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41.
-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride(MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride(SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. A novel ruthenium catalyst system consisting of Ru salts, trialkylphosphine and p-toluene sulfonic acid (p-TsOH) was found very effective for the hydrogenation of SAH affording GBL, which exhibited excellent catalyst performance, exceeding 97% selectivity for GBL and high activity. 相似文献
42.
Takeo Katami Tomokuni Hayakawa Masamichi Furukawa Shozo Shibata Tadashi Hara 《Analytica chimica acta》1986
An extraction-spectrophotometric method is described for the determination of traces of zinc with 2-[2-(3,5-dibromopyridyl)azo]-5-dimethylaminobenzoic acid. The reagent forms a stable, blue 1:2 zinc/reagent complex that can be extracted into chloroform. The apparent molar absorptivity of the zinc(II) complex is 1.26 × 105 l mol?1 cm?1 at 610 nm in chloroform. The reagent is relatively selective; interferences from cobalt, copper and nickel can be masked with dimethylglyoxime and aluminium and iron with a mixture of sodium fluoride and triethanolamine. The method is applied to the determination of zinc in coal fly ash and pond sediments with good precision and accuracy. 相似文献
43.
Xichen CaiMichihiro Hara Kiyohiko KawaiSachiko Tojo Mamoru FujitsukaTetsuro Majima 《Tetrahedron letters》2003,44(32):6117-6120
Some triplet energy-transfer reactions initiated by photoexcitation of the triplet excited state of dibenz[a,h]anthracene to higher triplet excited states (DBA(Tn)) were observed in the presence of the triplet energy quenchers (Q) such as naphthalene, biphenyl, p-dichlorobenzene, and o-dicyanobenzene. In the case of carbon tetrachloride (CCl4) as Q, DBA(Tn)-sensitized decomposition of CCl4 occurred. 相似文献
44.
Yoshimoto S Honda Y Murata Y Murata M Komatsu K Ito O Itaya K 《The journal of physical chemistry. B》2005,109(18):8547-8550
Adlayers of ZnOEP were prepared on reconstructed Au(100)-(hex) and unreconstructed Au(100)-(1 x 1) surfaces by immersing into a benzene solution containing ZnOEP molecules, and the adlayer structures were characterized by scanning tunneling microscopy (STM). A hexagonally arranged ZnOEP array was formed on an Au(100)-(hex) surface, whereas a rectangularly arranged ZnOEP array was found on an Au(100)-(1 x 1) surface. The adlayer structure of ZnOEP was dependent upon the underlying Au atomic arrangements. Furthermore, an investigation of the spuramolecular assembly for these modified surfaces was carried out by using an open-cage C(60) derivative (opened C(60)). A supramolecular assembled adlayer with a 1:1 composition of opened C(60)/ZnOEP was formed on Au(100)-(hex), whereas aggregates of opened C(60) were found on the ZnOEP-modified Au(100)-(1 x 1) surface. Electrochemical responses of opened C(60) were significantly influenced by underlying ZnOEP arrays. This finding suggests that precise control of underlying ZnOEP adlayers with the Au atomic structure is important to recognize the opened C(60) on them. 相似文献
45.
We apply the singular value decomposition to compress the degrees of freedom of T3 amplitude for the CCSDT-1 method (compressed CCSDT-1). This method enables us to make the number of the T3 amplitudes less than that of the T2 amplitudes, making CCSDT-1 calculations much less expensive without losing accuracy. We perform test calculations on some atoms and molecules to investigate the applicability of this method. Computational results for the electronic energies as well as timings of these calculations are presented. 相似文献
46.
Sakamoto M Cai X Hara M Fujitsuka M Majima T 《The journal of physical chemistry. A》2005,109(11):2452-2458
The properties and reactivities of the xanthone (Xn) ketyl radical (XnH*) in the doublet excited state (XnH*(D1)) were examined by using two-color two-laser flash photolysis. The absorption and fluorescence of XnH*(D1) were observed for the first time. Several factors governing the deactivation processes of XnH*(D1) such as interaction and reaction with solvent molecules were discussed. The remarkable change of reactivity of XnH*(D1) compared with that in the ground state (XnH*(D0)) was indicated from the experimental results. The rapid halogen abstraction of XnH*(D1) from some halogen donors such as carbon tetrachloride (CCl4) was found to occur. The halogen abstraction occurred more efficiently in the polar solvents than in the nonpolar solvents. It is suggested that the polar solvents promote the spin distribution of XnH*(D1) of the phenyl ring favorable to the halogen abstraction. 相似文献
47.
