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).     

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.     

Absolute intensity measurements of impurity emissions in a shock tunnel and their consequences for laser-induced fluorescence experiments

Absolute intensity measurements of impurity emissions in a shock tunnel nozzle flow are presented. The impurity emission intensities were measured with a photomultiplier and optical multichannel analyser and calibrated against an intensity standard. The various metallic contaminants were identified and their intensities measured in the spectral regions 290 to 330 nm and 375 to 385 nm. A comparison with calculated fluorescence intensities for predissociated laser-induced fluorescence signals is made. It is found that the emission background is negligible for most fluorescence experiments.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

Adsorption of anionic and cationic dyes by activated carbons, PVA hydrogels, and PVA/AC composite

The textural and adsorption characteristics of a series of activated carbons (ACs), porous poly(vinyl alcohol) (PVA) gels, and PVA/AC composites were studied using scanning electron microscopy, mercury porosimetry, adsorption of nitrogen (at 77.4 K), cationic methylene blue (MB), anionic methyl orange (MO), and Congo red (CR) from the aqueous solutions. Dye-PVA-AC-water interactions were modeled using the semiempirical quantum chemical method PM6. The percentage of dye removed (C(rem)) by the ACs was close to 100% at an equilibrium concentration (C(eq)) of less than 0.1 mM but decreased with increasing dye concentration. This decrease was stronger at C(eq) of less than 1 mM, and C(rem) was less than 50% at a C(eq) of 10-20 mM. For PVA and the PVA/AC composite containing C-7, the C(rem) values were minimal (<75%). The free energy distribution functions (f(ΔG)) for dye adsorption include one to three peaks in the -ΔG range of 1-60 kJ/mol, depending on the dye concentration range used and the spatial, charge symmetry of the hydrated dye ions and the structural characteristics of the adsorbents. The f(ΔG) shape is most complex for MO with the most asymmetrical geometry and charge distribution and adsorbed at concentrations over a large C(eq) range. For symmetrical CR ions, adsorbed over a narrow C(eq) range, the f(ΔG) plot includes mainly one narrow peak. MB has a minimal molecular size at a planar geometry (especially important for effective adsorption in slit-shaped pores) which explains its greater adsorptive capacity over that of MO or CR. Dye adsorption was greatest for ACs with the largest surface area but as molecular size increases adsorption depends to a greater extent on the pore size distribution in addition to total and nanopore surface areas and pore volume.     

Vibrational temperature measurements in a shock layer using laser induced predissociation fluorescence

Single shot spatially and spectrally resolved laser induced predissociation fluorescence measurements in a shock layer around a cylinder in a pulsed supersonic free stream are presented. Fluoresence signals were produced using the tuned output of an argon fluoride excimer laser to excite a mixture of rovibrational transitions in molecular oxygen. The signals produced along a line inside the shock layer were focussed onto a two dimensional detector coupled to a spectrometer, thus allowing spectral and spatial resolution of the fluoresence. In this way, it was possible to detect two fluoresence signals from two different transitions simultaneously, allowing the determination of vibrational temperatures without the need for calibration. To minimize problems associated with low signal to noise ratios, background subtraction and spatial averaging was required.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

ALUMINUM SULFONATED PHTHALOCYANINE DISTRIBUTION IN RODENT TUMORS OF THE COLON, BRAIN and PANCREAS

Abstract The most widely discussed aspect of photodynamic therapy (PDT) is the preferential uptake and retention of sensitisers by malignant tissues. The sensitiser usually used is hematoporphyrin derivative (HPD) but this compound is not an ideal photosensitiser for this purpose and we have therefore studied an aluminum sulfonated phthalocyanine (AlSPc) as a possible alternative. Here we have studied the uptake and retention of this compound in a rat colon cancer, a hamster pancreatic cancer and a mouse glioma, using an alkali extraction technique to estimate tissue AlSPc and comparing the results with those from the corresponding normal tissues. All of the tumors studied reached accumulation peaks at 24-48 h after intravenous administration of AlSPc compared with peaks at 1-3 h in the normal tissues. The tumors outside the central nervous system (CNS) reached peak tumor : normal tissue ratios of 2-3 : 1 and the tumor within the CNS, the malignant glioma, reached a far higher ratio of 28 : 1. These ratios are similar to those reported by others using HPD.     

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.     

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。     

Optogalvanic detection as a quantitative method in spectroscopy

The use of the optogalvanic effect for measuring spectroscopic quantities such as wavelengths, line profiles and line integrals is discussed. The quantitative aspects of absorption and optogalvanic spectroscopy are compared. It is experimentally demonstrated for calcium that optogalvanic line integral measurements are not simply linearly related to the oscillator strength. Measured optogalvanic and absorption profiles for Ne, Ar and Cu are compared and it is shown that both methods yield the same result for certain conditions of the observed plasma. The dependence of the optogalvanic profiles on the current in the plasma is demonstrated.     

A simple physical theory of weak Mach reflection over plane surfaces

It is shown that simple physical principles coupled with the inviscid shock jump relations can be applied to the problem of weak Mach reflection to the extent that the triple point path can be predicted from the incident shock Mach number , gas specific heat ratio and the inclination angle of the reflecting surface to the shock normal. Comparison with the Euler code data and with experiments show close agreement for conditions both far and close to transition and that the general shape of the reflected and Mach stem shocks follow simple curves except in the neighbourhood of the triple point. The conflict at the triple point in matching the flow deflection angles and pressures across the contact discontinuity remains. It is shown however that the simple model presented here gives a close match to the cfd and experimental overall shock and contact surface shapes although it cannot predict these or the flow properties in any detail. Received 10 May 1999 / Accepted 17 December 1999