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Cao B Wakahara T Tsuchiya T Kondo M Maeda Y Aminur Rahman GM Akasaka T Kobayashi K Nagase S Yamamoto K 《Journal of the American Chemical Society》2004,126(30):9164-9165
A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5). 相似文献
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Copper-catalyzed N-arylation of diazoles can be accomplished using air-stable CuI as a copper source and 1,10-phenanthroline in the presence of KF/Al2O3 as a base. This is a simple and efficient method for the coupling of aryl bromide with diazoles. Different functionalized aryl bromides were coupled with diazoles using this system. 相似文献
26.
M. S. Rahman Khan 《Applied Physics A: Materials Science & Processing》1984,35(4):263-265
The resistivity of thin films (80–200 Å) of ErH2 increases sharply when heated for 2 h at 300 °C in vacuum in the presence of hydrogen gas at 10–2 Torr. This confirms that the films, originally metallic conductor, have become converted to semiconducting ErH3 which is in conformity with the structural studies. The negative values of TCR also indicate the semiconducting nature of the hydrogen treated films. Activation energies of the films have been evaluated. 相似文献
27.
Tanaka T Murakami K Kanda A Patra D Yamamoto S Satoh N Kim SW Rahman SM Ohno H Iwata C 《The Journal of organic chemistry》2001,66(21):7107-7112
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us. 相似文献
28.
Xanthine Sensors Based on Anodic and Cathodic Detection of Enzymatically Generated Hydrogen Peroxide
A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10?6?1.0×10?4 M and 5.0×10?7 to 1.0×10?4 M, respectively. The detection limits were determined to be of 1.0×10?6 M and 9.0×10?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples. 相似文献
29.
The carbon ceramic electrode prepared with sol-gel technique is modified by a thin film of chlorogenic acid (CGA). By immersing the carbon ceramic electrode in aqueous solution of chlorogenic acid at less than 2 s a thin film of chlorogenic acid adsorbed strongly and irreversibly on the surface of electrode. The cyclic voltammetry of the resulting modified CCE prepared at optimum conditions shows a well-defined stable reversible redox couple due to hydroquinone/quinone system in both acidic and basic solutions. The modified electrode showed excellent electrocatalytic activity toward NADH oxidation and it also showed a high analytical performance for amperometric detection of NADH. The catalytic rate constant of the modified carbon ceramic electrode for the oxidation of NADH is determined by cyclic voltammetry measurement. Under the optimised conditions the calibration curve is linear in the concentration range 1-120 μm. The detection limit (S/N = 3) and sensitivity are 0.2 μM and 25 nA μM−1.The results of six successive measurement-regeneration cycles show relative standard deviations of 2.5% for electrolyte solution containing 1 mM NADH, indicating that the electrode renewal gives a good reproducible and antifouling surface. The advantages of this amperometric detector are: high sensitivity, excellent catalytic activity, short response time t < 2 s, remarkable long-term stability, simplicity of preparation at short time and good reproducibility. 相似文献
30.
5‐Acetyl‐3‐amino‐4‐aryl‐6‐methylthieno[2,3‐b]pyridine‐2‐carboxamides ( 5a,b ) were reacted with triethyl orthoformate or nitrous acid to give the corresponding pyrimidinones 6a,b and triazinones 7a,b . The reaction of 5a,b with acetic anhydride was carried out and its products were identified as a mixture of 8‐acetyl‐9‐aryl‐2,7‐dimethylpyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidine‐4(3H)‐one ( 9a,b ) and related 5‐acetyl‐4‐aryl‐3‐biacetylamino‐6‐methylthieno[2,3‐b]pyridine‐2‐carbonitrile ( 10a,b ). Reaction of 7a with some halocompounds afforded the N‐alkylated triazinones 8a‐c . Chlorination of 6a,b and 9a,b with phosphorus oxychloride produced 4‐chloropyrimidines 11a‐d which were used as precursors for the rest of the target heterocycles. Some of the prepared compounds were tested in vitro for their antimicrobial activities. 相似文献