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121.
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123.
We report studies of supersonically cooled indan using two-color resonantly enhanced multiphoton ionization and two-color zero-kinetic-energy photoelectron spectroscopy. With the aid of ab initio and density-functional calculations, vibrational modes of the first electronically excited state of the neutral species and those of the cation have been assigned, and the adiabatic ionization energy has been determined to be 68458 +/- 5 cm(-1). Similar to the ground state and the first electronically excited state of the neutral molecule, the ground state of the cation is also proven to be nonplanar, with an estimated barrier of 213 cm(-1) and a puckering angle of 15.0 degrees. These conclusions will be discussed in comparison with a previous study of an indan derivative 1,3-benzodioxole. 相似文献
124.
Dragulescu-Andrasi A Zhou P He G Ly DH 《Chemical communications (Cambridge, England)》2005,(2):244-246
Guanidine-based peptide nucleic acid (GPNA) with a d-backbone configuration and alternate spacing binds sequence-specifically to RNA and is readily taken up by both human somatic and embryonic stem (ES) cells. 相似文献
125.
The bicyclic keto lactone 26 was synthesized for the purpose of developing a viable route to marine diterpenes of the crenulatan type. Following the efficient conversion of (S)-citronellol ( 5 ) to the allylated alcohol 9a (Scheme 2), the αβ-unsaturated lactone 12 was efficiently accessed in preparation for stereocontrolled conjugate addition. The hydroxymethyl equivalent most suited to this task was (i-PrO)Me2SiCH2MgCl, which gave 13 predominantly in the presence of CuI and Me3SiCl. Once the OH group was deprotected (→ 14 ), it proved an easy matter to implement acid-catalyzed isomerization to lactone 15 , oxidation of which gave the pivotal aldehyde 16 . Condensation of 16 with PhSeCH2Li led via 21 to 22 (Scheme 3). Once the OH group was protected (→ 22b ), it proved possible to effect aldolization with crotonaldehyde (→ 23 ). Exposure of 23 to acid gave the sub-target compound 25 . Its subsequent oxidation and thermal activation resulted in sequential selenoxide elimination with Claisen rearrangement (→ 26 ). The structural features of 26 require that a chair-like transition state be adopted during the [3.3]sigmatropic event. With the clarification of these issues, a highly serviceable and more advanced assault on the crenulatans should prove capable of being mounted. 相似文献
126.
重铬酸钾氧化偶氮胂Ⅲ褪色催化光度法测定痕量钴的研究 总被引:3,自引:2,他引:3
在醋酸-醋酸钠缓冲介质中痕量钴(Ⅱ)对重铬酸钾氧化偶氮胂Ⅲ褪色反应有显著的催化作用,催化反应的表现活化能为25.62kJ.mol^-1,据此建立了测定痕量钴的催化动力学分析法,线性范围为0~350ng.mL^-1,检出限为2.0ng.mL^-1(Co),除Fe(Ⅱ)外,其余常见共存离子基本不影响钴的测定,本法重现性较好,用于测定人发,茶叶,土壤和废水中钴的含量,结果满意。 相似文献
127.
Zhuxing Tang Yun Zhou Yikun Zeng Shuliang Zang Pingang He Yuzhi Fang 《Chromatographia》2006,63(11-12):617-622
A method based on capillary electrophoresis with electrochemical detection has been developed for the separation and determination of epicatechin, isovanillic acid, vanillic acid and myricetin in Dioscorea bulbifera L. and its medicinal preparations. The effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time were investigated. Under optimum conditions, the analytes could be separated in a 40 mmol L?1 borate buffer (pH 8.7) within 15 min. A 300 μm diameter carbon disk electrode has a good response at + 0.95 V (vs. SCE) for all analytes. The response was linear over three orders of magnitude with detection limits (S/N = 3) ranging from 3.0 × 10?8 g mL?1 to 1.0 × 10?7 g mL?1. The method has been successfully applied to the analysis of real samples. 相似文献
128.
Wen-Jia Zhou Shu-Juan Bao Yan-Yu Liang Ben-Lin He Hu-Lin Li 《Journal of Solid State Electrochemistry》2006,10(5):277-282
Pure-phase and well-crystallized spinel LiMn2O4 powders were successfully synthesized by a simple rheological phase method. The thermal behavior and structure properties
of the powders prepared by the rheological phase method compared with the solid-state reaction were investigated by thermogravimetry,
powder X-ray diffraction , scanning electron microscopy and transmission electron microscopy. According to the results of
the electrochemical tests, it is obvious that the sample resulting from the rheological phase method shows higher discharge
capacity and better cycling stability than one formed in the solid-state reaction. The cyclic voltammogram and columbic efficiency
curves also confirm that the product by the rheological phase method has a good cycling performance due to its fine cubic
spinel structure and morphology. 相似文献
129.
Lingping Wang Aiguo Kong Bo Chen Hanming Ding Yongkui Shan Mingyuan He 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):143-150
Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N2 adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H2O2 (30%). The substituting element (Cu2+) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H2O2 by a radical substitution mechanism. 相似文献
130.
手性配体的空间结构与产物对映选择性的关系 总被引:2,自引:0,他引:2
首次采用4-烷氧羰基噻唑烷、E唑烷作为手性配体,诱导烷基锌对醛类的亲核加成反应,获得产物是烷基化的醛,最高达90%ee,产率98%的(S)-二级醇。系统地考察了该类手性配体三维空间结构变化与产物对映选择性的关系,当配体4-位烷氧羰基上的R、2-位R′基和环体上原子X发生变化时都会引起产物(S)-二 级醇的对映选择性发生规律性变化。对五种不同结构的底物醛在同一手性配体催化下,诱导烷基锌对醛类的亲核加成反应,底物结构变化也会引起(S)-二级醇对映选择性变化。 相似文献