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).     

Effect of isomeric butanols on the temperature corresponding to the adiabatic compressibility minimum of water

The effect of isomeric butanols on the temperature corresponding to the adiabatic compressibility minimum of water (T _β) was studied using a variablepath interferometer working at 3 MHz. The structural contribution to the shift inT _β, [ΔT _βstr]_exp, was found to be positive and to increase with concentration to a maximum atX ₂?0.0193, 0.0100, and 0.0090 fort-butanol, sec-butanol, and isobutanol, respectively. The results have been explained on the basis of stabilization of water structure at low concentrations of alcohol. The quantity [ΔT _βstr]_exp forn-butanol is practically zero at low concentrations, while at high concentrations it is negative, indicating rupture of the hydrogen-bonded structure of water by this solute. At any given concentration,t-butanol > sec-butanol > isobutanol >n-butanol is the order of increasing structural contribution to the shift inT _β. Theoretical values of the structural contribution to the shift inT _β are in good agreement with the experimental data.     

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.     

Energy absorption buildup factors for thermoluminescent dosimetric materials and their tissue equivalence

Gamma ray energy-absorption buildup factors were computed using the five-parameter geometric progression (G-P) fitting formula for seven thermoluminescent dosimetric (TLD) materials in the energy range 0.015–15 MeV, and for penetration depths up to 40 mfp (mean free path). The generated energy-absorption buildup factor data have been studied as a function of penetration depth and incident photon energy. Buildup factors determined in the present work should be useful in radiation dosimetry, diagnostics and therapy. The tissue equivalence of TLD materials is also discussed.     

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.     

Solvent effects on the absorption and fluorescence spectra of some laser dyes: estimation of ground and excited-state dipole moments

The absorption and fluorescence spectra of three extensively used laser dyes namely 1,1,4,4-tetraphenyl-1,3-butadiene (TPB), 2-(4'-t-butylphenyl)-5-(4'-biphenylyl)-1-oxa-3,4-diazole (BPBD), 1,4-bis[2-(2-methylphenyl)ethenyl]-benzene (Bis-MSB) have been recorded at room temperature (300K) in solvents of different polarities. The effects of the solvents upon the spectral properties are discussed. The ground-state dipole moments (mu(g)) were determined experimentally by Guggenheim and Higasi method separately and were compared with theoretical values obtained using quantum chemical method. The ground-state dipole moments obtained by using Guggenheim method were then used in the estimation of excited-state dipole moments (mu(e)) by using Lippert's, Bakhshiev's and Kawski-Chamma-Viallet's equations. In all the above three equations the variation of the Stokes shift with the solvent dielectric constant and refractive index was made use of. It was observed that dipole moments of excited state were higher than those of the ground state for all the dyes.     

Nonlinear fluorescence quenching of newly synthesized coumarin derivative by aniline in binary mixtures

The fluorescence quenching of newly synthesized coumarin (chromen-2-one) derivative, 4-(5-methyl-3-phenyl-benzofuran-2-yl)-6-chloro-chromen-2-one (MPBClC) by aniline in different binary solvent mixtures of benzene and acetonitrile have been reported by steady state fluorescence measurements. All the measurements were carried out at room temperature (296 K). A positive curvature from linearity was observed in the Stern–Volmer (S–V) plot in all the solvent mixtures. Various rate parameters for the fluorescence quenching have been determined by sphere of action static quenching model and finite sink approximation model. The results show that the positive curvature in the S–V plot is due to both static and dynamic quenching processes. Further, with the use of finite sink approximation model, it is concluded that these bimolecular reactions are diffusion-limited.     

Thermodynamic properties of ternary mixtures containing water, 2-ethoxyethanol,and <Emphasis Type="Italic">t</Emphasis>-butanol at 298.15 K

Ultrasonic speeds and isentropic compressibilities were measured at 298.15 K in the water-rich region of aqueous solutions of water + 2-ethoxyethanol (2EE) + t-butanol. The excess properties of ultrasonic speed and isentropic compressibility were also calculated and have been discussed in terms of molecular interactions. The concentrations of t-butanol at which ultrasonic speed becomes maximum and isentropic compressibility becomes minimum are found to decrease with increase in the concentration of 2EE in the cosolvent (aqueous 2EE). This behavior indicates that the aqueous ternary solutions are less structured than aqueous t-butanol. This behavior is explained as due to a decrease in the ability of t-butanol to form clathrate hydrates owing to the presence of 2EE. When the concentration of 2EE in the cosolvent (x _2EE) > 0.14, ultrasonic speed decreases and isentropic compressibility increases with concentration of t-butanol indicating that the ternary solution behaves as normal solution wherein any further addition of 2EE or t-butanol leads to destabilization of the hydrogen bonded structure of water and t-butanol looses its ability to form clathrate hydrates in aqueous solutions.     

怀孕期头发中一些元素含量的变化趋势

用同步辐射激发X射线荧光分析,对11个产妇怀孕期间头发内一些元素含量的变化趋势进行了测量,在各自对比的基础上,得到了一些结果。     

Synthesis and fabrication of highly functionalized Jeffamine antimicrobial polymeric coating

A simple, robust, and eco‐friendly technique for the fabrication of functionalized Jeffamine polymer in an aqueous medium is developed. The polymer is prepared by post polymerization modification of Jeffamine ED‐2003 of molecular weight 2000. The structure of the modified polymer was studied in detail using FTIR and NMR (¹H and ¹³C NMR) spectroscopic methods. The thermal properties and degradation of the polymer were examined by DSC and TGA techniques. The polymer exhibited glass transition temperature (T_g) at 115°C. The functionalized polymeric compound showed good antimicrobial activity against gram‐negative bacterium Escherichia coli, a tubercular variant Mycobacterium smegmatis, and gram‐positive bacterium Staphylococcus aureus with a zone of inhibition of 6 to 12, 9, and 5 to 9 mm diameter, respectively. The compound also showed good activity against the fungus, Candida albicans, with a zone of inhibition of 6 to 11 mm diameter. The morphology of the polymer films and interaction of the microbes with functionalized Jeffamine polymer were investigated by using scanning electron microscopy (SEM).