Dinuclear and heteropolynuclear complexes containing Mo2(4+) units

The quadruply bonded compound Mo2(DpyF)4 (1), where DpyF- is the anion of N,N'-di(2-pyridyl)formamidine, has been prepared by ligand substitution reactions of Mo2(OOCCF3)4 and either the neutral ligand, HDpyF, at ambient temperature or its lithium salt, LiDpyF, under refluxing conditions. An X-ray structural analysis shows that 1 has a paddlewheel structure with a [symbol: see text] distance of 2.1108(6) A. Reaction of 1 with CoCl2 in methanol produces the paramagnetic compound [Mo2Co(DpyF)4][CoCl4].2MeOH (2). The Co(II) atom in the cation [Mo2Co(DpyF)4]2+ resides on a low-spin hexacoordinate environment (S = 1/2) with a Co...Mo separation of 2.979(6) A, suggesting there is no direct bonding interaction between the Co and Mo atoms. The Mo-Mo distance of 2.1096(5) A is similar to that in 1. Reaction of 1 and CuCl in methanol yields [Mo2Cu4(DpyF)4Cl2][CuCl2]2.2MeOHxEt2O (3). In the cation there are two copper atoms on each side of the Mo2 core. Each is coordinated to two pyridyl nitrogen atoms of the cis DpyF- ligands and loosely bridged to the other by a chloride ion. As a result, the Cu(I) atoms are not aligned with the Mo2 unit. The Cu to Mo separations are in the range 3.003(1)-3.015(1) A, and the Mo-Mo distance of 2.127(1) A is comparable to those in 1 and 2.     

Prediction of paper permanence by accelerated aging II. Comparison of the predictions with natural aging results

Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.     

Copper(II) and nickel(II) complexes of 2-formylpyridine 3-piperidinyl-, 3-hexamethyleneiminyl- and 3-azabicyclo[3.2.2]nonylthiosemicarbazones

Summary Copper(II) and nickel(II) complexes of 2-formylpyridine 3-piperidinyl-, 3-hexamethyleneiminyl- and 3-azabicyclo-[3.2.2]nonylthiosemicarbazones were prepared and characterized spectroscopically. ¹H and ¹³C n.m.r. spectra of the thiosemicarbazones and a diamagnetic nickel(II) complex are reported, together with i.r., electronic and e.s.r. spectra of the metal complexes. The thiosemicarbazones and their copper(II) and nickel(II) complexes exhibit considerable growth inhibitory activity against Paecilomyces variotii, but show minimal activity against Aspergillus niger.     

VISCOELASTIC BEHAVIOR OF THE NON-HOOKE DEFORMATION BEFORE YIELDING IN UNIAXIAL DRAWING OF AMORPHOUS POLY(ETHYLENE TEREPHTHALATE)*

Viscoelastic behavior of the non-Hooke deformation of amorphous PET film before yield was investigated in thetemperature region 74--80.5℃ around the glass transition temperature. The film specimen was drawn to yield point followedby unloading to zero stress, then the residual deformation was held constant, while the subsequent evolution of the stress wasrecorded. An induction period was found in the course of stress evolution fol1owed by a stress step-increase. The inductionperiod decreases with increasing drawing temperature with an activation energy of 1.10 MJ/mol·K, which is attributed tothe time needed for the relaxation of rubbery deformation through cooperative internal rotations. At temperatures lower than74℃, there is no stress increase or the induction period becomes too long to be observed. Thus the nature of anelasticity inthe non-Hooke region before yielding is attributed to stress induced rubbery deformation. The experimental results areinterpreted in terms of Perez' rheological model of a series connected Hooke spring and a Voigt element consisting of aparallel connected elastic spring and a dashpot.     

On-column amperometric detection in capillary electrophoresis with an improved high-voltage electric field decoupler

The analysis of polyamide-6 oligomers and polymer is usually performed with expensive fluorinated alcohols like 2,2,2-trifluoroethanol (TFE) or 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). Formic acid is well known as a mobile phase additive to adjust pH in reversed-phase high-performance liquid chromatography. However, formic acid is seldom used as a modifier to perform gradient elution chromatography on octadecyl-modified silica-based columns. Here we demonstrate the determination of cyclic and linear polyamide-6 oligomers using formic acid as a modifier on an octadecyl-modified silica-based column. This column was shown to be stable for more than 5000 column volumes, even when a mobile phase of 65-95% formic acid in water at a flow of 1 ml/min is applied. With formic acid under the conditions used (65-95% formic acid in water) the oligomers are retained on the column, while the polymer does not precipitate. In comparison, during adsorption and separation with a HFIP gradient, precipitation of the polymer occurs. The implications of the different separation mechanisms, i.e., adsorption vs. precipitation chromatography are discussed. Loadability is shown to be much better with the formic acid system. However, with formic acid as a modifier UV detection below 250 nm is not feasible. The less sensitive evaporative light scattering detector is used to detect the polyamide oligomers in the formic acid phase. In addition it is shown that capillary zone electrophoresis (CZE) with UV-absorbance detection using HFIP is an attractive combination as HFIP is UV-transparent and CZE allows low modifier consumption.     

