The Photochemistry of Ch3I in Various Matrices at Low Temperature

The photodissociation of methyl iodide in various matrices at low temperature was studied. The observed Raman spectra excited by 514.5 nm laser radiation showed that there were two different photolytically produced iodine species isolated in the matrices after illumination by a medium pressure mercury lamp. One species which was dominant at lower iodine concentrations and exhibited a progression with an ωe of 201 cm^?1, belonged to the matrix isolated iodine monomer (I₂). The other species, which was dominant at higher iodine concentrations with an ω_e of approximately 180 cm^?1, belonged to the iodine aggregate ((I₂)_n). Five progressions of resonance Raman or resonance fluorescence of these two species were also observed in the other matrices. The iodine aggregate in the methyl iodide matrix at 77 K was formed in a crystalline structure, while the photolytically generated iodine aggregate from CH₃I/Ar (2/3) matrix at 10 K, after illumination with a mercury lamp, was in amorphous form. The rearrangement of photolytically produced iodine aggregate in methyl iodide matrix was observed as a function of the duration of illumination. Local heating effects of the laser radiation might induce the iodine monomer to aggregate in matrices. The photodissociation mechanism of methyl iodide in matrices is also proposed.     

Spectroscopic characterization of alkaline earth uranyl carbonates

A series of alkaline uranyl carbonates, M[UO₂(CO₃)₃]·nH₂O (M=Mg₂, Ca₂, Sr₂, Ba₂, Na₂Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba₂[UO₂(CO₃)₃]·6H₂O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO₂)(CO₃)₃ clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90±0.02 Å.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces.     

Method and algorithm of obtaining the molecular intrinsic characteristic contours (MICCs) of organic molecules

The molecular intrinsic characteristic contour (MICC) is defined as the set of all the classical turning points of electron movement in a molecule. Studies on the MICCs of some medium organic molecules, such as dimethylether, acetone, and some homologues of alkanes, alkenes, and alkynes, as well as the electron density distributions on the MICCs, are shown for the first time. Results show that the MICC is an intrinsic approach to shape and size of a molecule. Unlike the van der Waals hard-sphere model, the MICC is a smooth contour, and it has a clear physical meaning. Detailed investigations on the cross-sections of MICCs have provided a kind of important information about atomic size changing in the process of forming molecules. Studies on electron density distribution on the MICC not only provide a new insight into molecular shape, but also show that the electron density distribution on the boundary surface relates closely with molecular properties and reactivities. For the homologues of alkanes, Rout(H), Dmin, and Dmax (the minimum and maximum of electron density on the MICC), all have very good linear relationships with minus of the molecular ionization potential. This work may serve as a basis for exploring a new reactivity indicator of chemical reactions and for studying molecular shape properties of large organic and biological molecules.     

Spectroscopy, NMR and DFT studies on molecular recognition of crown ether bridged chiral heterotrinuclear salen Zn(II) complex

A barium-containing crown ether bridged chiral heterotrinuclear salen Zn(II) complex BaZn2L(ClO4)2, where L is a folded dinuclear chiral (R,R)-salen ligand, has been synthesized and characterized by elemental analysis, 1H NMR, UV-vis, IR, circular dichroism (CD) spectra, and mass spectra. As a folded dinuclear chiral host, its recognition with achiral guests (imidazole derivatives), rigid bidentate guest (1,4-diazobicyclo[2,2,2]octane, DABCO) and chiral guests (amino acid methyl esters) was investigated by means of UV-vis spectrophotometric titration, CD spectra. The association constants of D-amino acid methyl esters are found to be higher than those of their L-enantiomer. The sandwich-type binding of BaZn2L(ClO4)2-DABCO supramolecular assembly was specially studied via 1H NMR titration and 1H ROESY. To understand the recognition on molecular level, density functional theory (DFT) calculations on B3LYP/LanL2DZ were performed on the minimal energy conformations of host, guests, and host-guest complexes. The minimal energy conformations were obtained by molecular mechanics (MM) optimization and molecular dynamics (MD) simulation. The results of single point energy, HOMO energy, and charges transfer were analyzed. The results of theoretical calculations are in good agreement with the experimental data.     

Theory on the molecular characteristic contour (II)--Molecular intrinsic characteristic contours of several typical organic molecules

The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary.     

μs级负充电时不同体积分数去离子水与乙二醇混合液电性能的实验研究

 以去离子水与乙二醇的混合液（体积分数分别为36.5%,48.7%,59.0%及71.2%，以下简称混合液）作为同轴传输线的绝缘介质，进行了μs级高电压负充电条件下的正电极击穿实验，研究了混合液的击穿电压、击穿时间、相对介电常数及电阻率与体积分数的关系。实验结果表明：在充电电压为20kV时，71.2%的混合液比36.5%的混合液的平均击穿电压提高25.1%，平均击穿时间延长10.49%，而相对介电常数减小868%。同时，随着充电时间的缩短，混合液的击穿电压提高。     

Structural and optical properties of CuSe2 nanocrystals formed in thin solid Cu–Se film

This paper describes the structural and optical properties of Cu–Se thin films. The surface morphology of thin films was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Formation of Cu–Se thin films is concluded to proceed unevenly, in the form of islands which later grew into agglomerates. The structural characterization of Cu–Se thin film was investigated using X-ray diffraction pattern (XRD). The presence of two-phase system is observed. One is the solid solution of Cu in Se and the other is low-pressure modification of CuSe₂. The Raman spectroscopy was used to identify and quantify the individual phases present in the Cu–Se films. Red shift and asymmetry of Raman mode characteristic for CuSe₂ enable us to estimate nanocrystal dimension. In the analysis of the far-infrared reflection spectra, numerical model for calculating the reflectivity coefficient of layered system, which includes film with nanocrystalite inclusions (modeled by Maxwell-Garnett approximation) and substrate, has been applied.     

由季戊四醇合成季戊四硫醇的新方法

以季戊四醇为原料,先合成四对甲苯磺酸季戊四醇酯,然后四对甲苯磺酸季戊四醇酯与硫氰酸钾在N,N-二甲基甲酰胺中加热反应,生成了2,3,7,8-四硫螺[4,4]壬烷,2,3,7,8-四硫螺[4,4]壬烷经四氢化铝锂还原、酸化,得到季戊四硫醇.产物结构经熔点、红外光谱、质子核磁共振谱、拉曼光谱鉴定.     

微分学中构造函数的新方法

结合实例将常微分方程中的首次积分和特征方程理论应用于微分学中函数的构造,从而使之有章可循.     

A robust spin-coated optical sensing device for rapid determination of predominant metal ions in wastewater streams

The potential of an optical sensing material for determination of metal ions in wastewater streams is presented. The initial results in the development of a chromo-ionophore-based optical sensor for metal ions are detailed. An azo dye species, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (BrPADAP), together with an ionophore and plasticiser was immobilised in a film of poly(vinyl chloride) (PVC). Initial investigations using the dye-impregnated sensing film showed a reproducible and reversible response to Pb(II) ions in aqueous solution. The response of this sensing film to Pb(II) at pH 6 was found to be linear in the 0.1-10 mg/L range, with a %RSD of 1.55%. The film can be regenerated by immersion in a low-pH buffer solution. The authors demonstrate how this method shows potential for analysis using once-off sensing probes. The sensing film response for Pb(II) occurs within 30 s.