[Co(3,3-tri)(amp)Cl][ZnCl4]一对邻位差向异构体的晶体结构

The crystal structures of a pair isomers of [Co(3,3-tri)(amp)Cl][ZnCl₄] (here 3,3-tri = N-(3-Aminoprop- yl)-1,3-propanediamine; amp=2-(Aminomethyl)pyridine) have been determined by single crystal X-ray diffrac-tion. They are the epimers with the only difference of the orientation of the Sec-NH proton in 3,3-tri ligand. The crystals with the anti-epimer (m1[ZnCl₄]·CH₃OH·H₂O) are monoclinic, space group C2/c with eight molecules in a unit cell of dimensions a=30.401(5)?,b=8.0469(13)?,c=18.817(3)?,β=93.346(3)°,V=4595.3(12)?³,D_c=1.708g·cm^-3,Z=8,F₀₀₀=2416,R=0.0462,R_w=0.1304. The crystals of the syn-epimer (m2[ZnCl₄]·H₂O) are triclinic, space group P1 with two molecules in a unit cell of dimensions a=8.9752(12)?,b=9.8855(12)?,c=12.6886(16)?,α=89.228(3)°,β=76.447(2)°,γ=80.428(3)°,V=1078.8(2)nm³,D_c=1.721g·cm^-3,Z=2,F₀₀₀=568,R=0.0313,R_w=0.0929. The crystal parameters, such as bond lengths and angles, are well consistent with the data of an ab initio computational result (RHF/LANL2DZ opti-mised structure). The average error for bond length is about 1.6%, only two of them in the isomer m3 (Co-N2 and Co-N4) are over 3%, (3.09% and 4.28% respectively). The errormax for bond angle is 2.52%, the bond angles with an over 2% error are only 3.6% out of all bond angles.     

环状芴基张力半导体拉曼光谱理论与实验研究

环状芴基张力半导体由于其特殊的分子结构，发射状排布的p轨道和纳米级空腔等诸多特点，引起了科学家广泛的关注.相对于直链型芴基半导体，环状芴基张力半导体展现出独特的光电性质.然而，迄今为止其振动性质没有被报道.对四元环芴的晶体与直链四聚芴粉末样品进行拉曼光谱表征和归一化处理，并结合理论计算.结果表明，与直链寡聚芴相比，环芴类似于碳纳米管的G峰发生了偏移，并且低频区域拉曼频移峰的峰强增加.其原因是由于张力的引入，改变了芴基主链的骨架和电子结构，加强芴骨架上π电子离域，同时使环芴中每个芴单元都参与到振动中.该研究结果为芴基张力半导体材料拉曼光谱的研究提供了一定的工作基础.     

Quantum chemistry study on B32 and B32H2–32

The structures of B32 and B₃₂H^2–₃₂ with I_h symmetry have been investigated by means of ab initio calculations at STO-3G level. The relationship between molecular orbitals of them has been analyzed and their bonding properties have been discussed. Then the possibility of their existence, as well as the similarity and difference between B₃₂ (B₃₂H^2–₃₂) and C₆₀ (C₆₀H₆₀) have been inferred.     

取代基对氮和氧自由基稳定性影响的理论研究

用MNDO方法，全构型优化，研究了15个氮自由基4-RC6H4NH，和15个氧自由基4-RC6H4O（R＝－H；－OCH3，－Cl，－F，－CN，－COCH3，－NO2，－CH3，－CF3，－SCH3，－C6H5，－Nh2，－BH2，－PH2，－SiH3）的稳定化能．结果表明：－NH2，－CH3，－OCH3，－F基团对自由基起稳定化作用，－CF3，－NO2；－CN，－COCH3，－BH2基团对自由基起去稳定化作用．苯基对氧自由基有较大的稳定化作用，而对氮自由基的稳定性影响较小．－SCH3，－PH2，－SiH3，－Cl基团表现弱的去稳定化作用．计算和实验结果基本相符．     

基于近红外光谱的维生素C片无损鉴别分析

基于近红外光谱技术与化学计量学方法,建立了一种国内外不同品牌维生素C片的无损鉴别方法。采集了国内外8个品牌的维生素C片共计40个样本的近红外光谱数据,比较了完整样品以及粉末样品的近红外光谱,采用连续小波变换技术消除背景干扰和基线漂移,基于标准偏差与相对标准偏差的变量筛选方法筛选出具有代表性的波数点,结合主成分分析方法对国内外不同品牌维生素C片进行鉴别分析。结果表明:原始光谱存在着明显的背景干扰和基线漂移现象,且粉末样品的重现性要优于完整样品;单纯使用原始光谱无法辨别来自不同品牌的维生素C片;连续小波变换可以有效消除背景干扰,提高模型鉴别能力;完整样品的鉴别准确率优于粉末样品,说明国内外不同品牌维生素C片主要成分基本一致,可能是辅剂和工艺上存在细微差异。通过结合近红外光谱分析技术与化学计量学方法,可实现对国产以及进口不同品牌维生素C片的鉴别分析。     

A Quantum Chemical Study of N14 Cluster

Ab initio molecular orbital theory and density functional theory have been employed to study N₁₄ cluster with low spin at the HF/6-31G*, B3LYP/6-31G*, B3PW91/6-31G*, BP86/6-31G*, and BHLYP/6-31G* levels of theory. Twelve isomers were studied, including one previously investigated cage molecule. The most stable isomer of N₁₄ is a C _2h -symmetric molecule that contains two separated five-membered nitrogen rings connected by a —N=N—N=N— bridge. The second, third, and fifth most stable isomers each have one five-membered nitrogen ring. The theoretical results suggest that the five-membered nitrogen ring gives rise to a particularly stable structural unit, and the more side chains that the five-membered nitrogen ring links with, the less stable the structure will become.     

