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排序方式: 共有371条查询结果,搜索用时 0 毫秒
1.
Saracoglu N Talaz O Azizoglu A Watson WH Balci M 《The Journal of organic chemistry》2005,70(14):5403-5408
[reaction: see text] endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters have been synthesized, and their Diels-Alder cycloaddition reactions with maleic anhydride, dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of four adducts indicated the pyramidalization of the central double bond. Density functional theory calculations on the isolated products and model compounds showed excellent agreement between the experimental and theoretical determined butterfly angles. Furthermore, it has been shown that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the pyramidalization which is attributed to the steric interactions between the cyclopropyl group and ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their X-ray analysis could not be carried out. DFT calculations on model compounds showed increased bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester. 相似文献
2.
Uzun O Sanyal A Nakade H Thibault RJ Rotello VM 《Journal of the American Chemical Society》2004,126(45):14773-14777
Polystyrene functionalized with diamidopyridine (DAP) recognition units self-assembles in nonpolar media to form thermally reversible micrometer-scale spherical aggregates. The size and the thermal stability of these microspheres can be controlled by the molecular weight of the polymer. The addition of thymine-functionalized polymer to these self-assembled microspheres converted them into vesicular aggregates with a controlled size. The morphology change was reversible: the addition of DAP-functionalized polymer converted the vesicles back to microspheres. 相似文献
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Huang XJ Im HS Yarimaga O Kim JH Lee DH Kim HS Choi YK 《The journal of physical chemistry. B》2006,110(43):21850-21856
Carboxylated single-walled carbon nanotubes (SWCNT) chemically assembled on gold substrate was employed as netlike electrode to investigate the charge-transfer process and electrode process kinetics using uric acid as an example. The electrochemical behavior of uric acid in carboxylated SWCNT system was investigated using cyclic voltammetry, chronoamperometry, and single potential time-based techniques. The properties of raw SWCNT electrode were also studied for comparison purpose. Uric acid has better electrochemical behavior whereas ascorbic acid has no effective reaction on the carboxylated SWCNT electrode. Cyclic voltammograms indicate that the assembled carboxylated SWCNT increases more active sites on electrode surface and slows down the electron transfer between the gold electrode and uric acid in solution. The charge-transfer coefficient (alpha) for uric acid and the rate constant (k) for the catalytic reaction were calculated as 0.52 and 0.43 s(-1), respectively. The diffusion coefficient of 0.5 mM uric acid was 7.5 x 10(-6) cm2 x s(-1). The results indicate that electrode process in the carboxylated SWCNT electrode system is governed by the surface adsorption-controlled electrochemical process. 相似文献
7.
1-Bromo-1-fluoro-[1a,2,7,7a]-tetrahydro-1H-cyclopropa[b]naphthalene (19) has been prepared by the addition of bromofluorocarbene to 1,4-dihydronaphthalene (18). Treatment of a solution of 19 in dry ether with MeLi afforded the tricyclic hydrocarbon 17, resulting from the intramolecular C-H insertion of carbene 16, and two dimerization products, the head-to-head 20 and head-to-tail 21 allene dimers, confirming the formation of title cycloallene 15 as a reactive intermediate. B3LYP/6-31G(d) calculation predicts the activation barriers for insertion product 17 and allene product 15 as 3.70 and 9.52 kcal/mol, respectively. This prediction was in good agreement with our experimental results. 相似文献
8.
Sibel Irmak Kemal Solakyildirim Arif Hesenov Oktay Erbatur 《Journal of Analytical Chemistry》2010,65(9):899-906
The aim of this study was to examine the influence of storage conditions and duration on composition and antioxidant activity
of supercritical fluid (SCF) extracted essential oil of rosemary (Rosmarinus officinalis L.). Supercritical extraction was carried out sequentially by using SCF carbondioxide in the first two steps and with 5%
ethanol as entrainer in the third step. The compositions of the extracts were determined by gas chromatography/mass spectrometry.
The total phenolics were analyzed using Folin-Ciocalteau assay. Antioxidant activities of the extracts were tested by β-carotene-linoleic
acid bleaching method. 相似文献
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New tandospirone analogues containing a 1-[3-(trifluoromethyl)phenyl]piperazine (TFMPP) moiety have been synthesized by hydroarylation reactions with Pd(OAc)2. The perhydroisoindole derivatives were obtained by the reaction of reduced starting material with aryl-(heteroaryl) iodides under the same conditions. Spiro-1,3-indandionolylpyrrolidine derivatives having an array of stereocenters are reported. 相似文献