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61.
HUANG Xi-He SHENG Tian-Lu XIANG Sheng-Chang FU Rui-Biao HU Sheng-Min LI Ya-Min WU Xin-Tao ② 《结构化学》2007,26(3):333-337
The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of Cd(NO3)2 affords a novel 2D cadmium tetrazolyl-benzoate,{Cd(tzbz)(H2O)}n (H2tzbz is 2-(5-tetrazolyl)-benzoate). The tzbz ligand is generated in situ through the 2+3 Sharpless cycloaddition reaction and hydrolyzation. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the orthorhombic system,space group Pbca with a=9.6659(19),b=7.6366(15),c=25.964(5) ,V=1916.5(7) 3,Z=8,Mr=318.57,Dc= 2.208 g/cm3,F(000)=1232 and μ=2.276 mm-1. The Cd(Ⅱ) atom is coordinated by four tzbz ligands and one water molecule to form a severely distorted pentangle bipyramid. While each tzbz ligand connects to four Cd(Ⅱ) atoms in a μ4-η1,η2,η1,η1,η1 coordination mode to construct a 2D architecture of the title complex. Additionally,the title complex exhibits strong fluorescence at room temperature in the solid state. 相似文献
62.
Using geometry optimization and DFT method at the B3LYP/6-31G* level of theory for C30H20, an equilibrium geometry is identified that has the form of polyhedral hydrocarbon with five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage. Thus, this molecule is a tri-cage molecule with two pentaprismane cages and one dodecahedrane cage. Vibrational frequencies and the infrared spectrum are computed at the same level of theory. The heat of formation for C30H20 has been estimated in this paper. The heat of formation of C30H20 as well as the vibrational analysis indicates that this molecule enjoys sufficient stability to allow for its experimental preparation. 相似文献
63.
Rui Yan Li Zhi Ru Li Di Wu Xi Yun Hao Ru Jiao Li Chia Chung Sun 《International journal of quantum chemistry》2005,103(2):157-166
Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH2O? HF, CH2O? H2O, CH2O? NH3, and CH2O? CH4. The structures of CH2O? HF, CH2O? H2O, and CH2O? NH3 are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH2O and lone pair(s) on the F atom in HF, the O atom in H2O, or the N atom in NH3. In contrast with the above three dimers, for CH2O? CH4, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH2O? CH4 is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
64.
Ion/molecule reactions were explored in a newly developed miniature mass spectrometer fitted with a rectilinear ion trap (RIT) mass analyzer. The tandem mass spectrometry performance of this instrument is demonstrated using collision induced dissociation (CID) and ion/molecule reactions. The latter includes Eberlin transacetalization reactions and electrophilic additions. Selective detection of the chemical warfare simulant dimethyl methyl phosphonate (DMMP) was achieved through selective Eberlin reactions of its characteristic phosphonium fragment ion CH3OP(+)(O)CH3 (m/z 93), with 1,4-dioxane or 1,3-dioxolane. Efficient adduct formation as a result of electrophilic attack by the phosphonium ion on various nucleophilic reagents, including 1,1,3,3-tetramethyl urea, methanesulfonic acid methyl ester, dimethyl sulfoxide and methyl salicylate, was also observed using the RIT device. The product ions of these reactions were analyzed using CID and the characteristic fragmentation patterns of the ionic addition products were recorded using multiple-stage experiments in the miniature RIT instrument. This study clearly demonstrates that a small, home-built, miniature RIT mass spectrometer can be used to perform analytically useful ion/molecule reactions and also that instruments like this have the potential to provide a portable platform for in situ detection of organophosphorus esters and related compounds with high specificity using tandem mass spectrometry. 相似文献
65.
为将生物体内微观的蛋白行为可视化并以宏观信号呈现出来对蛋白进行实时、动态分析,借助SNAP-tag蛋白标签技术与有机小分子荧光染料,构建了一系列用于活细胞内实时监测目标蛋白的免洗荧光探针。标签蛋白SNAP-tag能够特异性识别探针中的苄基鸟嘌呤,从而使目标蛋白共价连接上荧光团(萘酰亚胺),携带上荧光信使。此外,由于萘酰亚胺从水环境中被牵引至SNAP-tag蛋白的疏水空腔,其荧光信号呈现出2~13倍的增强。通过SNAP-tag标签蛋白与目标蛋白的融合,该荧光探针实现了对活细胞内线粒体蛋白CoX8A及核内蛋白H2B特异性识别,在免洗条件下完成了对目标蛋白的实时追踪及原位分析。 相似文献
66.
67.
68.
With P(CH3)3 as the probe molecule adsorbed on titanium silicalite (TS-1) zeolite, the special and important role of T12 site in MFI-type zeolite was clearly elucidated. There are altogether three active sites present in TS-1 zeolite with Ti at the T12 site. Owing to the preferential adsorption of probe molecules on the first Brönsted acidic site, the Ti12 center will probably fail to show Lewis acidity. The ionic [HP(CH3)3]+ species can be stabilized by the first or second Brönsted acidic site, with the former energetically favored. The latter was formed through the transfer of the ionic [HP(CH3)3]+ species from the first to the second Brönsted acidic site. 相似文献
69.
von Niessen Wolfgang Cederbaum Lorenz S. Kraemer Wolfgang P. 《Theoretical chemistry accounts》1977,44(1):85-93
The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C3H6 the ordering of the ionization potentials is 2e(), 1e(), 2a1(), 1a2(), 1e(). The assignment of the 2a1 and the 1a2 ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C2H4O the ordering of the ionization potentials is 2b
1(), 4a
1, 1a
2(), 2b
2,3a
1, 1b
1(), 1b
2, 2a
1 and for C2H5N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory. 相似文献
70.
N. S. Mosyagin A. V. Titov R. J. Buenker H.‐P. Liebermann A. B. Alekseyev 《International journal of quantum chemistry》2002,88(5):681-686
Multireference single‐ and double‐excitation configuration interaction (MRD‐CI) calculations of transition energies for the Hg atom and spectroscopic constants for the HgH molecule are carried out with the generalized relativistic effective core potential (GRECP) method. A new selection criterium for the reference configurations is discussed. The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Improvement of accuracy is mainly observed for bond lengths from the GRECP/MRD‐CI calculations (without applying the T = 0 correction) with respect to the results of other groups. Analysis of the quality of the approximations employed is carried out. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献