甲醇在超临界环已烷中形成簇团的Monte Carlo初探

用Ｍｏｎｔｅ Ｃａｒｌｏ方法研究了甲醇－环己烷体系的微观结构随压力（密度）的变化情况，结果表明，在临界区域甲醇分子的聚集最为明显，形成的甲醇团簇尺寸最大，溶剂分子在甲醇周围的局部密度则在低于临界区或亚临界区较大。     

Nonequilibrium solid phase formation studied by lattice dynamics calculation and ion beam mixing in an immiscible Co-Ag system

For the equilibrium immiscible Co-Ag system, a proven realistic ab initio derived n-body potential is applied to study the nonequilibrium solid phase formation at three chemical stoichiometries of Co/Ag = 1:3, 1:1, and 3:1. To predict the structural stability, the elastic constants and the phonon spectra are calculated at the chosen stoichiometries with a total of eight hypothetical crystalline structures. The calculated results suggest that four compounds, that is, D0(3) CoAg3, B1 CoAg, B2 CoAg, and D0(3) Co3Ag, are unstable, as they all feature negative elastic constants as well as imaginary phonons, and that another four compounds of both fcc-type L1(2) and hcp-type D0(19) structures at chemical stoichiometries of Co/Ag = 1:3 and 3:1, respectively, may elastically be favored and therefore obtainable under some specific conditions. It is also found that all the calculated elastic constants and phonon spectra are coincident within the framework of the elastic theory. Moreover, the calculated elastic constants are in good agreement with those acquired directly from ab initio calculations, lending support to the validity of the ab initio derived n-body Co-Ag potential as well as its resultant elastic constants and the phonon spectra. Interestingly, some of the predicted nonequilibrium solid phases, that is, two hcp-type compounds at chemical stoichiometries of Co/Ag = 1:3 and 3:1, respectively, are indeed obtained in ion beam mixing experiments and their lattice constants determined by diffraction analysis are in good agreement with those from calculations.     

近红外漫反射光谱法对固态样品的无损分析

本文应用目标因子分析研究了固态样品的近红外漫反射光谱，用目标因子分析成功地确定了固态样品的物种数、物种种类和各物种的含量。     

碱改性γ－Al_2O_3催化剂表面碱强度分布与COS水解活性的研究

用非水滴定法和Ｈａｍｍｅｔｔ系列指示剂测定了ＣＯＳ水解碱改性γ－Ａｌ_２Ｏ_３催化剂的表面碱强度分布．发现表面碱强度分布不均匀与表面能量分布不均匀相呼应．采用零点酸碱强度（Ｈ_（０，ｍａｘ））及碱中心区域分析法，Ｂｒｏｎｓｔｅｄ催化定律，进一步证实ＣＯＳ水解反应具有明显碱催化特征，较高活性催化剂的Ｈ_（０，ｍａｘ）一般为１０左右，对ＣＯＳ水解反应起主要作用的碱性中心的碱强度（Ｈ_０）为４．８≤Ｈ_０≤９．８．对碱金属氧化物改性后的γ－Ａｌ_２Ｏ_３催化剂，Ｂｒｏｎｓｔｅｄ规律在每个碱强度分区域内是适用的．     

Preparation and optical properties of Eu(III) complexes J-aggregate formed on the surface of silver nanoparticles

Ag colloidal nanoparticles coated with Eu(TTA)₃ · 2H₂O complexes were prepared, and it was found that Eu(TTA)₃ · 2H₂O complexes J-aggregate was formed on the surface of Ag nanoparticles according to a red shift (18.2 nm) in UV–Vis spectra. However, there had similar excitation wavelength, which was attributed to existence of Ag nanoparticles. Highly luminescent properties of Ag colloidal nanoparticles were observed, and it was believed to result from low energy transfer between Eu(III) complexes and Ag and the large electromagnetic field arising from the excitation of surface plasmon polariton of Ag nanoparticles.     

