependent) Density Functional Theory calculations. The possibility of rapid analysis of conformational changes with the fluorescence spectroscopy technique may be rather important outcome obtained from the spectroscopic studies presented in this article. Additionally, the presented results seem to be highly important as they can be easily observed in solutions and biologically important samples.     

On a reduced load equivalence for fluid queues under subexponentiality

We propose a general framework for obtaining asymptotic distributional bounds on the stationary backlog in a buffer fed by a combined fluid process A ₁ + A ₂ and drained at a constant rate c. The fluid process A ₁ is an (independent) on–off source with average and peak rates ρ₁ and r₁ , respectively, and with distribution G for the activity periods. The fluid process A ₂ of average rate ρ₂ is arbitrary but independent of A ₁. These bounds are used to identify subexponential distributions G and fairly general fluid processes A ₂ such that the asymptotic equivalence P[W ^A1+A2,c >ϰ]∼P[W ^A1,c—ρ2>ϰ] (ϰ → ∞) holds under the stability condition ρ₁ + ρ₂ < c and the non-triviality condition c – ρ₂ < r ₁. In these asymptotics the stationary backlog results from feeding source A ₁ into a buffer drained at reduced rate c – ρ₂. This reduced load asymptotic equivalence extends to a larger class of distributions G a result obtained by Jelenkovic and Lazar [19] in the case when G belongs to the class of regular intermediate varying distributions. This revised version was published online in June 2006 with corrections to the Cover Date.     

Theoretical calculations of homoconjugation equilibrium constants in systems modeling acid-base interactions in side chains of biomolecules using the potential of mean force

The potentials of mean force (PMFs) were determined for systems forming cationic and anionic homocomplexes composed of acetic acid, phenol, isopropylamine, n-butylamine, imidazole, and 4(5)-methylimidazole, and their conjugated bases or acids, respectively, in three solvents with different polarity and hydrogen-bonding propensity: acetonitrile (AN), dimethyl sulfoxide (DMSO), and water (H(2)O). For each pair and each solvent a series of umbrella-sampling molecular dynamics simulations with the AMBER force field, explicit solvent, and counterions added to maintain a zero net charge of a system were carried out and the PMF was calculated by using the Weighted Histogram Analysis Method (WHAM). Subsequently, homoconjugation-equilibrium constants were calculated by numerical integration of the respective PMF profiles. In all cases but imidazole stable homocomplexes were found to form in solution, which was manifested as the presence of contact minima corresponding to hydrogen-bonded species in the PMF curves. The calculated homoconjugation constants were found to be greater for complexes with the OHO bridge (acetic acid and phenol) than with the NHN bridge and they were found to decrease with increasing polarity and hydrogen-bonding propensity of the solvent (i.e., in the series AN > DMSO > H(2)O), both facts being in agreement with the available experimental data. It was also found that interactions with counterions are manifested as the broadening of the contact minimum or appearance of additional minima in the PMF profiles of the acetic acid-acetate, phenol/phenolate system in acetonitrile, and the 4(5)-methylimidazole/4(5)-methylimidzole cation conjugated base system in dimethyl sulfoxide.     

MAGICTRAC, a novel method for conversion of whispering-gallery modes into a free-space Gaussian-like beam

A novel device, MAGICTRAC, is described for efficient conversion at millimeter wavelengths of the TE _m,n whispering-gallery mode into a linearly polarized, free-space Gaussian-like beam. MAGICTRAC uses a mode-converting waveguide taper and three mirror optics, one of which incorporates a twist reflector to linearly polarize the output beam. An example design is presented for the TE_15,2 mode at 140 GHz with a calculated efficiency of 96%. Related possible applications include (1) installation of the MAGICTRAC within the vacuum envelope of a gyrotron to separarate the spent e-beam from the generated rf, (2) generation of a whispering-gallery mode by injection of a Gaussian-like beam into the output end, and (3) conversion of TE _m,n modes into TE_0n modes for low-loss transmission in smooth-wall waveguide.Work performed by LLNL for USDOE under contract W-7405 ENG-48.