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1.
A new method involving efficient, widely applicable, and highly selective alpha-chlorination of simple silyl enolate with Lewis acid and an alpha,alpha-dichloro-1,3-dicarbonyl controller unit was reported. Diastereoselectivity and enantioselectivity of the reaction were investigated. High reactivity and selectivity were achieved by using alpha,alpha-dichlorinated malonic ester. 相似文献
2.
Spin preference and S-T gaps of localized 1,3-diradicals were studied by an orbital phase theory and theoretical calculations. The orbital phase theory was applied to rationalize thermodynamic and kinetic stabilities of diradicals. We theoretically designed some singlet localized 1,3-diradicals, substituted trimethylenes, which are more stable than the lowest triplets. Some diradicals with the four-membered rings, 2,4-disilacyclobutane-1,3-diyls, were designed and shown to have singlet ground states and to be more stable than the sigma-bonded isomers, 2,4-disilabicyclo[1.1.0]butanes. The ab initio calculations supported predictions of the stable carbon-centered localized singlet 1,3-diradicals. 相似文献
3.
A capillary electrophoretic method for the simultaneous determination of sulfamethoxazole and trimethoprim in plasma was developed. Sulfamethoxazole and trimethoprim extracted from human plasma with ethyl acetate were analyzed at 20 kV and 25 degrees C using 15 mm phosphate buffer (pH 6.2) as the electrolyte. The detection was by UV at 220 nm. The run time was 8.0 min and the limit of quantification was 10.00 microg/mL for sulfamethoxazole and 2.00 microg/mL for trimethoprim. The recovery was >99% for both compounds. This method enabled the detection of sulfamethoxazole and trimethoprim in plasma of patients after oral ingestion of their combined formulation. The present simple and rapid method is applicable to drug monitoring in immunocompromised patients who are taking the combined formulation of these compounds for the treatment or prophylaxis of Pneumocystis carinii pneumonia. 相似文献
4.
Bo Jiang Hui Song Yunqing Kang Shengyao Wang Qi Wang Xin Zhou Kenya Kani Yanna Guo Jinhua Ye Hexing Li Yoshio Sakka Joel Henzie Yamauchi Yusuke 《Chemical science》2020,11(3):791
Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO2 into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.Generating high surface area mesoporous transition metal boride is challenging but interesting because incorporation of boron atoms can generate lattice distortion to form amorphous metal boride which has unique properties in catalysis. 相似文献
5.
Masaki Takeguchi Kazutaka Mitsuishi Miyoko Tanaka Kazuo Furuya 《Microscopy and microanalysis》2004,10(1):134-138
About 1 monolayer of palladium was deposited onto a silicon (111) 7 x 7 surface at a temperature of about 550 K inside an ultrahigh vacuum transmission electron microscope, resulting in formation of Pd2Si nanoislands and a 1 x 1 surface layer. Pd clusters created from an excess of Pd atoms on the 1 x 1 surface layer were directly observed by in situ plan view high-resolution transmission electron microscopy. When an objective aperture was introduced so that electron diffractions less than 0.20 nm were filtered out, the lattice structure of the 1 x 1 surface with 0.33 nm spacing and the Pd clusters with a trimer shape were visualized. It was found that image contrast of the 1 x 1 lattice on the specific height terraces disappeared, and thereby an atomic structure of the Pd clusters was clearly observed. The appearance and disappearance of the 1 x 1 lattice was explained by the effect of the kinematical diffraction. It was identified that a Pd cluster was composed of three Pd atoms without a centered Si atom, which is consistent with the model proposed previously. The feature of the Pd clusters stuck at the surface step was also described. 相似文献
6.
Tsuda M Izui N Shimbo K Sato M Fukushi E Kawabata J Katsumata K Horiguchi T Kobayashi J 《The Journal of organic chemistry》2003,68(13):5339-5345
A novel cytotoxic 16-membered macrodiolide, amphidinolide X (1), has been isolated from a marine dinoflagellate Amphidinium sp. (strain Y-42). The gross structure of 1 was elucidated on the basis of spectroscopic data including one-bond and long-range (13)C-(13)C correlations. The relative and absolute stereochemistries were determined by combined analyses of NOESY data and (1)H-(1)H and (1)H-(13)C coupling constants of 1 and NMR data of the degradation products. Amphidinolide X (1) is the first macrodiolide consisting of polyketide-derived diacid and diol units from natural sources. The biosynthetic origins of 1 were investigated by means of feeding experiments with (13)C-labeled acetates. 相似文献
7.
Gold-dendrimer nanocomposites are prepared in aqueous solutions in the presence of poly(amidoamine)dendrimers (PAMAM) (generation 3 and 5) or poly(propyleneimine)dendrimers (PPI) (generation 3 and 4) by wet chemical NaBH(4) method. Thus prepared gold-dendrimer nanocomposites are irradiated by laser at 532 nm. UV-vis absorption spectroscopy and transmission electron microscopy reveal that the gold nanoparticles grow with the laser irradiation time as well as the fluence of the laser; in particular, the gold nanoparticles prepared at lower concentrations of PAMAM dendrimer as well as lower generations of PAMAM grow significantly. On the other hand, in the case of PPI dendrimers, the gold nanoparticles hardly grow by irradiation. In addition, dynamic light-scattering measurements show that the laser irradiation markedly promotes the association of the gold-PAMAM G3 dendrimer nanocomposites compared to that of the gold-PAMAM G5 dendrimer nanocomposites, while the sizes of association for the gold-PPI G3, G4 dendrimer nanocomposites hardly change by laser irradiation. 相似文献
8.
