Molecular mobility in amorphous maltose and maltitol from phosphorescence of erythrosin B

We have used phosphorescence from erythrosin B (tetraiodofluorescein) dispersed in amorphous thin films of maltose and maltitol at mole ratios of 0.8:10(4) dye:sugar to monitor the molecular mobility of these matrixes over the temperature range from -25 to over 110 degrees C. Analysis of the emission peak frequency and bandwidth (full width at half-maximum) and time-resolved intensity decay parameters provided information about thermally activated modes of matrix mobility that enhanced the rate of dipolar relaxation around the triplet state and the rate of intersystem crossing to the ground state (k(TS0)). Detectable dipolar relaxation began in the glassy state about 50 degrees C below T(g) in both maltose and maltitol; the relaxation rate, however, while 3-4 orders of magnitude slower than literature values for the beta relaxation determined from dielectric relaxation, had an activation energy only 2-fold smaller. Dipolar relaxation was further enhanced in the melt above T(g); the dipolar relaxation rates in the melt scaled nearly exactly with rates for the alpha relaxation determined from dielectric relaxation. Intensity decays were well fit using a stretched exponential decay function in which the lifetime (tau) and the stretching exponent (beta) were the physically significant parameters. In maltose, the magnitude of k(TS0) was essentially constant in the glass and increased dramatically at the T(g); in maltitol k(TS0) increased moderately at T(g) = -50 degrees C and more dramatically in the melt at T(g) = +20 degrees C. The value of k(TS0) in maltose:maltitol mixtures was significantly smaller than that seen in pure maltose and maltitol, suggesting that specific interactions decreased the mobility of the mixed sugar matrix; this phenomenon was comparable to the antiplasticization seen in mixtures of small molecule plasticizers with synthetic polymers and starch. The extent of inhomogeneous broadening and dynamic heterogeneity were essentially constant in the glass and increased dramatically in maltose and more gradually in maltitol at the glass transition.     

Efficient method for the synthesis of novel substituted thieno[2,3-d]pyrimidine-4-carboxylic acids,their derivatization,and antimicrobial activity

Chemistry of Heterocyclic Compounds - An effective method for accessing novel substituted thieno[2,3-d]pyrimidine-4-carboxylic acids in 63–71% yields based on Pd(dppf)Cl2-catalyzed...     

On p-norm linear discrimination

We consider a p-norm linear discrimination model that generalizes the model of Bennett and Mangasarian (1992) and reduces to a linear programming problem with p-order cone constraints. The proposed approach for handling linear programming problems with p-order cone constraints is based on reformulation of p-order cone optimization problems as second order cone programming (SOCP) problems when p is rational. Since such reformulations typically lead to SOCP problems with large numbers of second order cones, an “economical” representation that minimizes the number of second order cones is proposed. A case study illustrating the developed model on several popular data sets is conducted.     

Dianthracenylazatrioxa[8]circulene: Synthesis,Characterization and Application in OLEDs

A soluble, green-blue fluorescent, π-extended azatrioxa[8]circulene was synthesized by oxidative condensation of a 3,6-dihydroxycarbazole and 1,4-anthraquinone by using benzofuran scaffolding. This is the first circulene to incorporate anthracene within its carbon framework. Solvent-dependent fluorescence and bright green electroluminescence accompanied by excimer emission are the key optical properties of this material. The presence of sliding π-stacked columns in the single crystal of dianthracenylazatrioxa[8]circulene is found to cause a very high electron-hopping rate, thus making this material a promising n-type organic semiconductor with an electron mobility predicted to be around 2.26 cm² V⁻¹ s⁻¹. The best organic light-emitting diode (OLED) device based on the dianthracenylazatrioxa[8]circulene fluorescent emitter has a brightness of around 16 000 Cd m⁻² and an external quantum efficiency of 3.3 %. Quantum dot-based OLEDs were fabricated by using dianthracenylazatrioxa[8]circulene as a host matrix material.     

