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101.
The reactions of poly(4-vinylbiphenyl) (denoted as PVB) polymers and biphenyl molecules with solvated electrons in the 2-methyltetrahydrofuran (MTHF) solvent have been studied at 100–120 K by electron-pulse radiolysis. The formation of PVB polymer anions as well as biphenyl anions was observed by the electron-pulse irradiation of the MTHF-PVB(or biphenyl) solution. The anions are formed by two processes; a rapid formation during the pulse irradiation (<20 ns) and a slow formation after the pulse irradiation. The slow formation is due to a diffusion-controlled reaction between solutes, such as PVB and biphenyl, and solvated electrons. It was found that the reaction efficiency, expressed in monomer unit, of PVB polymers is 1/27 of that of biphenyl molecules. The reaction radius for the electron capture reaction of PVB polymers is estimated as 200–370 A, which is much larger than the gyration radius (107 A) of polymer coils in MTHF solution. 相似文献
102.
The behavior ofp-nitrotoluene adsorbed at zeolite/n-heptane interface has been investigated by the electronic spectroscopy under pressure up to 300 MPa. The uv-vis absorption bands of adsorbedp-nitrotoluene were deconvoluted into ones for the species adsorbed on the cation sites, and one for that on the pore wall of zeolite. The peak of adsorbed species on the cation site red-shifted by 20–80 nm from the position of the same species in the liquid phase, and their magnitudes of shift depended on the strength of electric field generated by the cation in zeolites. The peak intensities of adsorbed species on the cation site were enhanced but these or the pore wall site were reduced with the increase in pressure, suggesting that a part ofp-nitroluene molecules on the pore wall site desorbed and the adsorption on the cation site was enhanced by compression. The pressure dependence of peak intensity indicated that the behavior of this adsorption system was strongly governed by the solvation structure of the adsorbate in the zeolite pore. In particular, it was found that the adsorption of solvent molecules on the cation site strongly affected the volume change of the adsorption system. 相似文献
103.
Makoto Masuda Satoru Takamatsu Noriyuki Nishimura Saburo Komatsubara Tetsuya Tosa 《Applied biochemistry and biotechnology》1992,37(3):255-265
Serratia marcescens T-2000 was previously reported to be an l-threonine-producing strain that harbors the recombinant plasmid carrying the mutant-type
threonine operon. This strain produced 55 g of l-threonine/L of the medium containing urea as a nitrogen source after 72 h
of cultivation. In the urea-containing medium, transitory stop of the growth was observed during the early period of cultivation
when the entire amount of ammonium ion formed from urea via heat decomposition disappeared in the medium. This indicated that
the shortage of ammonium supply in cells might delay both the cell growth and the l-threonine production. The use of ammonia
water as a nitrogen source for l-threonine production was therefore studied, because microbial cells generally assimilate
this source more readily than urea. When ammonia water was automatically fed to the medium so as to maintain the pH of the
medium at around 7, the growth was accelerated, and the l-threonine production reached a maximum of 65 g/L at 48 h. Under
these conditions, sucrose, a carbon source, was continuously fed to the medium, resulting in the production of 100 g of l-threonine/L
at 96 h. Thus, the l-threonine productivity of the recombinant l-threonine-producing strain could be increased by devising
the method for supply of a nitrogen source. 相似文献
104.
Shimada Y Akane H Taniguchi N Matsuhisa A Kawano N Tanaka A 《Chemical & pharmaceutical bulletin》2005,53(5):589-590
Stereoselective synthesis of methyl (Z)-(4,4-difluoro-2,3,4,5-tetrahydro-1H-1-benzazepin-5-ylidene)acetate (1a) is described. Z-selectivity of the Horner-Wadsworth-Emmons (HWE) reaction was obtained based on an investigation of the reaction conditions for introduction of a methylidene group onto the 5-position of benzazepine. 相似文献
105.
Yamagiwa N Tian J Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2005,127(10):3413-3422
Full details of a catalytic asymmetric cyano-ethoxycarbonylation reaction promoted by a heterobimetallic YLi3 tris(binaphthoxide) complex (YLB 1), especially mechanistic studies, are described. In the cyanation reaction of aldehydes with ethyl cyanoformate, three achiral additives, H2O, tris(2,6-dimethoxyphenyl)phosphine oxide (3a), and BuLi, were required to achieve high reactivity and enantioselectivity (up to >99% yield and up to 98% ee). The roles of achiral additives and the reaction pathway were investigated in detail. In situ IR analysis revealed that the initiation step to generate LiCN from H2O, BuLi, and ethyl cyanoformate is rather slow. On the basis of mechanistic studies of the initiation step to generate an active nucleophilic species, reaction conditions were optimized by using a catalytic amount of acetone cyanohydrin as an initiator. Under the optimized conditions, the induction period decreased and the reaction completed within 9 min using 5 mol % YLB at -78 degrees C. Catalyst loading was successfully reduced to 1 mol %. Kinetic experiments and evaluation of the substituent effects of phosphine oxide revealed that phosphine oxide had beneficial effects on both the reaction rate and the enantioselectivity. The putative active species as well as the catalytic cycle of the reaction are also discussed. 相似文献
106.