Damla Durak Anıl Delikanlı Cahit Demetgül İbrahim Kani Selahattin Serin 《Transition Metal Chemistry》2013,38(2):199-206
An unsymmetrical tetradentate Schiff base (H2L) was synthesized by the reaction of 3-methoxysalicylaldehyde, o-phenylenediamine, and salicylaldehyde in EtOH. H2L was characterized by single-crystallographic X-ray analysis. Its Co(II) and Mn(III) complexes ([CoL] and [MnLCl]) were prepared and immobilized on 3-aminopropyltriethoxysilane functionalized silica gel. The immobilized materials were found to be efficient catalysts for epoxidation of styrene in the presence of tert-BuOOH in acetonitrile at 40 °C. The catalysts can be reused several times without significant loss of performance. 相似文献
9.
New 3,3‐diphenylpropoxyphthalonitrile (5) was obtained from 3,3‐diphenylpropanol (3) and 4‐nitrophthalonitrile (4) with K2CO3 in DMF at 50 °C. The novel cobalt(II) phthalocyanine complexes, tetrakis‐[2‐(1,4‐dioxa‐8‐azaspiro[4.5]dec‐8‐yl)ethoxy] phthalocyaninato cobalt(II) (2) and tetrakis‐(3,3‐diphenylpropoxy)phthalocyaninato cobalt(II) (6) were prepared by the reaction of the phthalonitrile derivatives 1 and 5 with CoCl2 by microwave irradiation in 2‐(dimethylamino)ethanol for at 175 °C, 350 W for 7 and 10 min, respectively. These new cobalt(II)phthalocyanine complexes were characterized by spectroscopic methods (IR, UV–visible and mass spectroscopy) as well as elemental analysis. Complexes 2 and 6 are employed as catalyst for the oxidation of cyclohexene using tert‐butyl hydroperoxide (TBHP), m‐chloroperoxybenzoic acid (m‐CPBA), aerobic oxygen and hydrogen peroxide (H2O2) as oxidant. It is observed that both complexes can selectively oxidize cyclohexene to give 2‐cyclohexene‐1‐ol as major product, and 2‐cyclohexen‐1‐one and cyclohexene oxide as minor products. TBHP was found to be the best oxidant since minimal destruction of the catalyst, higher selectivity and conversion were observed in the products. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
10.
Oxygen bridged Homobinuclear Mn(II) compounds with Anthranilic acid: Theoretical calculations,oxidation and catalase activity
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Two new homobinuclear manganese compounds with mixed ligands, [Mn2(μ1,1–2‐NH2C6H4COO)2(phen)4](ClO4)2(CH3OH) ( 1 ), and [Mn2(μ1,3–2‐NH2C6H4COO)2(bipy)4](ClO4)2 ( 2 ) (NH2C6H4COOH = anthranilic acid, bipy = 2,2′‐bipyridine, phen = 1,10‐ phenanthroline) were synthesized and thoroughly characterized by elemental analysis, IR, UV and single crystal X‐ray crystallography. X‐ray structure analysis shows that in the mono‐ and bidentate carboxylate bridged compounds, Mn–Mn distances of 1 and 2 are 3,461 Å, and 4,639 Å, respectively. The energy of the compounds was determined with a DFT (Density Functional Theory) calculation on B3LYP/6‐31G(d,p) optimized geometry by using the B3LYP/6‐31G(d,p) basis set. These compounds acts as biomimetic catalyst and show catalase‐like activity for the hydrogen peroxide dismutation at room temperature in different solvents with remarkable activity (TOF, Turnover frequency = mol of subst./(mol of cat. × time)) up to 12640 h?1 with 1 , and 17910 h?1 with 2 in Tris–HCl buffer). Moreover, the catalytic activity of 1 and 2 has been studied for oxidation of alcohols (cinnamyl alcohol, benzyl alcohol, cyclohexanol, 1‐octanol and 1‐heptanol) and alkenes (cyclohexene, styrene, ethyl benzene, 1‐octene and 1‐hexene) in a homogeneous catalytic system consisting t‐butylhydroperoxide (TBHP) as an oxidant in acetonitrile. Both compounds exhibited very high activity in the oxidation of cyclohexene to cyclohexanone (~80% selectivity, ~99% conversion in 1 h, TOF = 243 h?1 and 226 h?1) and cinnamyl alcohol to cinnamaldehyde (~64% selectivity) as the main product with very high TOF value (9180 h?1 and 13040 h?1 in the first minute of reaction) (~100% conversion in 0.5 h) with TBHP at 70 °C in acetonitrile, for 1 and 2 , respectively. 相似文献