Direct Trifluoromethylthiolation of Alcohols under Mild Reaction Conditions: Conversion of ROH into RSCF3

A direct process for the trifluoromethylthiolation of allylic and benzylic alcohols under mild conditions has been developed. A wide range of free alcohols underwent nucleophilic substitution in the presence of stable CuSCF₃ and BF₃ ? Et₂O to give the corresponding products in good to excellent yields.     

On the influence of alpha-particle cyclotron damping on the lower hybrid current drive

Some preliminary results of the influence of the cyclotron harmonic damping of lower hybrid waves by thermonuclearly produced alpha-particles are presented. Recently, the usefulness of the lower hybrid current drive (LHCD) in reactor regime was doubted in connection with this effect. The quasilinear change of the slope of the alpha-particle distribution function is taken into account. Analytical estimates are obtained showing that at a sufficiently high wave energy density the power absorped by alpha-particles saturates (in the approximation used). For the parameters of a hybrid reactor, the saturated power was found much lower than that computed from the linear theory. It seems, therefore, that, at least for hybrid reactor conditions, the alphaparticles need not represent a serious obstacle to LHCD. Some further aspects of this effect are discussed.The authors are grateful to Drs. R. Klima, V. A. Petrílka and J. Preinhealter for valuable discussions.     

Chemical dynamics of the CH(X2Π) + C2H4(X1A1g), CH(X2Π) + C2D4(X1A1g), and CD(X2Π) + C2H4(X1A1g) reactions studied under single collision conditions

The crossed beam reactions of the methylidyne radical with ethylene (CH(X(2)Π) + C(2)H(4)(X(1)A(1g))), methylidyne with D4-ethylene (CH(X(2)Π) + C(2)D(4)(X(1)A(1g))), and D1-methylidyne with ethylene (CD(X(2)Π) + C(2)H(4)(X(1)A(1g))) were conducted at nominal collision energies of 17-18 kJ mol(-1) to untangle the chemical dynamics involved in the formation of distinct C(3)H(4) isomers methylacetylene (CH(3)CCH), allene (H(2)CCCH(2)), and cyclopropene (c-C(3)H(4)) via C(3)H(5) intermediates. By tracing the atomic hydrogen and deuterium loss pathways, our experimental data suggest indirect scattering dynamics and an initial addition of the (D1)-methylidyne radical to the carbon-carbon double bond of the (D4)-ethylene reactant forming a cyclopropyl radical intermediate (c-C(3)H(5)/c-C(3)D(4)H/c-C(3)H(4)D). The latter was found to ring-open to the allyl radical (H(2)CCHCH(2)/D(2)CCHCD(2)/H(2)CCDCH(2)). This intermediate was found to be long lived with life times of at least five times its rotational period and decomposed via atomic hydrogen/deuterium loss from the central carbon atom (C2) to form allene via a rather loose exit transition state in an overall strongly exoergic reaction. Based on the experiments with partially deuterated reactants, no compelling evidence could be provided to support the formation of the cyclopropene and methylacetylene isomers under single collision conditions. Likewise, hydrogen/deuterium shifts in the allyl radical intermediates or an initial insertion of the (D1)-methylidyne radical into the carbon-hydrogen/deuterium bond of the (D4)-ethylene reactant were found to be-if at all-of minor importance. Our experiments propose that in hydrocarbon-rich atmospheres of planets and their moons such as Saturn's satellite Titan, the reaction of methylidyne radicals should lead predominantly to the hitherto elusive allene molecule in these reducing environments.     

Photovoltaic cells based on nickel phthalocyanine and zinc oxide formed by atomic layer deposition

The introduction of an ultrathin zinc oxide (ZnO) layer formed by the atomic layer deposition (ALD) technique was found to improve the operation parameters of nickel phthalocyanine (NiPc) based photovoltaic cells with a transparent bottom electrode, indium tin oxide (ITO). This improvement is attributed to several reasons, such as I) increase of photovoltaic yield in ITO/p-NiPc/n-ZnO/Al cells incorporating a hybrid heterojunction as compared to single-layer ITO/NiPc/Al cells, II) enhancement of the overall spectral response in the double-layer cells and III) extension of long-term operational stability.