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51.
采用密度泛函理论(DFT), 在B3LYP/6-311++G(d,p)基组上计算得到了21种N8H8链状异构体, 并研究了这些异构体间可能的互变异构情况. 为了得到更为精确的能量信息, 计算了QCISD(T)/6-311G(d,p)基组水平上各物质的能量. 所得的21种异构体分为4类(4种类型链状化合物): A为直链, B有一个支链, C有2个支链, D有3个支链; D类只有一种, A类稳定构型2种, B类稳定构型12种, C类稳定构型6种; 相对稳定的分别为: B2-1构型, B2-3构型和C23-2构型. 我们研究发现N8H8链状异构体中含有明显N=N双键特征有利于化合物稳定性的提高. 相似文献
52.
The relative permittivity of 1,2-dimethoxyethane and N,N-dimethylformamide mixtures from −10 to 40°C
Gianni Goldoni Luigi Marcheselli Andrea Marchetti Lorenzo Tassi Giuseppe Tosi 《Journal of solution chemistry》1992,21(9):953-962
Binary solutions of N,N-dimethylformamide and 1,2-dimethoxyethane have been investigated by means of dielectric measurements at temperatures ranging from –10 to +40°C, and for nine mixtures covering the whole miscibility field expressed by the mole fraction of one component (0X11). The experimental data were used to study the dependence of on T and X1, of the type = (T), = (X1), and = (T,X1). Further, the excess mixing function E has been evaluated in order to identify particular patterns of interaction between unlike molecules and any other factor that could modify such patterns. The minimum in the E vs. composition plots suggests the formation of an adduct of stoichiometric ratio DMFDME=11 at all the investigated temperatures. 相似文献
53.
K. Ramulu B. M. Rao P. Madhavan M. Lalitha Devi M. K. Srinivasu K. B. Chandrasekhar 《Chromatographia》2007,65(3-4):249-252
A simple and new isocratic normal phase chiral HPLC method has been developed for the determination of enantiomeric purity
of pemetrexed disodium (l-enantiomer) in bulk drugs with a short run time of about 20 min. Chromatographic separation of l and d-enantiomers of pemetrexed disodium was achieved on an amylose based chiral stationary phase using a mobile phase consists
of hexane, ethanol and trifluoro acetic acid. The resolution between the enantiomers was found to be more than 2.0. The system
precision and method precision were found to be within 5% RSD for the distomer (d-enantiomer) at its specification level (i.e. not more than 1.0% w/w). The limit of detection and limit of quantification of distomer were 1.6 and 5 μg mL−1, respectively for 10 μL injection volume. The percentage recovery of distomer was ranged from 90.6 to 105.7 in bulk drug
samples. The test solution was found to be stable in the diluent for 48 h. The method was found to be specific for the enantiomers
of pemetrexed disodium and can be conveniently used for the quantification of undesired d-enantiomer present in the bulk drug samples of pemetrexed disodium. 相似文献
54.
Federico Moscardó Miguel Paniagua Emilio San-Fabián 《Theoretical chemistry accounts》1979,53(4):377-381
Anab initio study of the relative stability for the states2
A
1g
and2
E
g of C2H
6
+
has been carried out. The results of the Open Shell Restricted Hartree-Fock calculations lead to assign the2
A
1
g
as the ground state of the molecule in agreement with previous SCF calculations.The correlation energy associated to both states has been calculated within the correlation hole model and the results, contrary to those obtained from Configuration Interaction calculations, do not alter qualitatively the conclusions from SCF. 相似文献
55.
Abdelfetah Mounir Mohamed El Guendouzi Abderrahim Dinane 《Journal of solution chemistry》2002,31(10):793-799
Ternary aqueous solutions of MgSO4 and K2SO4 have been studied by the hygrometric method at 25°C. The relative humidity of this system is measured at total molalities from 0.35 mol-kg–1 to about saturation for three ionic-strength fractions (y = 0.25, 0.50, and 0.80 of MgSO4. The data allow calculation of water activities and osmotic coefficients. From these measurements, the Pitzer ionic mixing parameters are determined and used to predict the solute activity coefficients in the mixture. The results are used to calculate the excess Gibbs energy at total molalities for ionic-strength fraction y. 相似文献
56.
采用密度泛函理论的b3lyp方法在6-311++G**基组上对15种分子式为N6H6的氮氢化合物进行了理论计算, 并且应用了自然键轨道理论(Nature Bond Orbital, NBO)和分子中的原子理论(Atoms In Molecules, AIM)分析了这些化合物的成键特征和相对稳定性. NBO分析表明N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的主要因素, AIM计算的氮氮键的键临界点电荷密度与键长呈反比关系. 而且, NBO的立体和超共轭分析表明立体交换排斥能和超共轭作用对这些分子的相对稳定性起了重要作用. G3MP2计算结果表明氮氢化合物的生成热均为正, 并且环状分子的能量和生成热都高于链状分子. 相似文献
57.
Xinquan Zhang Yong Yi Yonglin Liu Xiang Li Jinglei Liu Yumei Jiang Yaqin Su 《Analytica chimica acta》2006,555(1):57-62
A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of 165Ho(100) and 169Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g−1, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er2O3 and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS. 相似文献
58.
云南省位于多个地块交界处,构造活动活跃且地震活动频发。利用中国静止气象卫星风云二号系列相当黑体温度TBB数据,应用小波变换和相对傅氏功率谱的时频相对功率谱方法(T-F RPS),提取并分析了云南省2008年至今发生的5.5级以上地震热红外异常信息,且对比分析了特征周期、特征幅值、异常形态、异常演化过程等参数。结果表明:(1)该系列地震热红外异常信息易于用时频相对功率谱方法(T-F RPS)提取识别,且异常特征具有"出现-扩大-减小-消失"的规律;(2)异常特征周期和持续时间也具有一定的规律性;(3)异常沿着断层延展,震中位于异常边缘一侧或者异常区域交汇地带,发震时刻多位于相对功率谱幅值下降阶段;(4)震级与相对功率谱峰值有一定的相关性,震级高,峰值也较高;(5)地震类型与异常面积有一定的相关性,双震型地震异常面积较大。此外,讨论了地震热红外异常与构造活动、气候状况、天气情况和季节等因素的关系。 相似文献
59.
60.
P. Madhavan Bandlamudi Mallikarjuna Rao B. Pravin S. Abhishek P. R. Kumar M. Sreenivasulu K. B. Chandrasekhar 《Chromatographia》2007,66(3-4):243-246
A chiral liquid chromatographic method for enantiomeric resolution of β-amino-β-(3-methoxyphenyl) propionic acid was developed
and validated. The “hybrid” π-electron donor–acceptor based stationary phase (R,R) Whelk-01 was found to be enantiomerically
selective for (R) and (S) enantiomers of β-amino-β-(3-methoxyphenyl) propionic acid with a resolution greater than 2.0. The effects of isopropyl alcohol
and ethanol on enantioselectivity and resolution of enantiomers were evaluated. Calibration curves were linear over the range
of 0.10–1.00, with a regression coefficient (r) of 0.999. The limit of detection (LOD) and limit of quantification (LOQ) were 300 and 1,000 ng mL−1 respectively for 10 μL injection volume. The percentage RSD of the peak area of six replicate injections of (S) enantiomer at LOQ concentration was 2.8. The percentage recovery of (S) enantiomer from (R) enantiomer samples ranged from 92 to 102. The test solution was observed to be stable up to 24 h after the preparation.
The developed normal phase chiral LC method can be used for the enantiomeric purity evaluation of R-β-amino-β-(3-methoxyphenyl) propionic acid. 相似文献