The cyclodimerisation of 3-methyl-2-butenenitrile

3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3).     

Novel fluorescent probe as aggregation predictor and micro-polarity reporter for micelles and mixed micelles

Aggregational behaviour of micelles sodium dodecyl sulphate (SDS and Triton X-100, TX-100 both in pure and mixed form) and micelle like aggregates such as polymer-surfactant system [polymer poly(vinyl pyrrolidone), PVP]-SDS have been studied by using fluorescence characteristics of a newly synthesized probe. The critical micelle concentration (CMC) values determined at various surfactant compositions are lower than the ideal values indicating a synergistic effect. The value of the interaction parameter for the surfactant mixture has been determined which agrees well with the value calculated according to molecular thermodynamic theory. The total aggregation number of surfactant in mixed micelle shows a drastic variation in the SDS mole fraction range 0 < or = alpha1 < or = 0.3 and beyond the range it remains practically constant. Molar-based partition coefficients for the dye between the micellar and aqueous phase have been determined and a non-linear variation is obtained for the mixed micellar system. Variations of micro-polarity in the mixed micellar region have been investigated as a function of surfactant composition and results have been explained in terms of a suitable realistic model.     

Conical parametric scattering of a single extraordinary beam in BaTiO3 crystal

In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO₃ photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering.     

Photophysics of representative ketocyanine dyes: dependence on molecular structure

Spectral properties of a new fluorescent ketocyanine dye have been discussed. The energy of maximum absorption/fluorescence of the dye exhibits bathochromic shift with increasing polarity of the medium. Both dipolarity-polarisability and hydrogen bond donation interaction contribute to solvation of the dye. Study of fluorescence parameters points to existence of different emitting states of the dye for aprotic and protic solvents. While the emitting state is the (1)(π, π*) state for aprotic solvents, fluorescence supposedly take place from a different emitting state involving H-bond formation in the excited state in protic solvents. Fluorescence parameters of the dye have been compared with those for a structurally similar symmetric ketocyanine dye. The faster decay of the dye relative to its symmetric counterpart has been explained as due to an increase of nonradiative decay.     

Polychromatic Colorings of Plane Graphs

We show that the vertices of any plane graph in which every face is incident to at least g vertices can be colored by ⌊(3g−5)/4⌋ colors so that every color appears in every face. This is nearly tight, as there are plane graphs where all faces are incident to at least g vertices and that admit no vertex coloring of this type with more than ⌊(3g+1)/4⌋ colors. We further show that the problem of determining whether a plane graph admits a vertex coloring by k colors in which all colors appear in every face is in ℘ for k=2 and is -complete for k=3,4. We refine this result for polychromatic 3-colorings restricted to 2-connected graphs which have face sizes from a prescribed (possibly infinite) set of integers. Thereby we find an almost complete characterization of these sets of integers (face sizes) for which the corresponding decision problem is in ℘, and for the others it is -complete. Research of N. Alon was supported in part by the Israel Science Foundation, by a USA–Israeli BSF grant, and by the Hermann Minkowski Minerva Center for Geometry at Tel Aviv University. Research of R. Berke was supported in part by JSPS Global COE program “Computationism as a Foundation for the Sciences.” Research of K. Buchin and M. Buchin was supported by the Netherlands’ Organisation for Scientific Research (NWO) under BRICKS/FOCUS project no. 642.065.503. Research of P. Csorba was supported by DIAMANT, an NWO mathematics cluster. Research of B. Speckmann was supported by the Netherlands’ Organisation for Scientific Research (NWO) under project no. 639.022.707.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Use of fluorescence probes for studying Kamlet-Taft solvatochromic parameters of micellar system formed by binary mixture of sodium dodecyl sulfate and Triton-X 100

Fluorescence probes have been used to estimate Kamlet-Taft solvatochromic parameters alpha and pi* representing hydrogen-bond donation ability and dipolarity/polarizability, respectively, of sodium dodecyl sulfate (SDS)-Triton X 100 (TX100) mixed aggregates with varying compositions. The hydrogen-bond donation ability of the mixed aggregate has been found to increase with SDS composition, whereas the dipolarity/polarizability parameter decreases. The relative contribution of electrostatic and steric effect toward the total free energy of micellization have been calculated for the mixture. The solvatochromic parameters alpha and pi* depend linearly on the total free energy of micellization, indicating a correlation between aggregational and solvatochromic properties.     

Electronic structure, magnetic and electrical properties of multiferroic PbFe1/2Ta1/2O3

Structural analysis of the synthesized lead iron tantalate, PbFe_1/2Ta_1/2O₃ (PFT) is performed by the refinement of the X-ray diffraction data at room temperature using the GSAS code. Energy dispersive X-ray spectrometry analysis is done to find out the chemical composition. The electronic structure of PFT is calculated by the first principles full potential linearized augmented plane wave method. The spin polarized density of states shows the insulating nature. The magnetic moment of 4.3 μB per Fe ion is obtained from the electronic structure calculation using the GGA+U method and compared with the available experimental data. The electronic structure of the PFT is verified by X-ray photoemission spectroscopy. The dielectric spectroscopy is applied to investigate the electrical properties of PFT in the frequency range from 100 Hz to 1 MHz and in the temperature range from 183 to 253 K. The frequency dependent electrical data are analyzed by conductivity formalism. The relaxation mechanism is explained using the Cole-Cole approach.