Tomoe Sanada Kazuhiro Yamamoto Kazuo Kojima Noriyuki Wada 《Journal of Sol-Gel Science and Technology》2007,41(3):237-243
To obtain red luminants, MgO-GeO2 gel glasses and glass ceramics doped with manganese ions were prepared by a sol-gel method and their properties were investigated
by measuring X-ray diffraction (XRD), electron spin resonance (ESR), and luminescence and excitation spectra. Under UV irradiation
at 254 nm, the gel glasses and glass ceramics showed red luminescence at 620–665 nm, the intensity of which became strong
with increasing the heat-treatment temperature. A glass ceramic with the composition 1.0MnO-25MgO-75GeO2 heat treated at 1000°C exhibited the strongest red luminescence at 661 nm. From the results of XRD and ESR, this luminescence
is found to be due to the transition from the 4T1g to the 6A1g state of octahedrally coordinated Mn2+ ions located in MgGeO3 polycrystals. The luminescence wavelength of the glass ceramics (∼665 nm) is long compared with Eu3+-containing phosphors (612 nm), therefore the glass ceramics can be expected for red luminants. 相似文献
107.
Hongbo Qin Noriyuki Yamagiwa Dr. Shigeki Matsunaga Dr. Masakatsu Shibasaki Prof. Dr. 《化学:亚洲杂志》2007,2(1):150-154
Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)3/[Cu(CH3CN)4]PF6 system previously developed for catalytic intermolecular hydroamination of 1,3‐dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)4/[Cu(CH3CN)4]PF6 system was determined to be highly suitable. The combination of Hf(OTf)4 and [Cu(CH3CN)4]PF6 efficiently promoted the hydroamination of various vinyl arenes, including less‐reactive vinyl arenes with electron‐withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99 % yield with 0.3–10 mol % catalyst loading. 相似文献
108.
Toshinobu?TokumotoEmail author Ayami?Kondo Junko?Miwa Ryo?Horiguchi Mika?Tokumoto Yoshitaka?Nagahama Noriyuki?Okida Katsutoshi?Ishikawa 《BMC biochemistry》2003,4(1):6
Background
During Xenopusoocyte maturation, the amount of a 48 kDa protein detected in the 26S proteasome fraction (p48) decreased markedly during oocyte maturation to the low levels seen in unfertilized eggs. The results indicate that the interaction of at least one protein with the 26S proteasome changes during oocyte maturation and early development. An alteration in proteasome function may be important for the regulation of developmental events, such as the rapid cell cycle, in the early embryo. In this study, we identified p48. 相似文献109.
Horikiri H Hirano N Tanaka Y Oishi J Hatakeyama H Kawamura K Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):664-669
Syntheses of 10-oxo, 10alpha-hydroxy, and 10beta-hydroxy derivatives of a potent kappa-opioid receptor selective agonist, TRK-820, are described. These derivatives were supposed to be potential degradation products in formulation of TRK-820 as a result of autoxidation. 10-Oxo-TRK-820 11 was derived from 10-oxo-4,5-epoxymorphinan 14 in 10 steps in 32% overall yield. Reduction of the 10-oxo group in 4,5-epoxymorphinan with NaBH(4) gave 10beta-hydroxy-4,5-epoxymorphinan, exclusively. A stepwise inversion method of the 10beta-hydroxy group to produce 10alpha-hydroxy-4,5-epoxymorphinan was established. By HPLC analyses, 10alpha-hydroxy-TRK-820 12 was confirmed to be one of the degradation products in developing formulation of TRK-820. 相似文献
110.
Yasumichi Matsumoto Noriyuki Tanaka Hideki Kato 《Journal of solid state chemistry》2004,177(11):4205-4212
Photoelectrochemical measurements of TiO2, NaTaO3, and Cr or Sb doped TiO2 and SrTiO3 photocatalysts were carried out in H2 and O2 saturated electrolytes in order to evaluate the reverse reactions during water photolysis. The poor activity of TiO2 as a result of reverse photoreactions of O2 reduction and H2 oxidation was revealed with the respective high cathodic and anodic photocurrents. The rise in the photocurrents at NaTaO3 after La doping was in harmony with the doping-induced increase in the photocatalytic activity. NiO loading suppresses the O2 photoreverse reactions, which declines photocatalytic activity, and/or promotes the photo-oxidation of water, because the O2 photo-reduction current was scarcely observed near the flatband potential. Photocurrents of O2 reduction and H2 oxidation were observed under visible light for the Cr and Sb doped SrTiO3 and TiO2, respectively. These phenomena are in harmony with the previous reports on the photocatalysts examined with sacrificial reagents. 相似文献