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181.
A series of rare-earth iron borates having general formula LnFe3(BO3)4 (Ln=Y, La-Nd, Sm-Ho) were prepared and their magnetic properties have been investigated by the magnetic susceptibility, specific heat, and 57Fe Mössbauer spectrum measurements. These borates show antiferromagnetic transitions at low temperatures and their magnetic transition temperatures increase with decreasing Ln3+ ionic radius from 22 K for LaFe3(BO3)4 to 40 K for TbFe3(BO3)4. In addition, X-ray diffraction, specific heat, and differential thermal analysis (DTA) measurements indicate that the phase transition occurs for the LnFe3(BO3)4 compounds with Ln=Eu-Ho, Y, and its transition temperature increases remarkably with decreasing Ln3+ ionic radius from 88 K for Ln=Eu to 445 K for Ln=Y. 相似文献
182.
183.
The hardness variation of amphoteric gel according to the surrounding solution conditions is quite unique. It hardens and softens reversibly regardless of its molecular network density. But this has been understood merely qualitatively. For the purpose of elucidation of the details of its behavior, we performed quantitative potential and hardness measurements on it. We observed the constant potential of amphoteric gels, approximately -60 mV, regardless of their swelling ratio and hardness. Such observations can be interpreted as the maintenance of the constant charge density of *COO- for any amphoteric gel, and they are further interpreted as intermolecular salt-linkage formation/disruption dominating the hardness of amphoteric gels. 相似文献
184.
Tetsuya Takeya Hirohisa Doi Tokutaro Ogata Tsuyoshi Otsuka Iwao Okamoto Eiichi Kotani 《Tetrahedron》2004,60(30):6295-6310
A simple method for the direct synthesis of 2,2′-binaphthols 2 and dinaphtho[1,2-b;2′,1′-d]furans 3 under mild conditions was developed, utilizing a biaryl coupling reaction via electron donor-acceptor complexes of 1-naphthols with SnCl4. Heating of the complex in a sealed tube for (18-24 h) afforded the corresponding o-o coupled product 2 in excellent yield. Prolonged reaction (56-65 h) under the same conditions afforded 3 in high yield in one step. We also found that in the case of α-naphthol without substituents other than a hydroxyl group at the C-1 position, regioselective o-o coupling reaction proceeded. The products 2a, 2b and 2g should be useful as synthetic intermediates for naturally occurring 3,3′-bijuglone, 3,3′-biplumbagin and elliptinone. 相似文献
185.
Tsuge T Yano K Imazu S Numata K Kikkawa Y Abe H Taguchi S Doi Y 《Macromolecular bioscience》2005,5(2):112-117
Eleven laboratory-evolved polyhydroxyalkanoate (PHA) synthases which originated from Pseudomonas sp. 61-3 enzyme (PhaC1(Ps)), together with the wild-type enzyme, were applied for PHA synthesis from fructose using Ralstonia eutropha PHB(-)4 as a host strain. The evolved PhaC1(Ps) mutants had amino acid substitution(s) at position 325 and/or position 481. In these mutants, serine-325 (S325) was replaced by cysteine (C) or threonine (T), while glutamine-481 (Q481) was replaced by lysine (K), methionine (M) or arginine (R). All recombinant strains harboring the genes of the evolved PhaC1(Ps) mutants produced a significantly increased amount of PHA (55-68 wt.-%) compared with the one harboring the wild-type gene (49 wt.-%). Particularly, those evolved PhaC1(Ps) mutants having multiple amino acid substitutions showed higher activities for PHA synthesis. Characterization of the PHA by NMR spectroscopy revealed that they were copolymers consisting of (R)-3-hydroxybutyrate (98-99 mol-%) and medium-chain-length comonomers (1-2 mol-%). This study also confirmed that amino acid substitution at position 481 in PhaC1(Ps) led to an increasing molecular weight of PHA. The number-average molecular weight (Mn) of PHA (Mn = 240,000) synthesized by the evolved PhaC1(Ps) (Q481K) mutant was 4.6-fold greater than that (Mn = 52,000) synthesized by the wild-type enzyme. 相似文献
186.
