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41.
The unprecedented role of a CuII cryptand in the luminescence properties of a EuIII cryptate complex
Hideki Ohtsu Tomoya Suzuki Hajime Ohtsuka Ayumi Ishii Miki Hasegawa 《Monatshefte für Chemie / Chemical Monthly》2009,25(6):783-787
Abstract
A EuIII cryptate complex constructed from a CuII cryptand with an L tBu ligand, [EuIIICu2II(L tBu)2(NO3)3(MeOH)], and the corresponding CaII and NaI cryptates, [CaIICu2II(L tBu)2(NO3)2(MeOH)2] and [NaICu2II(L tBu)2(Me2CO)](BPh4), have been synthesized and characterized in order to shed light on the essential role of CuII in the luminescence of a EuIII cryptate. The unprecedented role of a CuII cryptand makes it possible to produce lanthanide luminescence in a EuIII cryptate complex and is successfully elucidated by comparison with the corresponding CaII and NaI cryptates. 相似文献42.
Cho J Furutachi H Fujinami S Tosha T Ohtsu H Ikeda O Suzuki A Nomura M Uruga T Tanida H Kawai T Tanaka K Kitagawa T Suzuki M 《Inorganic chemistry》2006,45(7):2873-2885
The reaction of [Ni2(OH)2(Me2-tpa)2]2+ (1) (Me2-tpa = bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) with H2O2 causes oxidation of a methylene group on the Me2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(III) ([Ni2(O)2(Me2-tpa)2]2+ (2)), a bis(mu-superoxo)dinickel(II) ([Ni2(O2)2(Me2-tpa)2]2+ (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni2(OH)(Me2-tpa)(Me-tpa-CH2OO)]2+ (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni2(Me-tpa-CH2OO)2]2+ (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) and a ligand-coupling dimer (Me-tpa-CH2)2. The formation of (Me-tpa-CH2)2 suggests that a ligand-based radical Me-tpa-CH2* is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2* is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence of O2 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)2, indicating that the reaction of Me-tpa-CH2* with O2 is faster than the coupling of Me-tpa-CH2* to generate ligand-based peroxyl radical Me-tpa-CH2OO*. Although there is a possibility that the Me-tpa-CH2OO* species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the aldehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction. 相似文献
43.
Successful control of photo-driven NAD(+)/NADH type hydrogenation reactions in ruthenium complexes has been accomplished by using a new NAD(+) model ligand with modulated distortion of the ligand taking advantage of the substituent effect. 相似文献
44.
K. Tokuhara Y. Ohtsu F. Ono O. Yamada M. Sagawa Y. Matsuura 《Solid State Communications》1985,56(4):333-336
Magnetization and torque measurements on single crystal specimens of Nd2Fe14B have been carried out. The magnetization values measured always in the direction of easy magnetization and those in the [001] direction have been precisely determined at temperatures from 4.2K to 600K with a superconducting magnet up to 52.65 kOe. Below the spin reorientation temperature 135K, the magnetization value of the direction of easy magnetization increases anomalously with decreasing temperature. The direction of easy magnetization tilts from the [001] axis to the [110] axis and this tilt angle has been also precisely determined by torque measurement in the temperature range below the spin reorientation temperature. The four-fold symmetry in torque curve for the (001) plane is continously observed at even up to near room temperature and the [110] direction of easy magnetization and the [100] direction of hard magnetization do not change below and above the spin reorientation temperature. 相似文献
45.
T. Yatsui Y. Nakajima W. Nomura M. Ohtsu 《Applied physics. B, Lasers and optics》2006,84(1-2):265-267
We propose a novel method to increase the resolution of imprint lithography by introducing strong localization of the optical
near-field intensity, depending on the mold structure. By optimizing the thickness of the metallic film on a SiO2 line-and-space (LS) mold without a sidewall coating, we confirmed that the optical near-field strongly localizes at the edge
of the mold, using a finite-difference time-domain calculation method. Based on the calculated results, we performed optical
near-field imprint lithography using a mold with metallized (20-nm-thick Al without a sidewall coating) SiO2 LS with a 300-nm half-pitch that was 200-nm deep with illumination using the g-line (λ=436 nm), and obtained features as
narrow as 50 nm wide.
PACS 81.16.Nd; 81.16.Rf 相似文献
46.
47.
Y. Ohtsu H. Fukui T. Kanda K. Nakamura M. Nakano O. Nakata Y. Fujiyama 《Chromatographia》1987,24(1):380-384
Summary Silicone polymer-coated silica gels modified with octadecyl and octyl groups (S/S-C18, S/S-C8), or “capsule-type silica gels” were developed as packing materials for reversed-phase liquid chromatography. They were obtained
by coating the surface of totally porous silica gel with a homogeneous silicone polymer film, and thereafter modifying the
coating polymer with octadecyl or octyl groups. Retaining the advantages of silica-based packings, they show strong resistance
of alkali-like organic porous polymeric materials. 相似文献
48.
Naomichi Furukawa Toshiaki Yoshimura Masami Ohtsu Takeshi Akasaka Shigeru Oae 《Tetrahedron》1980,36(1):73-80
The Michael type additions of diphenyl N-unsubstituted sulfimide (free sulfimide) to various electrophilic olefins were carried out. The reaction with cis- and trans-dibenzoylethylene, dimethyl-fumarate, dimethylmaleate, benzalacetophenone and benzalacetone gave mainly the corresponding trans-2-acylaziridines and trans-enaminoketones. However, phenyl vinyl sulfone or acrylonitrile afforded not the corresponding aziridine but diphenyl-N-2-cyano or N-2-phenylsulfonylethylsulfimide, a simple Michael adduct When optically active (+)-(R)-o-methoxyphenyiphenyl free sulfimide was treated with such an α,β-unsaturated carbonyl compound as benzalacetopbenone, an optically active 2-acylazindine, i.e., (-)-trans-2-benzoyl-3-phenylaziridine was obtained in ca 30% optical purity and its absolute configuration was assigned as (2R,3S) upon chemical transformation to the configuration-ally known 2-phenyl-2-benzoylamino-1-ethanol or by comparing its CD spectrum with that of (1R,2R)-1-phenyl-2-benzoyl-cyclopropane. Meanwhile, (-)-(S)-o-methoxyphenylphenyl free sulfimide was found to react with benzalacetophenone to afford (+)-trans-2-benzoyl-3-phenylaziridine of 25% optical purity. Effects of solvent and temperature on both die distribution of the products ratio and the optical yield were examined. 相似文献
49.
50.