Solvent-assisted catalysis mechanism on Keto–enol tautomerism of cyameluric acid

The keto–enol tautomerism of cyameluric acid, both in gas phase and in water and methanol solution, has been studied at the B3LYP/6-31++g(d,P) level of theory in this paper. The harmonic frequencies of all the structures are calculated. The results show that the transition states of the tautomerism are 4-membered ring conformations in gas phase, whereas 6-membered ring conformations in solution. In the first proton transfer, activation energy ΔE^# is 56.4 and 50.9 kJ/mol for water and methanol solution, respectively, which is much lower than that in gas phase (163.2 kJ/mol). Solvent molecules (water and methanol) produce an important catalytic effect in the tautomerism, especially for methanol-solvated system. NBO analysis shows that there is a strong interaction between cyameluric acid and solvent molecules in transition states. AIM charge analysis indicates that the keto–enol tautomerism shows a certain degree of proton transfer character. From the reaction enthalpy and reaction rate point of view, keto–enol tautomerism in water-solvated and methanol-solvated system is easier than that in gas phase. The keto–enol tautomerisms are endothermic both in gas phase and in solution, so the enol forms are less stable than the keto ones.     

C_(60)离子束撞击固体表面的坍塌沉积(Ⅰ)共焦显微拉曼光谱研究

为了研究C60的结构特性，我们最近在实验中将加这后的C60离子束沉积在固体表面，对其沉积后的形态进行了共焦显微拉曼光谱的表征．在记录的光谱中已检测不出C60原有的特征谱问，说明C60离子在高速憧击固体表面后，已经完全失去了原有的球状构型．C60的t）［R实验在自制的串级飞     

Building addressable libraries: the use of electrochemistry for spatially isolating a heck reaction on a chip

Pd(0) was generated at preselected sites on an electrochemically addressable chip and then utilized to effect a Heck reaction. The Pd(0) was confined to the preselected electrodes with the use of allylmethyl carbonate. Unlike most mediated electrochemical reactions, the electrolysis in this case was not used to convert a stoichiometric process into a catalytic one by recycling the metal. Instead, the unique environment of the chip was used to interfere with a catalytic process to make it stoichiometric. This was done to gain spatial control over the reaction. The development of a strategy for conducting Pd(0)-catalyzed reactions on the chips should greatly expand the synthetic chemistry available for building chip-based libraries.     

A SAPO-11 Silicoaluminophosphate Molecular Sieve with Stable Crystal Structure

A SAPO-11 silicoaluminophosphate molecular sieve with stable crystal structure was synthesized for the first time. After removing template by calcination, its crystal space group still retains Icm2 which the as-synthesized has. The catalyst deriving from the present SAPO-I 1 materials shows higher isomerization selectivity and higher paraffin hydroisomerization yield than those reported elsewhere.     

Morin applied in speciation of aluminium in natural waters and biological samples by reversed-phase high-performance liquid chromatography with fluorescence detection

A reversed-phase high-performance liquid chromatographic method with fluorescence detection for the determination of labile monomeric aluminium has been developed through pre-column complexation using morin as the analytical reagent. The highly fluorescent aluminium-morin complex (excitation wavelength 418 nm, emission wavelength 490 nm) was separated on a Spherisorb ODS 2 column with an eluent consisting of 30% methanol and 70% water (pH 1.0 with perchloric acid). The most remarkable point of this protocol was that only the most toxic aluminium species, that is, free aqua-aluminium ion and its monomeric hydroxo complex ions, selectively respond among various aluminium complexes. This strategy has been successfully applied to direct fractionation of the toxic aluminium in natural waters and biological samples without any pretreatment.     

