Unusual pi-donating effects of pi-accepting substituents on the stabilities of benzylic cations: a theoretical study

The pi-donating effects of pi-accepting X-substituents in substituted benzylic cations, X-C(6)H(5)-CHR(+) where R = CF(3), H and OCH(3), and X = p-NH(2), p-OCH(3), p-CH(3), H, p-F, p-Cl, p-CHO, m-CN, p-CN, m-NO(2) or p-NO(2), have been studied theoretically by using isodesmic hydride transfer reactions at various levels of theory. It might be difficult to determine the pi-donating effects of pi-acceptors using the simple Hammett-type linear equation, because it is not sensitive enough to include small pi-donating effects. Therefore, this effect was estimated using the NBO deletion energy (DeltaE(D)) of the second-order charge-transfer interaction (DeltaE(ct)) between the pi-orbitals (or lone pair orbitals) of the X-substituent and the pi-orbitals of phenyl ring. The extents of pi-donating effects increased in the order X = p-NO(2) < p-CHO < p-CN < p-Cl for both neutral and cationic species, and these effects were found to be more important for para- than for meta-substituents. Moreover, this could represent a general trend for pi-donation by pi-acceptors. On the other hand, the effects of R-substituents on this pi-donating effect were found to be in the order R = OCH(3) < H congruent with CF(3), as predicted by natural resonance theory (NRT) analyses.     

Time-resolved imaging of VUV emission from a He-Xe micro surfacedischarge

A direct observation of two-dimensional, time dependent behavior of 147 nm and 173 nm vacuum ultra violet emission from a single surface discharge type AC plasma display panel cell were obtained using a gated, image intensified charge-coupled device (ICCD). The images on the ICCD are formed by a pinhole. The two lines show similar spatial profile but quite different temporal behavior     

Characterizations for Vinylimidazolium Based Ionic Liquid Polymer Stationary Phases for Capillary Gas Chromatography

Six polyvinylimidazolium based ionic liquids were prepared for use as stationary phases for gas chromatography. The influences of the attached side-chains (hexyl-, octyl- and phenylpropyl-) on the vinylimidazolium cations and of different counter ions (bromide, hexafluorophosphate, bis-trifluoromethanesulfonlyimide, and bis-trifluoroethanesulfonylimide) were studied. Linear solubility parameter experiments were conducted to characterize the specific interactions of these stationary phases. Some of the polymerized ionic liquid stationary phases exhibited unique structural selectivity. m-, and p-xylenes could be distinguished. The preparation of the polymerized ionic liquid column is simple and reliable. This work provides detailed information for designing polymerized ionic liquids, and shows that these materials have great potential extending the range of options for stationary phases in gas chromatography.     

High uniform illumination of light-emitting diodes lighting with applying the multiple-curvature lens

Light-emitting-diode (LED) sources will play a very important role in the future. Nowadays, there are many traditional light sources gradually being replaced by LED sources. From the viewpoint of illumination, different environments have the same requirement uniformity of illumination. The basic reason for this is to insure human comfort. Therefore, the promotion of illumination uniformity is an especially important key issue. In this article, we propose one effective design to improve the uniformity of illumination of LEDs with Lambertian radiation profiles by inserting into the lighting system, multiple-curvature lens. The enhanced illumination uniformity of LEDs, in this system, is due to energy redistribution by controlling the direction of incident light, using geometrical optics theory. Ray tracing was applied for the simulations required. Finally, the uniformity of illumination is 76.17% in LEDs using multiple-curvature lens, which is twice the uniformity of conventional LEDs. Furthermore, the phenomenon of overload in the multiple-curvature lens is reduced by increasing the numbers of rings on the lens. The overload is less than 0.02 lm in the case of lens designed with 23 rings.     

Calculating specific absorbed fractions with standard Korean male adults

Based on data representing standard Korean male adults, a mathematical anthropomorphic phantom was developed to calculate the specific absorbed fraction for several organs. The results were then compared against values calculated with other phantoms (OTOKO of Japan, MIRD of the U.S. and GOLEM of Germany). We compared the specific absorbed fractions of six organs (the adrenals, kidneys, liver, lungs, pancreas and spleen) for two cases: when the source and target organs are the same, and when they are different. When both the source and target organs are the same the organ with the highest specific absorbed fraction regardless of energy level was found to be the adrenals in all phantoms. In comparing phantoms, the phantom developed on the basis of standard Koreans produced the highest specific absorbed fraction. Also, as a result of conducting an assessment by separating source organs from target organs, the phantom developed on the basis of standard Koreans displayed relatively high specific absorbed fractions although there were slight differences per organ.     

Maximum-entropy TFμSR study of vortex states in 1/2/3 cuprates

A maximum-entropy (ME) method has been applied to TFSR vortex data of RBa₂Cu₃O₇ (R1237; R=Er, Gd and Eu). The obtained information on the field distribution is of much better quality than that resulting from Fourier transformation and curve-fitting of the same data. ME application to R1237 TFSR data taken below T_c at LAMPF show asymmetrical, nearly triangular, field distributions, which broaden with decreasing temperature. Significant deviations from Abrikosov predictions have been observed for the estimated R1237-vortex field distributions. Below 10 K, for Er1237 and Gd1237, the non-Abrikosov features appear to be influenced by the rare-earth magnetism. The low-field tail in the field distribution and the ME-intensity anomaly near T_c suggest glassy features in the 1/2/3 cuprate vortex states.     

Nucleophilic substitution reactions of aryl dithioacetates with pyridines in acetonitrile

Kinetic studies of the pyridinolysis (XC(5)H(4)N) of aryl dithioacetates (CH(3)C(=S)SC(6)H(4)Z) are carried out in acetonitrile at 60.0 degrees C. A biphasic Br?nsted plot is obtained with a change in slope from a large value (beta(X) congruent with 0.9) to a small value (beta(X) congruent with 0.4) at pK(a) degrees = 5.2, which is attributed to a change in the rate-limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, T(+/-), in the reaction path as the basicity of the pyridine nucleophile increases. A clear-cut change in the cross-interaction constants rho(XZ) from a large positive value (rho(XZ) = +1.34) to a small negative value (rho(XZ) = -0.15) supports the mechanistic change proposed.     

Effects of pH During the Base Catalyzed Reaction of Two-Step Acid/Base Catalyzed Process on the Microstructures and Physical Properties of Poly(dimethylsiloxane) Modified Silica Xerogels

Poly(dimethylsiloxane) (PDMS) modified silica xerogels were prepared by two-step acid/base catalyzed sol-gel process. By keeping the acid amount and hydrolysis period in acidic environment fixed, and adding different amounts of base to the sol afterwards, attempts had been made to study the effect of the different amounts of base catalyst on the micro-structure and physical properties of the prepared ORMOSILs. DTA, SEM, BET, FTIR were performed to characterize the derived specimens. The microstructure and physical properties are greatly influenced by the amount of base added to the sol. With increasing base content the crystallite size and porosity increase and the pore size distribution takes a broad spectrum. Whereas, the glass transition temperature seems to decrease with increasing of base catalyst amount. This is explained in terms of the change in the relative amounts of hydrolysis and condensation reactions due to the addition of different amount of base catalyst, which predominantly influences the condensation reactions. The results are reported in this communication along with possible explanations behind the observations.