New alternating ferro- and antiferromagnetic one-dimensional complexes. Synthesis, characterization, crystal structure, and magnetic properties of

The preparation, X-ray crystal structure, and magnetic properties of alternating 1,1- and 1,3-azido-bridged copper(II) complex [Cu(4,4'-dmbpy)(N3)2]n (1, 4,4'-dmbpy = 4,4'-dimethylbipyridine) have been reported. It crystallizes in triclinic system, space group P1, a = 7.9903(1) A, b = 9.3545(9) A, c = 10.754(2) A, alpha = 113.485(1) degrees, beta = 101.399(1) degrees, gamma = 101.897(1) degrees, Z = 2. The magnetic properties of 1 have been investigated in the temperature range 1.5-300 K. Alternating antiferromagnetic (-J = 191.0 cm(-1)) interaction through a 1,3-N3- bridge and ferromagnetic (J = 297.1 cm(-1)) interaction through a 1,1-N3- bridge are obtained for 1 by analyzing the magnetic susceptibility data with the Hamiltonian H = -Jsigma(S2iS2i-1--alphaS2iS2i+1). It's derivatives ([Mn(4,4'-dmbpy)(N3)2]n (2), [Ni(4,4'-dmbpy)(N3)2]n (3), and [Fe(4,4'-dmbpy)(N3)2]n (4) and the heterometallic derivatives [NiMn(4,4'-dmbpy)2(N3)4]n (5) and [CuMn(4,4'-dmbpy)2(N3)4]n (6) have also been synthesized and characterized by electronic and IR spectra. The X-ray powder diffraction and the magnetic properties of 6 have also been discussed.     

Preparation and Characteristics of Porous Silica Films by a Modified Base-Catalyzed Sol-Gel Process Containing PVA: II. Film Preparation

Porous SiO₂ films were successfully deposited on silicon substrates by a modified base-catalyzed Sol-Gel process (MBCP) containing polyvinyl alcohol (PVA). The process conditions, such as the gelation time, the synthesis temperature, the stabilizing agent of the precursor solution and the spin coating speed, the heat-treatment, the annealing temperature of the film on the microstructure and porosity of porous SiO₂ films were systematically investigated by SEM, XRD and ellipsometry techniques. This study provides a novel preparation technique for the porous SiO₂ film. Using this process, the resultant film can reach a thickness of 3.6 m for one layer, a porosity of 25–50%, a low thermal conductivity of 0.11 W/m·K. This film will be used as a low dielectric layer, an thermal-insulating layer and a low refractive index layer.     

毛细管电泳-单链构象多态性分析检测K-ras基因突变

K ras癌基因的点突变在结直肠癌的发生起重要作用。以异丙醇为聚合反应链转移剂,水相法合成 特性粘度为0.70×10-3m3/kg,分子量为6.5×104的低粘度短链线性聚丙烯酰胺。以6%线性聚丙烯酰胺为 筛分介质,分离温度27℃,分离电压9kV为电泳条件,建立了检测K ras基因突变的毛细管电泳 单链构象多 态性方法。利用该方法检测36例结直肠癌患者肿瘤组织,发现12例K ras基因突变。结果表明:该方法具有 快速、高灵敏的优点,为大规模进行结直肠肿瘤的早期诊断提供了可靠方法。     

Ln(η6-m-C6H4Me2)(AlCl4)3, (Ln=Pr,Er)的合成及Pr配合物的晶体结构

LnCl₃(Ln=Pr,Er)与AlCl₃在二甲苯中反应，合成了η⁶-(m-Me₂C₆H₄)Ln(AlCl₄)₃这两个新配合物并对其进行了元素分析、红外光谱和质谱的表征。测定了Pr配合物的晶体结构。该配合物具有扭曲的五角双锥几何构型。二甲苯和一个氯原子处于两个顶点，Pr配合物属单斜晶系，空间群P相似文献   

杨村烟煤与石油渣油共处理反应特性的研究

用共振搅拌反应器研究了山东兖州杨村的烟煤与北京燕山石化公司的石油渣油共处理液化的反应过程，考察了反应温度和反应时间对煤液化转化率及产物中前涸青烯，苯可溶组分的影响。