Theoretical study of initiated reaction mechanism of polymerization of maleic anhydride catalyzed by OH−1 anion

A theoretical study of the polymerization reaction mechanism of maleic anhydride (MA) initiated by hydrate is presented. The reaction pathway has been studied with the density functional theory (DFT) method at the B3LYP/6‐311G** level. The geometrical parameters of transition states (TS) are optimized; intrinsic reaction coordinate (IRC) calculations have also been performed to obtain further credible features. Frequency analyses of all the stationary points are calculated at the same basis sets. The total energies of all geometries are corrected at second‐order Møller–Plesset (MP2)/6‐311G**. Calculation results reveal that the reaction mechanism is attributable to anion polymerization. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Preparation and Crystal Structures of 4-(4′-Pyridylthio)-1-methylpyridinium Salts: Assembly of a Donor-Acceptor-Type Molecule Containing a Sulfide Bridge

A series of ionic 4-(4′-pyridylthio)-1-methylpyridinium salts with different counteranions (1, I⁻; 2, BF⁻₄; 3, PF⁻₆; and 4, OTf⁻, where OTf=trifluoromethanesulfonate) have been prepared. Structural analysis reveals that the cation exhibits a variety of stacking structures dependent on the anion. Compound 1 crystallizes in space group P2_1/n (#14), with a=10.764(3) Å, b=9.601(5) Å, c=13.105(3) Å, β=108.35(2), V=1285.4(8) ų, and Z=4. In this compound, each cation moiety is stacked in a helical arrangement along the c-axis. Compound 2, which is isomorphous to 1, has space group P2_1/n (#14), with a=11.647(2) Å, b=9.203(3) Å, c=13.232(2) Å, β=108.42(2), V=1345.6(5) ų, and Z=4. Compound 3 crystallizes in space group P2_1/n (#14), with a=8.06(1) Å, b=17.43(1) Å, c=10.30(1) Å, β=103.0(1), V=1410(3) ų, and Z=4. In this salt, the cation molecules assume a head-to-tail stacking arrangement, forming a polar pseudo 1-D chain. Compound 4 crystallizes in space group Pb? (#2), with a=7.585(4) Å, b=15.443(7) Å, c=6.775(4) Å, α=99.33(4), β=108.35(2)^o, γ=98.37(4), V=756.6(7) ų, and Z=2. The structure of 4 consists of a columnar stacking of pyridine moieties, with the cation moieties surrounded by the counteranions. Calculations show that the 4-(4′-pyridylthio)-1-methylpyridinium cation may be a good building block for second harmonic generation (SHG) materials, even though salts 1-4 crystallized in centrosymmetric structures and were SHG inactive.     

{\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 Processing of non-isothermal TG data \par }

Decomposition of dichlorodifluoromethane in thermal plasma was investigated theoretically by computing the equilibrium composition of the gas mixtures involving carbon, chlorine and fluorine in presence of argon (which is assumed to be the main plasma gas) and/or in addition of hydrogen and calcium together with hydrogen. The calculations were carried out for the temperature range between 500 and 6000 K and for the total pressure of the system of 1 bar. Use is made of the fact that a thermal plasma is a plasma in (local) thermal equilibrium, which makes possible the theoretical determination of its equilibrium composition at definite temperature by employing Gibbs free energy data for the compounds present in the system and assuming that the equilibrium of the system corresponds to its minimum energy state. The results of calculations show that toxic molecules and radicals can be, under convenient conditions (appropriate temperature and amount of added substances), converted into stable non-toxic species like CaF₂ and CaCl₂.     

Toward direct determination of conformations of protein building units from multidimensional NMR experiments. V. NMR chemical shielding analysis of N-formyl-serinamide,a model for polar side-chain containing peptides

Knowledge of chemical shift-structure relationships could greatly facilitate the NMR chemical shift assignment and structure refinement processes that occur during peptide/protein structure determination via NMR spectroscopy. To determine whether such correlations exist for polar side chain containing amino acid residues the serine dipeptide model, For-L-Ser-NH(2), was studied. Using the GIAO-RHF/6-31+G(d) and GIAO-RHF/TZ2P levels of theory the NMR chemical shifts of all hydrogen ((1)H(N), (1)H(alpha), (1)H(beta1), (1)H(beta2)), carbon ((13)C(alpha), (13)C(beta), (13)C') and nitrogen ((15)N) atoms have been computed for all 44 stable conformers of For-L-Ser-NH(2). An attempt was made to establish correlation between chemical shift of each nucleus and the major conformational variables (omega(0), phi, psi, omega(1), chi,(1) and chi(2)). At both levels of theory a linear correlation can be observed between (1)H(alpha)/phi, (13)C(alpha)/phi, and (13)C(alpha)/psi. These results indicate that the backbone and side-chain structures of For-L-Ser-NH(2) have a strong influence on its chemical shifts.