Ab initio study of the complexes of halogen-containing molecules RX (X=Cl, Br, and I) and NH3: towards understanding the nature of halogen bonding and the electron-accepting propensities of covalently bonded halogen atoms

Ab initio calculations have been performed on a series of complexes formed between halogen-containing molecules and ammonia to gain a deeper insight into the nature of halogen bonding. It appears that the dihalogen molecules form the strongest halogen-bonded complexes with ammonia, followed by HOX; the charge-transfer-type contribution has been demonstrated to dominate the halogen bonding in these complexes. For the complexes involving carbon-bound halogen molecules, our calculations clearly indicate that electrostatic interactions are mainly responsible for their binding energies. Whereas the halogen-bond strength is significantly enhanced by progressive fluorine substitution, the substitution of a hydrogen atom by a methyl group in the CH(3)X...NH(3) complex weakened the halogen bonding. Moreover, remote substituent effects have also been noted in the complexes of halobenzenes with different para substituents. The influence of the hybridization state of the carbon atom bonded to the halogen atom has also been examined and the results reveal that halogen-bond strengths decrease in the order HC triple bond CX > H(2)C=CHX approximately O=CHX approximately C(6)H(5)X > CH(3)X. In addition, several excellent linear correlations have been established between the interaction energies and both the amount of charge transfer and the electrostatic potentials corresponding to an electron density of 0.002 au along the R-X axis; these correlations provide good models with which to evaluate the electron-accepting abilities of the covalently bonded halogen atoms. Finally, some positively charged halogen-bonded systems have been investigated and the effect of the charge has been discussed.     

Molecularly imprinted solid-phase extraction of (-)-ephedrine from Chinese Ephedra

Method of molecularly imprinted solid phase extraction (MISPE) of (-)-ephedrine from Chinese Ephedra has been developed in the research. The molecularly imprinted polymer (MIP) with good selectivity and affinity for (-)-ephedrine was synthesized with (-)-ephedrine as the template, methacrylic acid as the functional monomer. The washing and elution conditions in MISPE were selected and optimized for efficient analyte extraction and sample clean-up. A clean analytical HPLC base line of ephedra extract was obtained after MISPE, which indicated that the sample pre-treatment was efficient. Good recovery and precision were obtained in the assessment for the MISPE-HPLC procedure, which demonstrated it is a reliable method and can be used for the determination of (-)-ephedrine in herbal ephedra.     

Study of the binding characteristics and transportation properties of a 4-aminopyridine imprinted polymer membrane

Molecularly imprinted polymer membranes containing artificial recognition sites for 4-aminopyridine have been prepared by photopolymerization using 4-aminopyridine as template. Reference membranes were prepared with the same monomer mixture but in the absence of the template. The binding characteristics of the imprinted polymer membrane were investigated by a batch method and the transport properties of the membranes were investigated using diffusion chambers. The results showed that the binding amount of 4-aminopyridine is higher than that of 2-aminopyridine whereas the latter can transport the 4-aminopyridine imprinted polymer membrane faster than 4-aminopyridine.     

氮硫杂冠醚及其衍生物的合成

以噻吩、水杨醛、二胺、溴乙酸、烯丙基氯和丙烯腈为原料合成了 4,5 :14 ,15 二苯 3 ,16 二氧 2 1 硫 7,12 二氮双环[16.2 .1]二十一环 1( 2 0 ) ,18 二烯 (简称氮硫杂冠醚 )及其 5种衍生物 ,经元素分析 ,IR ,1 HNMR和MS谱表征了这些化合物的结构 .     

Thermal degradation behaviors of some branched and linear polysiloxanes

The thermal degradation behaviors of some branched and linear polysiloxanes were studied by thermogravimetric (TG) analysis and infrared (IR) spectroscopy, and the effect of phenyl content on the thermal stability of the tested branched polysiloxanes was investigated. The branched polysiloxanes with phenyl obtain higher thermal stability at lower temperature. The degradation residues of the examined branched polysiloxanes at 800 °C are rather high, 65.1-77.6% in N₂ and 40.5-66.5% in air, respectively. However, the amount of solid residue increases with decrease in phenyl content in both N₂ and air atmospheres. It was found that the thermal stability of the branched polysiloxanes is higher than that of the linear one, which indicated that the branched structure benefits the formation of a crosslink in the solid residue.