Shigeru Shimada Osamu Yamazaki Yohichi Suzuki 《Journal of organometallic chemistry》2004,689(19):3012-3023
Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substituents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key compound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine, which is a precursor for other azabismocines, has been synthesized by two different procedures; one is based on Akiba’s method using 2-bromobenzylbromide as one of the starting materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12 new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to be highly flexible and the hypervalent Bi-N bond distances vary ranging from 2.568(3) to 2.896(5) Å, depending on the electronic nature of the substituents on the bismuth atom. The Bi-N bond distances have good linear relationship against Hammett’s σm constants. 相似文献
48.
Osamu Matsumoto Eiji Hayami Mamoru Samejima Yasushi Kanzaki 《Plasma Chemistry and Plasma Processing》1984,4(1):33-42
The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10–10–10–8 g2 cm–4 s–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed. 相似文献
49.
Electrochemical and electrocatalytic properties of thin films Au(111-25 nm), which are quasi-single-crystal electrodes 25
nm thick made of gold with the (111) preferential orientation, and same electrodes modified with a monolayer (ML) of palladium
are studied in 0.1 M solutions of HClO4 and H2SO4 employing voltammetric techniques and surface enhanced infrared reflection absorption spectroscopy (ATR-SEIRAS). Spectroscopic
experiments demonstrate strong adsorption of electrolyte species (H2O, OHads, anions) on the Pd surface. The weak and reversible adsorption of CO on Au(111-25 nm) does not change the interfacial-water
structure. Adsorption of CO on the Pd-modified film results in an irreversibly adsorbed CO adlayer stabilized by co-adsorbed
isolated water species. Various electrooxidation mechanisms are discussed. Electrochemical and spectroscopic investigations
on the adsorption and electrooxidation of HCOOH on bare and 1 ML Pd-Au(111-25 nm) electrodes reveal that electrooxidation
proceeds in both cases via a direct or dehydrogenation pathway. This mechanism involves the formation of formate as intermediate,
which is detected by in situ ATR-SEIRAS. The reactivity on Pd-modified surfaces is higher than on bare gold. The specifically
adsorbed anions (sulfate/bisulfate) and the oxide formation on the substrate surface lower the reactivity for CO and HCOOH
on both surfaces.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1312–1329.
Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22,
2005, Moscow.
The text was submitted by the authors in English. 相似文献
50.
Murakami K Irie K Ohigashi H Hara H Nagao M Shimizu T Shirasawa T 《Journal of the American Chemical Society》2005,127(43):15168-15174
Amyloid fibrils mainly consist of 40-mer and 42-mer peptides (Abeta40, Abeta42). Abeta42 is believed to play a crucial role in the pathogenesis of Alzheimer's disease because its aggregative ability and neurotoxicity are considerably greater than those of Abeta40. The neurotoxicity of Abeta peptides involving the generation of free radicals is closely related to the S-oxidized radical cation of Met-35. However, the cation's origin and mechanism of stabilization remain unclear. Recently, structural models of fibrillar Abeta42 and Abeta40 based on systematic proline replacement have been proposed by our group [Morimoto, A.; et al. J. Biol. Chem. 2004, 279, 52781] and Wetzel's group [Williams, A. D.; et al. J. Mol. Biol. 2004, 335, 833], respectively. A major difference between these models is that our model of Abeta42 has a C-terminal beta-sheet region. Our biophysical study on Abeta42 using electron spin resonance (ESR) suggests that the S-oxidized radical cation of Met-35 could be generated by the reduction of the tyrosyl radical at Tyr-10 through a turn structure at positions 22 and 23, and stabilized by a C-terminal carboxylate anion through an intramolecular beta-sheet at positions 35-37 and 40-42 to form a C-terminal core that would lead to aggregation. A time-course analysis of the generation of radicals using ESR suggests that stabilization of the radicals by aggregation might be a main reason for the long-lasting oxidative stress of Abeta42. In contrast, the S-oxidized radical cation of Abeta40 is too short-lived to induce potent neurotoxicity because no such stabilization of radicals occurs in Abeta40. 相似文献