Electron propagator theory study of N-/O-methylglycine conformers

The low-lying conformers of N-/O-methylglycine are studied by ab initio calculations at the B3LYP, MP3, and MP4(SDQ) levels of theory with the aug-cc-pVDZ basis set. The conformers having the intramolecular hydrogen bonds N-H...O=C or O-H...N are more stable than the others. Vertical ionization energies for the valence molecular orbitals of each conformer predicted with the electron propagator theory in the partial third-order quasiparticle approximation are in good agreement with the experimental data available in the literatures. The relative energies of the conformers and comparison between the simulated and the experimental photoelectron spectra demonstrate that there are at least three and two conformers of N- and O-methylglycine, respectively, in the gas-phase experiments. The intramolecular hydrogen bonding O-H...N effects on the molecular electronic structures are discussed for the glycine methyl derivatives, on the basis of the ab initio electronic structure calculations, natural orbital bond, and atoms-in-molecules analyses. The intramolecular hydrogen bonding O-H...N interactions hardly affect the electronic structures of the O-NH2-CH2-C(=O)-O-CH3 and alpha-methylated NH2-CH2-C(CH3)OOH conformers, while the similar intramolecular interactions lead to the significantly lower-energy levels of the highest occupied molecular orbitals for the N-(CH3-NH-CH2-COOH) and beta-methylated (NH2-CH2-CH2-COOH) conformers.     

Crystal and Molecular Structure of a New Mono－substituted Titanocene Complex，｛（η~5－Cp）［η~5－（1－（4－OCH_3）C_6H_4）C_6H_（10）Cp］（TiCl_2）｝·0．3（n－C_6H_（14））

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆａＮｅｗＭｏｎｏ－ｓｕｂｓｔｉｔｕｔｅｄＴｉｔａｎｏｃｅｎｅＣｏｍｐｌｅｘ，｛（η~５－Ｃｐ）［η~５－（１－（４－ＯＣＨ_３）Ｃ_６Ｈ_４）Ｃ_６Ｈ_（１０）Ｃｐ］（ＴｉＣｌ_２）｝·０．３（ｎ－...     

Catalytic asymmetric cyanosilylation of ketones with chiral Lewis base

The development of broadly applicable and practical catalytic approaches for the enantioselective creation of quaternary stereocenters remains a highly desirable yet challenging goal. In this Communication, we describe a highly enantioselective cyanosilylation of acetal ketones (alpha,alpha-dialkoxy ketones) catalyzed by modified cinchona alkaloids. This reaction is the first highly enantioselective cyanosilylation of ketones catalyzed by an organic chiral Lewis base and is found to be highly efficient with acetal ketones bearing a broad range of alkyl, aryl, alkenyl, and alkynyl substituents. This new catalytic asymmetric reaction, coupled with the versatility of the acetal functionality, provides a broadly useful synthetic method for chiral building blocks bearing quaternary stereocenters. Acetal ketones, readily accessible but previously unexplored in asymmetric synthesis, demonstrate unusual reactivity and selectivity toward the nucleophilic cyanosilylation, thereby suggesting that they may be interesting substrates for other catalytic enantioselective reactions.     

The Color Reaction of Mercury(II) with the New Reagent 2-Methylthiophenyldiazoaminoazobenzene and Its Application

A new and very sensitive and selective chromogenic reagent, 2-methylthiophenyldiazoaminoa-zobenzene (MTDAA), was synthesized and studied in detail for the determination of trace mercury(II) in water samples. The method is based on the color reaction between MTDAA and mercury(II). It was found that mercury(II) reacts with MTDAA in Na₂B₄O₇-NaOH buffer solution (pH = 10.0) to form 1 : 2 red complexes; these show maximum absorption at 520 nm. Beer’s law is obeyed in 0–15 µg of mercury(II) in 25 mL of solution. The apparent molar absorptivity of the complex is 1.33 × 10⁵ L/(mol cm); its limit of quantification, limit of detection, and relative standard deviation are 0.75 ng/mL, 0.27 ng/mL, and 1.0%, respectively, giving better sensitivity. The influence of the reaction variables and the effect of interfering ions are reported; most of the metal ions in water samples can be tolerated in considerable amounts. Only a few ions can interfere with the determination of trace mercury(II), but these can be eliminated by prior extraction. The proposed method is sensitive, simple, and rapid. It has been applied to the determination of trace mercury(II) in water samples with satisfactory results.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 7, 2005, pp. 703–706.Original English Text Copyright © 2005 by Guo, Din, Tian, Liu, Chang, Meng.The text was submitted by the authors in English.