吡啶酮系偶氮类化合物可见吸收光谱的预测

利用密度泛函的B3LYP方法, 在6-311G*基组水平对吡啶酮系偶氮类化合物进行构型优化, 并进行了自然键轨道(NBO)分析, 然后用TDDFT方法和ZINDO/S方法分别计算了它们的可见吸收光谱, 结果均与实验值十分吻合. 通过对比发现, 对于最高吸收波长的计算, ZINDO/S能以较快的速度得到较好的结果. 在用ZINDO/S计算的过程中, 回归分析发现π-π重叠加权因子(OWF_π-π)与染料分子吡啶环上两个羰基氧原子平均电荷Z_O有较好的线性关系: OWF_π-π＝0.11425－1.04178ZO, 这一关系不仅可从量子化学的角度进行解释, 而且可用于同类染料可见吸收光谱的预测. 分子轨道的研究表明, 这些化合物的最高可见吸收波长主要对应着共轭体系中给电子体到受电子体的电子跃迁.     

Structure and magnetic properties of Ca14MnP11

The compound Ca₁₄MnP₁₁ crystallizes in the Ca₁₄AlSb₁₁ structure type with the tetragonal space group I4₁/acd (Z=8) and lattice parameters of , c=20.7565(9) at 90 K. The structure consists of MnP₄⁹⁻ tetrahedron, P₃⁷⁻ trimer, 4 P³⁻ isolated anions and 14 Ca²⁺ cations. Similar to other compounds of this structure type containing phosphorous, the P₃⁷⁻ trimer has a central P atom that is best modeled in the structure as being equally split between two sites. In addition, there is no additional distortion of the manganese-containing tetrahedron compared with the main group analog, Ca₁₄GaP₁₁, suggesting that the Mn oxidation state is Mn²⁺. Temperature-dependent magnetic susceptibility shows that the compound is paramagnetic over the entire temperature range measured (2-300 K). The data can be fit with a modified Curie-Weiss law and provide an effective magnetic moment of 5.80 (2) B.M. with a Weiss constant of −2.13(2) K and . This moment is significantly higher than those measured for any of the Mn-containing analogs and is consistent with Mn²⁺. This result will be discussed in light of the electron counting scheme for Mn compounds of the Ca₁₄AlSb₁₁ structure-type.     

The Biological Effects of Forsythia Leaves Containing the Cyclic AMP Phosphodiesterase 4 Inhibitor Phillyrin

Forsythia fruit (Forsythia suspensa Vahl (Oleaceae)) is a common component of Kampo medicines for treating the common cold, influenza, and allergies. The main polyphenolic compounds in the leaves of F. suspensa are pinoresinol β-d-glucoside, phillyrin and forsythiaside, and their levels are higher in the leaves of the plant than in the fruit. It is known that polyphenolic compounds stimulate lipid catabolism in the liver and suppress dyslipidemia, thereby attenuating diet-induced obesity and polyphenolic anti-oxidants might attenuate obesity in animals consuming high-fat diets. Recently, phillyrin was reported as a novel cyclic AMP phosphodiesterase 4 (PDE4) inhibitor derived from forsythia fruit. It was expected that the leaves of F. suspensa might display anti-obesity effects and serve as a health food material. In this review, we summarized our studies on the biological effects of forsythia leaves containing phillyrin and other polyphenolic compounds, particularly against obesity, atopic dermatitis, and influenza A virus infection, and its potential as a phytoestrogen.     

Cathodic materials for lithium-ion batteries based on spinels Li x Mn2−y Me y O4: Synthesis, phase composition, and structure of Li x Mn2−y Cr y O4 at x = 1.0−1.2 and y = 0−0.5

Extralithiated chromium-doped finely divided lithium-manganese spinels are synthesized as a result of a two-step solid-phase process with use made of the fusion-saturation method. The spinels are intended for application as cathodic materials in lithium-ion batteries. The phase composition and structural characteristics of samples of cathodic materials of the type Li _x Mn_2?y Cr _y O₄ are studied. The samples with x = 1.0?1.2 and y = 0?0.5 are characterized by phase purity and cubic syngony with parameter a = 0.817?0.823 nm and a disperseness equal to 1–2 nm. The maximum content of chromium and lithium in Li _x Mn_2?y Cr _y O₄ that does not lead to violation of cubic syngony is determined. Lithium excess in the cathodic material that does not exceed 0.2 formula units may be used for compensating the irreversible capacity. Replacing some manganese atoms by chromium may facilitate retention of the structures’s integrity in the course of cycling.     

Possibilities of nitric acid preparation of powder cellulose forms

For preparation of various modified forms of microcrystalline cellulose, an optional combination is proposed of hydrolytic activity with other properties of nitric acid such as, adduct forming ability (manifested as Knecht compound formation), oxidizing, bleaching and nitrating. The manifestation of a chosen acid function is reached by variation of the reaction conditions: concentration, temperature, time, etc. The sole-reagent continuous procedure involving several operations made in a predetermined sequence allows the use of a more simple technological scheme and saves energy, time and materials. The features of transformation of fibrous and microcrystalline forms of native cellulose into cellulose-II through the Knecht compound are discussed. Purely acidic transformation schemes of native cellulose into microcrystalline cellulose hydrate and amorphous low-nitrate powder cellulose according to the above scheme are considered. Morphological features as well as distinguishing properties — enhanced hydrophilicity, sorption activity and degree of whiteness — of the prepared materials are pointed out. The possibility of obtaining uniformly oxidized forms of powder cellulose according to this scheme and the outlook for the use of nitrogen(IV) oxide as a multifunctional reagent are discussed.     

