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21.
A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH3OH]+ and [M + H]+ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]+) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H]– ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach. 相似文献
22.
Rabindra N. Roy James J. Gibbons Guilio LaCross Jr. Charles W. Krueger 《Journal of solution chemistry》1976,5(5):333-343
The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K
1)for the process HG+H++G± is expressed as a function ofT(oK) by the equation pK
1 = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK
1is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole–1, G°=4038 cal-mole–1, S°=–8.52 cal-°K–1-mole–1, and C
p
o
=–53 cal-°K–1-mole–1. The second acidic dissociation constant (K
2)for the process G±H++G– over the temperature range studied is given by the equation pK
2 = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK
2is 9.578 in MeOH–H2O as compared with 9.780 in water, whereas H° is 10,257 cal-mole–1, G° is 13,063 cal-mole–1, S° is –9.41 cal-°K–1-mole–1, and C
p
o
is –43 cal-°K–1-mole–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C). 相似文献
23.
The molar heat capacity of the azeotropic mixture composed of ethanol and toluene was measured by a high precision adiabatic calorimeter from 80 to 320 K. The glass transition and phase transitions of the azeotropic mixture were determined based on the heat capacity measurements. A glass transition at 103.350 K was found. A solid-solid phase transition at 127.282 K, two solid-liquid phase transitions at 153.612 and 160.584 K were observed, which correspond to the transition of metastable crystal to stable crystal of ethanol and the melting of ethanol and toluene, respectively. The thermodynamic functions and the excess ones of the mixture relative to the standard temperature 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature. 相似文献
24.
This paper concerns the application of excess adsorption isotherms, measured for solvent mixture/adsorbent systems, to the characterization of TLC data. For this purpose the excess adsorption isotherms for three liquid mixtures: cyclohexane/ benzene, benzene/acetone, and carbon tetrachloride/ethyl acetate on silica gel at 20°C have been measured. These mixtures have been used as binary mobile phases in TLC measurements. It has been shown for a given solute in binary mobile phase that the quantity RM is a simple function of the excess adsorption. Parameters of this function have been used to characterize chromatographic systems with binary mobile phases. 相似文献
25.
A novel alcohol dehydration membrane with a three layer structure has been prepared. The top layer is a thin dense film of chitosan (CS), and the support layer is made of microporous polyacrylonitrile (PAN). Between the dense and microporous layer, there is an intermolecular cross-linking layer. This novel composite membrane has a high separation factor of more than 8000 and a good permeation rate of 0.26 kg/m2 h for the pervaporation of 90 wt% ethanol aqueous solution at 60°C, 0.8 kg/m2 h flux for a n-PrOH/water system and around 1 kg/m2 h flux for an i-PrOH/water system using 80 wt% alcohol concentration at 60°C. The separation factor for both cases is more than 105. The separation performance varies with feed composition, operating temperature and conditions of membrane preparation. The results show that the separation factor and flux of this membrane increase with raising the operating temperature. At the same time, the crosslinking layer improves durability of the composite membrane, and the pervaporation performance can be adjusted by changing the structure of the cross-linking layer. The cross section of the composite membrane has been examined by SEM. 相似文献
26.
The adsorption of a surfactant mixture, based on an anionic surfactant, sodium dodecyl benzenesulfonate (SDBS) and a nonionic
surfactant (Triton X-100, or TX100), on alumina nanoparticles was determined by solution depletion method combined with spectrometric
measurement. It is shown that the light scattering, originated from the residual adsorbent alumina particles in the supernatant
after centrifugation separation, interferes with the measurements of absorbance of the surfactant molecules, and therefore
constitutes an error source for determination of the surfactant concentration in the supernatant by spectrometric means. The
intensity of this light scattering, namely the influence of the residual alumina nanoparticles upon the surfactant adsorption,
was related to the surfactant adsorption and its equilibrium concentration and varied among a batch. In this paper we report
a Kalman filter method in order to eliminate the variational scattering background caused by non-separated residual alumina
nanoparticles in each supernatant. This method is of interest as it is simple, easy to carry out and of high precision. 相似文献
27.
Baeva M. Luo X. Schäfer J. H. Uhlenbusch J. Zhang Z. 《Plasma Chemistry and Plasma Processing》1998,18(4):429-446
The present work deals with a pulsed microwave discharge in an Ar/CF
4
gas mixture under a low pressure (1–10 mbar). The discharge chamber developed has a cylindrical geometry with a coupling window alternatively made of quartz or alumina. The setup allows one to investigate the plasma–wall interactions (here etching of the quartz window) and the ignition process of the pulsed microwave plasma. Microwave pulses with a duration of 50–200 s and repetition rate between 1 and 10 kHz are typical for the experiments. The space-time behavior of the fluorine number density in the discharge has been investigated experimentally by optical actinometry. The discharge kinetics is modeled using electron-transport parameters and rate coefficients derived from solutions of the Boltzmann equation. Together with the solution of the continuity and electron balance equations and the rate equations describing the production of CF
x
(x=2, 3, 4) radicals and F atoms, a good agreement between experimental and theoretical data can be achieved. 相似文献
28.
LI Rui ZHANG Duan-Ming HUANG Ming-Tao SU Xiang-Ying CHEN Zhi-Yuan ZHU Hong-Ying ZHANG Lin 《理论物理通讯》2007,48(8):343-347
We propose a two-dimensional model of polydisperse granular mixtures with a power-law size distribution in the presence of stochastic driving. A fractal dimension D is introduced as a measurement of the inhomogeneity of the size distribution of particles. We define the global and partial granular temperatures of the multi-component mixture. By direct simulation Monte Carlo, we investigate how the inhomogeneity of the size distribution influences the dynamic properties of the mixture, focusing on the granular temperature, dissipated energy, velocity distribution, spatial clusterization, and collision time. We get the following results: a single granular temperature does not characterize a multi-component mixture and each species attains its own "granular temperature"; The velocity deviation from Gaussian distribution becomes more and more pronounced and the partial density of the assembly is more inhomogeneous with the increasing value of the fractal dimension D; The global granular temperature decreases and average dissipated energy per particle increases as the value of D augments. 相似文献
29.
30.
氨吸收式串联型动力/制冷复合循环 总被引:3,自引:0,他引:3
本文提出了一种新型的采用氨水混合工质的动力/制冷复合循环,该循环以中低温工业余热或燃气轮机排气为热源,将动力、制冷子循环采用串联方式连接,基础循环工质为氨质量浓度为0.27的氨水溶液,热源为365℃/104.3 kPa 的热空气,透平进气参数为350℃/3750 kPa,,以热效率η1、(火用)效率η2作为评价准则,模拟计算表明本循环的热效率η1 为17.8%,炯效率η2为45%,通过与其它有代表性的分供系统及联供系统进行热力性能方面的比较,表明本循环η1、η2均有不同程度提高。 相似文献