Solution-grown chain-folded lamellar single crystals of poly(tetramethylene adipate) (PTMA) were prepared from a dilute solution of 2-methyl-1-propanol by isothermal crystallization. PTMA crystals were hexagonal-shaped and polyethylene decoration of the crystals resulted in a "six cross-sector" surface morphology and showed that the average direction of chain folding is parallel to the crystal growth planes of [110] and [010]. Chain-folded lamellar crystals gave well-resolved electron diffraction diagrams corresponding to all the equatorial reflections of the X-ray fiber diagram obtained from stretched PTMA melt-quenched film (beta structure). The unit cell parameters of the beta structure of PTMA were determined as a = 0.503 nm, b = 0.732 nm and c (fiber axis) = 1.442 nm with an orthorhombic crystal system. The fiber repeat distance is appropriate for an all-trans backbone conformation for the straight stems. The setting angle, with respect to the a axis, is +/-46 degrees for the corner and center chains. Thermal behavior of lamellar crystals has been investigated by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM). The lamellar thickness at the edges of the crystal increased after thermal treatment with taking the molecular chains into recrystallization parts; the holes then opened up at the thickening front of the crystal. The morphological changes of lamellar crystals after enzymatic degradation by Lipase type XIII from Pseudomonas sp. and water-soluble products were characterized by TEM, AFM, gel permeation chromatography, high performance liquid chromatography and fast atom bombardment mass spectrometry. The degradation progressed mainly from the edges of the lamellar crystals without decreasing the molecular weights and the lamellar thicknesses. The central portion of single crystals was often degraded by enzymatic attacks. This result combined with thermal behavior indicates that the loosely chain-packing region exists inside the single crystal, and that molecular chains in this region have higher mobility against thermal and enzymatic treatments. 相似文献
187.
Doi H Barletta J Suzuki M Noyori R Watanabe Y Langstrom B 《Organic & biomolecular chemistry》2004,2(21):3063-3066
The reaction with phenyl azide and [11C]carbon monoxide to give N,N'-diphenyl[11C]urea and ethyl phenyl[11C]carbamate has been studied with the aim of development of a new methodology for carbonylation using [11C]carbon monoxide with high specific radioactivity. The synthesis of 11C-labelled N,N'-diphenylurea from phenyl azide and [11C]carbon monoxide, with 1,2-bis(diphenylphosphino)ethane-bound Rh(I) complex at 120 degrees C at a pressure of 35 MPa in the presence of aniline was accomplished in 82% trapping efficiency and 82% conversion yield. This approach was also useful for the synthesis of ethyl phenyl[11C]carbamate with lithium ethoxide as a nucleophilic reagent giving 90% trapping efficiency and 76% conversion yield. These reactions can be considered to proceed via a [11C]isocyanate or a [11C]isocyanate-coordinated Rh complex to give the corresponding 11C-products. This protocol provides the chemical basis for the synthesis of [11C]urea and [11C]carbamate derived from [11C]isocyanates. 相似文献
188.
Kenji Doi 《Journal of Non》1982,51(3):367-380
Wide angle, small angle, and very-small angle X-ray scatterings (WAXS, SAXS and VSAXS) as well as optical microscopy are observed for amorphous silica before and after neutron irradiation [3×1010nth/cm2, (48±2)°C]. The results are analyzed by employing the continuous random network (CRN) model [Zachariasen, J. Am. Chem. Soc. 54 (1932) 3841] that is topologically equivalent to the dense random packing (DRP) model for metallic glass (hard spheres being replaced by deformable spheres containing Si2O4 structural units).The effects of irradiation, as deduced from the broadening of the innermost haloes in WAXS, are interpreted in terms of an enhancement of randomness in the packing of the spheres materializing the structural unit, and in the internal structures of the spheres. This involves the rearrangements of the OSiO network that results in the local invalidation of the CRN-DRP equivalence. Consequently, small (25 Å) and large () structural inhomogeneities are produced that can effectively be disclosed by WAXS, SAXS, VSAXS, and optical microscopy. Arguments are advanced in which these structural changes are viewed as deviations from the DRP-equivalent CRN model in an analogous way as interpreting the radiation effects of amorphous Pd80Si20 (Doi et al., J. Non-Crystalline Solids 34 (1979) 405). 相似文献
189.
190.