甲烷在二元碱土金属复合体系催化剂上的氧化偶联

碱土金属氧化物或碳酸盐为多种类型甲烷氧化偶联制取C_2烃催化剂的重要组分之一.有关纯碱土金属氧化物及含氧酸盐的研究表明,这类化合物具有较强的表面碱性及高温P型半导性而对活化甲烷生成C_2烃有较高活性,关于不同碱土金属化合物之间混合形成的二元碱土金属复合体系催化剂的报导仍不多见,Aika等人曾报导用BaO与CaO或MgO混合的催化剂上在1073K时可以获得61.1%C_2烃选择性和14.2%的C_2烃收率,但BaO易在反应条件下与水反应生成Ba(OH)_2而腐蚀器壁,不利于长期操作.本文报导了一系列不同碱土金属化合物之间形成的二元碱土复合体系催化剂上甲烷氧化偶联的反应结果.结果表明,这类催化剂由于其结构稳定、活性好而值得进一步研究.     

Maskierung mit Kaliumjodid bei direkten Titrationen von Kupfer(II) mit Äthylendiamintetraessigsäure

Zusammenfassung Die Jodidoxydation durch Cu(II) wird in Anwesenheit von Ammoniak, Natriumtartrat, citrat oder -oxalat infolge Komplexbildung verhindert. Daher kann man z. B. Quecksüber(II) in Anwesenheit der genannten Komplexbildner mit Kaliumjodid maskieren und Kupfer(II) durch direkte Titration mit ÄDTA gegen Murexid, Brenzcatechinviolett, Chromazurol S, PAN oder PAR als Indikator bestimmen.

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Masking with potassium iodide in direct titrations of copper(II) with ethylenediamine tetraacetic acid

Summary The formation of a complex prevents the iodide oxidation by Cu(II) in the presence of ammonia, sodium tartrate, citrate, or oxalate. Hence mercury(II) for instance, can be masked against potassium iodide in the presence of these complex formers, and Cu(II) can be determined by direct titration with EDTA in the presence of murexide, pyrocatechol violet, chromazurol, PAN or PAR as indicator.

     

Crystal Structure and Characterization of a Large Polyoxotungstate (NH4)21{La(H2O)5[Ni(H2O)]2As4W40O140}·53H2O

The heteropolytungstate (NH4)₂₁{La(H₂O)₅[Ni(H₂O)]₂As₄W₄₀O₁₄₀}·53H₂O is obtained by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]· 60H₂O with NiCl₂·6H₂O, La(NO₃)₃·6H₂O and NH₄Cl at pH‐4.5. The structure and chemical composition are determined by X‐ray diffraction analysis and elemental analysis. The crystal data and main structure refinement are a = 1.9551(3) nm, b = 2.4156(4) nm, c= 3.7068(6) nm, β = 91.505(3)°, V = 17.500 (5) nm³, monoclinic crystal system with space group P2₁/n, Z = 4, R₁ = 0.0573, wR₂ = 0.0717 [I >2<s?(I)], R₁, = 0.2463 and wR₂ = 0.1199 (all data). [La(H₂O)₅] {Ni(H₂O)}₂AS₄W₄₀O₁₄₀ has C₂, symmetry. IR spectra of the ligand [NaAs₄W₄₀O₁₄₀]^27‐ and its three complexes were discussed.     

Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane.A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy.     

Photophysical properties of borondipyrromethene analogues in solution

The photophysical properties of seven new 8-(p-substituted)phenyl analogues of 4,4-difluoro-3,5-dimethyl-8-(aryl)-4-bora-3a,4a-diaza-s-indacene (derivatives of the well-known fluorophore BODIPY) in several solvents have been studied by means of absorption and steady-state and time-resolved fluorimetry. For each compound, the fluorescence quantum yield and lifetime are lower in solvents with higher polarity owing to an increase in the rate of nonradiative deactivation. Increasing the electron withdrawing strength of the p-substituent on the phenyl group in position 8 also leads to lower fluorescence quantum yields and lifetimes. When the p-substituent on the phenyl group in position 8 is a tertiary amine [8-(4-piperidinophenyl), 8-(4-N,N-dimethylaminophenyl), and 8-(4-morpholinophenyl)], the low quantum yields of these compounds in more polar solvents can be rationalized by the inversion of the energy levels of an apolar, highly fluorescent and a polar, nonfluorescent excited state, where charge transfer from the tertiary amine to the BODIPY unit occurs. These amine analogues can be protonated at low pH in aqueous solution. Fluorescence titrations yielded pK(a) values of their conjugate ammonium salts which are in agreement with the electron donating tendency of the amine group: piperidino (4.15) > dimethylamino (2.37) > morpholino (1.47), with the pK(a) values in parentheses. The rate constant of radiative deactivation (k(f)) is the same for all compounds in all solvents studied (k(f) = 1.4 x 10(8) s(-1)).     

Z/E-photoisomerizations of olefins with 4npi- or (4n + 2)pi-electron substituents: zigzag variations in olefin properties along the T(1) state energy surfaces

[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields.     

C9‐Iridoids from Scrophularia buergeriana

Four new iridoids, buergerinins B–E ( 1 – 4 ), along with three known iridoids, were isolated from the roots of Scrophularia buergeriana. Their structures were identified on the basis of spectroscopic analysis.     

An Efficient Synthesis of Pyrazolo[3,4‐b]Pyridine Derivatives in Aqueous Media

A series of pyrazolo[3,4‐b]pyridines was synthesized by the reaction of 5‐aminopyrazole with benzylidenemalononitrile in aqueous media. The structures were characterized by IR, ¹H NMR, and elemental analysis and were further confirmed by X‐ray diffraction analysis.     

混合模式硅胶基质毛细管电色谱整体柱的制备及其电色谱性能研究

采用温和条件下的溶胶-凝胶技术,成功制备了阴离子交换-反相混合模式硅胶基质毛细管电色谱整体柱.通过调整反应液中不同前体的比例,优化了整体柱的制备条件.通过扫瞄电镜,对柱床进行了表征和分析.实验发现,所制备的整体柱电渗流的方向和大小可随流动相pH值的改变而改变,在酸性和中性条件下,具有从阴极流向阳极的电渗流;当流动相pH值升至约7.5时,电渗流方向发生了反转(由阳极流向阴极).在优化的实验条件下,用所制备的整体柱对所考察的酸性(中性)化合物实现了快速分离,并获得了高达160,000 N/m的柱效.     

Lamellar Organo-Bridged Silicones

The acid-hydrolysis of an organo-bridged bisdiethoxysilylated molecular precursor bearing urea groups, (EtO)₂MeSi(CH₂)₃NHCONH(CH₂)₁₂NHCONH(CH₂)₃SiMe(OEt)₂, has been performed in pure aqueous medium. Scanning electron microscopy (SEM) analysis of the resulting insoluble solid revealed plate-like forms with a lamellar structure as determined by powder X-ray diffraction (PXRD) studies with a sharp peak at 28.5 Å. The solid state ²⁹Si MAS-NMR spectrum of this bridged siloxane hybrid is consistent with a moderately condensed material with complete preservation of the Si–C bonds throughout the hybrid network. In comparison, the classical sol–gel hydrolysis-condensation of the molecular precursor in ethanol with stoichiometric amount of water and fluoride anion as catalyst produced an amorphous featureless solid.