固相萃取-气相色谱-高分辨质谱法测定巢湖水中半挥发性有机化合物

描述了巢湖水中半挥发性有机化合物的提取、测定过程和初步结果。湖水中半挥发性有机化合物的提取采用XAD-2和XAD-4混合树脂富集，用气相色谱-高分辨质谱法测定了所萃取的有机化合物，并给出相应的分子式和结构式。春季湖水中检测到14种有机化合物。     

Crystal and Molecular Structure of 3，4－diphenyl－5－ethyl－5－methyl－1，3，4－diazaphospholidin－2－thione－4－oxide

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆ３，４－ｄｉｐｈｅｎｙｌ－５－ｅｔｈｙｌ－５－ｍｅｔｈｙｌ－１，３，４－ｄｉａｚａｐｈｏｓｐｈｏｌｉｄｉｎ－２－ｔｈｉｏｎｅ－４－ｏｘｉｄｅ￥ＦｅｎｇＫｅ－Ｓｈｅｎｇ；ＣｈｅｎＲｕ－Ｙｕ（Ｉ...     

Synthesis and characterization of ionic organotin compounds [R2SnCl2(2-quin)](HNEt3) and crystal structures of [(2,4-Cl2-C6H3CH2)2SnCl2(2-quin)](HNEt3)

Eight ionic organotin compounds [R₂SnCl₂(2-quin)]⁻(HNEt₃)⁺ have been synthesized by reactions of 2-quinH with R₂SnCl₂ (R = PhCH₂1, 2-Cl-C₆H₄CH₂2, 4-Cl-C₆H₄CH₂3, 2-F-C₆H₄CH₂4, 4-F-C₆H₄CH₂5, 4-CN-C₆H₄CH₂6, Ph 7, 2,4-Cl₂-C₆H₃CH₂8) in the presence of organic base NEt₃, and their structures have been characterized by elemental analysis, IR and multinuclear NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. The structure of [(2,4-Cl₂-C₆H₃CH₂)₂SnCl₂(2-quin)]⁻(NEt₃)⁺ (8) has been determined by X-ray diffraction study. Studies show that compound 8 has a monomeric structure with the central tin atom six-coordinate in a distorted octahedral configuration and the nitrogen atoms of the 2-quin ligands are coordinating to the tin atom in all the eight compounds.     

A novel microwave dielectric ceramic Ca2Zn4Ti16O38: Preparation and dielectric properties

A novel microwave dielectric powder with composition of Ca₂Zn₄Ti₁₆O₃₈ was synthesized through a citrate sol-gel process. The development of crystalline phases with heat-treating temperature for the gel derived powders was evaluated by using thermo-gravimetric analysis and X-ray powder diffraction analysis techniques. The pure phase of Ca₂Zn₄Ti₁₆O₃₈ with crichtonite crystal structure was obtained at relatively low temperature of 1000 °C. The synthesized powder has high reactivity and the dense ceramics with single crystalline phase were obtained at low sintering temperature of 1100 °C. Impedance spectroscopy and microwave dielectric measurements on sintered samples showed the present compound to be a modest dielectric insulator with excellent dielectric properties of ε_r∼47-49, Qf value ∼27,800-31,600 GHz and τ_f∼+45 to +50 ppm/°C. It shows comparable microwave dielectric properties to other moderate-permittivity microwave dielectrics, but much lower sintering temperature of 1100 °C.     

Synthesis and crystal structure of inclusion compounds: Trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid with boric acid and tetrabutylammonium salt

Two new inclusion compounds (n-C₄H₉)₄N⁺C₁₈-H₁₃O₄ ⁻·B(OH)₃ (1) and (n-C₄H₉)₄N⁺C₁₈H₁₃O₄ ⁻ (2) were prepared and characterized by X-ray crystallography. Crystal data: compound 1, monoclinic P2(1)/c, a = 1.569 9(1) nm, b = 0.995 5(6) nm, c = 2.293 3(1) nm, β = 109.962(3)°, Z = 4, and R ₁ = 0.0434, wR = 0.075 9; compound 2, monoclinic C2/c, a = 1.400 5(3) nm, b = 1,282 1(2) nm, c = 1.765 7(3) nm, β = 100.388(1)°, Z = 4, and R ₁ = 0.0584, wR = 0.096 6. In the crystal structure of 1, the tetramers formed by two trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (EADA) anions and two boric acid molecules were connected through O—H⋯O hydrogen bonds to generate a channel type host lattice. The tetra-n-butylammonium cations were stacked to give two columns within each channel with cross-sectional size of about 2.30 nm × 0.93 nm. In the crystal structure of 2, similar honeycomb host lattices with big size were also formed along the [101] direction by three-dimensional accumulation of EADA anions. The tetra-n-butylammonium cations were accommodated in a zigzag fashion within each channel. Translated from Acta Chimica Sinica, 2006, 64(18): 1904–1910 [译自: 化学学报]