Syntheses and Crystal Structures of Two New Macrocyclic Compounds

Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I > 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073 , the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I > 2σ(I).     

氯化1-(4-氨基丁基)-3-甲基咪唑离子液体电子结构性质研究

采用密度泛函理论方法 B3LYP/6-311++G(d,p)计算了氯化1-(4-氨基丁基)-3-甲基咪唑离子液体气相下几何构型、离子对结合能和二阶微扰稳定化能等。得到了8种不同的稳定结构,不同结构所具有的能量差异最大为11.1 kcal·mol~(-1)。能量最小稳定构型的氯化1-(4-氨基丁基)-3-甲基咪唑自然价键前线轨道分析结果表明:超共轭作用主要发生在咪唑环内,LP(1)N1→BD*(2)N4-C5电子离域引起的稳定化能达73.54 Kcal·mol~(-1)。氯阴离子和1-(4-氨基丁基)-3-甲基咪唑阳离子作用生成氯化1-(4-氨基丁基)-3-甲基咪唑时,轨道对称性匹配占主导作用,阴离子的HOMO轨道与阳离子具有更高能量的非占据σ*轨道相互作用,形成了σ型的C-H…Cl氢键。     

A Novel Tripyridyldiamine Nickel Complex:Synthesis,Structure and Characterization

A novel nickel(II)complex[Ni(H2 tpda)(NCS)2(CH3 OH)]was synthesized by using tripyridyldiamine as ligand and Ni(NCS)2 as starting materials,and characterized by a variety of techniques including single-crystal X-ray diffraction,IR spectroscopy and TG-DSC.The single-crystal structure reveals that the complex exhibits as a neutral molecule and that the central atom Ni(II)is octahedrally coordinated by an H2 tpda,two NCS-ions and a ligand molecule CH3 OH.The 3 D supramolecular network is formed through hydrogen bonds andπ-πinteractions.The complex can catalyze the addition reaction of carbon dioxide and propylene oxide.     

优化条件下过氧化氢降解壳聚糖的光谱学研究

在最佳反应条件下制备过氧化氢对壳聚糖的降解产物,通过测定原料及降解产物(Mw=1 500～166.53 kDa)的氮、碳含量,分析它们的红外光谱、核磁共振碳谱、X射线衍射谱及圆二色谱,考察各产物是否保持其天然结构。结果表明：各降解产物与原料的碳含量,氮含量及脱乙酰度的最大相对偏差分别为2.4%,2.3%与6.9%,且后两者随着反应时间的延长而减小;各降解样品的红外光谱及核磁共振碳谱与原料壳聚糖的相似,说明降解过程几乎不改变原料的化学结构;经相同方法处理过的原料及降解产物在2θ=10.4°和19.8°处均存在X射线衍射峰,在210 nm处均存在一个负的圆二吸收峰,表明产物的固态结构与其在溶液中的构象均没有发生变化。说明在优化的降解条件下过氧化氢氧化降解没有改变壳聚糖的天然结构。     

A Carboxylate-bridged Co(Ⅱ) Layer Complex: Synthesis,Structure and Magnetic Property

A 2D coordination polymer, [Co(NPA)(H_2 O)_2]_n(1, H_2 NPA = 3-nitrophthalic acid), has been synthesized by solvothermal method and characterized by single-crystal X-ray diffraction analysis, FT-IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. Complex 1 crystallizes in orthorhombic space group Pbca with a = 7.2261(2), b = 14.6450(5), c = 19.6671(7) ?, V = 2081.31(11) ?~3, Z = 8, C_8 H_7 CoNO_8, M_r = 304.08, D_c = 1.941 mg/m~3, μ = 1.686 mm~(-1), S = 1.054, F(000) = 1224, the final R = 0.0248 and wR = 0.0603 for 1834 observed reflections(I 2σ(I)). The crystal structural analysis demonstrates that the Co(Ⅱ) ions in 1 are linked by single and double μ_2-1,3-bridging carboxylate bridges, forming a 2D layer structure. Moreover, magnetic property of 1 was also discussed.     

Analysis of the Electronic Structure of 1-(4-Aminobutyl)-3-methylimidazolium Chloride via DFT Method

Density functional theory and natural bond orbital analysis are applied to study the microelectronic structural properties of 1-(4-aminobutyl)-3-methylimidazolium chloride(C_4NH_2C_1imCl). We obtain 48 stable cation conformers at the B3LYP/6-311++G(d, p) level of theory. When the Cl anion is located at different positions around the two stable cation conformers,optimization and frequency are calculated at the same level of theory, and seven stable C_4NH_2C_1imCl structures are obtained. Ion-pair association energies, natural population analysis(NPA) charges, and the second-order stabilization energies are also calculated. Results show that three energy-degenerated states are present in seven conformers. The calculated ion-pair association energy, NPA charges, and second-order stabilization energy values are the same as those with the same energy level conformers. Finally, H bond formation in the molecule is analyzed by the interactions of frontier molecular orbitals. The lone pair of N(11) atom in the amino group exhibits higher reactivity than that of the N(4) atom in the ring.     

相依人群中联合基因型概率分析

考虑相依人群中任意选择的 n个个体之间的所有可能的同源遗传关系 ,定义了相应的δ概率以及它们之间的乘积运算 ,提出了基本基因型概念 ,得到了这 n个个体的联合基因型概率分布公式 .具体研究了 3个个体的所有同源遗传关系 ,给出了所有的δ概率 ,α概率 ,δ概率与α概率的关系 ,以及分别用δ概率和α概率表示的联合基因型概率分布公式 ,并在进化平衡状态下得出了所有的δ概率与θ概率之间的关系 .