铜离子交换改性的沸石催化剂上甲烷的非氧芳构化

已有研究表明，ＭｏＯ３／ＨＺＳＭ５是甲烷非氧芳构化的优良催化剂，在９７３Ｋ下甲烷转化率达６％～８％，苯选择性高于８０％，这为非氧气氛下甲烷的芳构化反应展示了非常诱人的前景［１～１２］．但是，该催化剂的活性和稳定性尚有待进一步提高，目前已有使用Ｐｔ，...     

The benzene ring as a dipolarophile: Reactions of monosubstituted benzenes with tetracyanoethylene oxide

Summary The reaction of tetracyanoethylene oxide on one hand and toluene, chlorobenzene, fluorobenzene, anisole, and nitrobenzene, on the other, has been studied. Toluene and the halogenobenzenes yield mixtures of monoadducts, anisole yieldp-methoxyphenylmalononitrile and its dimer and nitrobenzene does not react. These results are discussed with the help of a qualitative orbital model.¹H-NMR analysis of some monoadducts has been carried out.

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Der Benzolring als Dipolarophil: Reaktionen monosubstituierter Benzole mit Tetracyanoethylenoxid

Zusammenfassung Es wurden die Reaktionen von Tetracyanoethylenoxid mit Toluol, Chlorbenzol, Fluorbenzol, Anisol und Nitrobenzol untersucht. Toluol und die Halogenbenzole ergaben Mischungen von Monoaddukten, Anisol ergabp-Methoxyphenylmalononitril und sein Dimer, Nitrobenzol zeigte keine Reaktion. Diese Resultate werden mit Hilfe eines qualitativen Orbitalmodells diskutiert. Die Analyse einiger Monoaddukte erfolgte mittels¹H-NMR-Analyse.

     

Mechanistic aspects of the Wolff-Kishner reaction. V. The cation effect on the reaction of benzophenone hydrazone in butyl carbitol and decyl alcohol

The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated.     

Alginate Properties and Heavy Metal Biosorption by Marine Algae

The physical properties of the alginate component in four different brown seaweeds (Sargassumfluitans, Ascophyllum nodosum, Fucus vesiculo-sus, andLaminaria japonica) were characterized using potentiometric titration,¹³C-nuclear magnetic resonance (NMR), chemical analysis, and viscosity measurements. The heavy metal binding capacities of the corresponding seaweeds were directly proportional to their respective total carboxyl group content, and related to the electronegativity of the elements investigated (Ca, Zn, Cd, Cu, and Pb). The uronic acid composition or sequence of the alginate component did not affect the metal uptake properties of the biosorbents studied here. However, the alginate leaching owing to its solubilization by Na ions was observed to decrease with increasing intrinsic viscosity of the extracted alginate, related to its molecular weight, and with increasing apparent acidic dissociation constant, related to the alginate density inside the biomass.     

Synthesis and Antiradical Activity of 5-Acetyl-2-alkylthio-4-aryl-6-methyl-1,4-dihydropyridine-3-carboxylic Acid Nitriles

The alkylation of 3-cyano-1,4-dihydropyridine-2(3H)-thiones or the condensation of an aromatic aldehyde, cyanothioacetamide, acetylacetone, and methyl iodide in the presence of piperidine has given a series of novel 5-acetyl-2-alkylthio-4-aryl-6-methyl-1,4-dihydropyridine-3-carboxylic acid nitriles. A compound was obtained from 3,5-di(tert-butyl)-4-hydroxybenzaldehyde in the molecule of which were combined the active part of the antioxidant ionol and a 1,4-dihydropyridine ring. It was found that, among the compounds synthesized, the highest antiradical activity occurred in a compound having two hydroxyl groups in the 4-phenyl substituent.     

DFT and CIS(D) theoretical study on the ground and excited states of pentanitrogen cation

Different isomers of N₅⁺ were modeled at DFT(PBE0)/aug-cc-pV(Q + d)Z, and their ground(transition) state characteristics were assessed through frequency calculations. Single-point energies were accomplished at PBE0/aug-cc-pV(5 + d)Z. Nonlinear optical susceptibilities (NLO) of isomers were accomplished using Firefly, while the linear optical invariant was examined using the finite-field method, Firefly, and modified dipole field tensor in the presence of two different screening factors. The excited states, singlets and triplets, of were modeled at the CIS and CIS(D) and then their optical parameters were estimated at TDFT(PBE0)/aug-cc-pV(Q + d)Z using Firefly. The singlet is found the most stable isomer, with the inversional rate constant larger than that of the Cs isomer and high energy barrier with the triplet counterpart. Isomers 2 , 3 , and 4 are found local minima, while 5 and 6 are saddle points: transition states between equivalent invertomers. Energy calculations of the singlet and triplet isomers were in excellent agreement with the literature. An excellent correlation is found between the average polarizability and the impulse factor. Substantial variations were found between the singlet and triplet excited states in terms of energy, geometry, and optical properties from one side and with from the other side. Reactivity indices showed that N1 and N5 are the optimum nucleophilic and electrophilic reactivity sites.     

First radical cation salts of 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions: β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4

New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)₄Cu₂Cl₆ and (BDA-TTP)₂CuCl₄, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting BDA-TTP layers alternate with the [Cu₂Cl₆]²⁻ or [CuCl₄]²⁻ anions. Both salts show the semiconductor-type temperature dependence of the conductivity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007.     

Reactivity of Radical Cations of Trimesitylphosphine

Anodic oxidation of trimesitylphosphine in the presence of typical nucleophilic reactants is studied by cyclic voltammetry. The results and the literature data suggest that the manifestation of radical properties is more typical for radical cations of trimesitylphosphine, because, when realizing an electrophilic path of reacting, additional energy is needed for altering the configuration of radical cations of trimesitylphosphine.     

Use of the Second Derivative of TG Curves for Investigation of the Exchanged Interlayer Cation in Montmorillonite

Various cation-exchanged montmorillonites (Li+, Na+, Ba2+, Mg2+, Ca2+, Mn2+, Co2+, Cu2+, Ag+, Cd2+, Hg2+, Al3+, Pb2+ and NH4+) were prepared from calcium montmorillonite and their properties were studied by means of X-ray diffraction and thermal analysis. The two methods give information on the cation exchange in the interlayer space only. X-ray diffraction studies at room temperature are mainly suitable for estimation of the exchange of cations of different valencies. At 500°C, when the structure is completely collapsed, the d value of montmorillonite depends on the non-hydrated ionic radius of the interlayer cation, but the measurement interval is limited for fine interpretation. The thermoanalytical method is suitable for a better distinction of different exchangeable cations of higher hydration energy on the basis of the DTG or DDTG curve. This revised version was published online in July 2006 with corrections to the Cover Date.     

激光等离子体反应生成的AgP+n、AumP+n的结构分析

原子簇化合物的合成方法,由于条件限制,只有B、C、St等非金属元素与过渡金属袈基化合物等较为成熟．贵金属原子簇的合成则较困难．然而,应用激光等离子体反应,可使周期表内几乎所有元素都生成原子簇,为原子簇的生成与研究提供了一条新途径．该方法生成的原子簇在飞行时间质谱仪上可记录到一系列信号,某些信号呈现区域极大（或被称为‘匈数’吵］．郑兰芬等用纯化的红磷粉分别与金粉、银粉混合,在激光等离子作源飞行时间质谱仪上得到一系列谱图【2］：ig与P作用只得到单核xg与P形成的lgy：iE离子簇．谱图较简单,＊沪X最大可达叱叱…