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81.
Mesoionic 4-trifluoroacetyl-1,3-oxazolium-5-olates (1), obtained from the reaction of N-acyl-N-alkylglycines (2) with trifluoroacetic anhydride, react with ammonia to give 4-trifluoromethyl-3,4-dihydroimidazoles (3) in high yields. Dehydration of 3 gives 4-trifluoromethylimidazoles (4) in high yields. The novel ring transformation of 1 into 3 occurs via a regioselective attack of ammonia on the C-2 position of the ring. 相似文献
82.
Noboru Mizushima 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2007,83(2):39-46
Autophagy is in principle a non-selective degradation system within cells, which is conserved in all eukaryotic cells. Autophagy is usually suppressed at low levels but can be upregulated during periods of nutrient starvation, which facilitates cell survival. In addition to this fundamental role, basal autophagy was recently revealed to be important for constitutive turnover of intracellular proteins and organelles. Autophagy has been considered to be involved also in presentation of endogenous antigens, degradation of invasive bacteria, tumor suppression, cell death and development. This review will discuss the biological significance of autophagy, particularly focusing on its implications in protein metabolism in mammals. 相似文献
83.
Noboru Takeuchi 《Surface science》2007,601(16):3361-3365
The adsorption of acetylene on the Si(0 0 1)-c(2 × 4) surface at low and full coverage is studied by first principles density functional calculations using the generalized gradient approximation. For a single acetylene molecule, the most stable configuration corresponds to the di-σ site, on-top of a silicon dimer. This configuration is 0.36 eV more stable than the end-bridge site between two adjacent Si dimers. However, if there are two acetylene molecules, the paired end bridge configuration becomes the most stable. We have also studied the kinetics of the adsorption of a single acetylene molecule. Our calculations show that the reaction is barrier-free for adsorption in the di-σ configuration, while there is an energy barrier of 0.19 eV for adsorption in the end-bridge site. At monolayer coverage, the most stable configuration corresponds to acetylene molecules in the pair-end bridge configuration, in agreement with previous calculations. We have found a noticeable coverage dependence only for the end-bridge site, but not for the di-σ. Our results show that to have an accurate picture of the adsorption of acetylene on the Si(0 0 1) surface, a large unit cell is needed. 相似文献
84.
Shin‐Ichi Yusa Shigeki Awa Masanori Ito Takeshi Kawase Tadao Takada Kenichi Nakashima Dian Liu Shigeru Yamago Yotaro Morishima 《Journal of polymer science. Part A, Polymer chemistry》2011,49(13):2761-2770
Water‐soluble diblock copolymer, poly(N‐isopropylacrylamide)‐block‐poly(N‐vinyl‐2‐pyrroridone) (PNIPAMm‐b‐PNVPn), was found to associate with fullerene (C60), and thus C60 can be solubilized in water. The 63C60/PNIPAMm‐b‐PNVPn micelle formed a core‐shell micelle‐like aggregate comprising a C60/PNVP hydrophobic core and a thermoresponsive PNIPAM shell. The C60‐containing polymer micelle formation and its thermoresponsive behavior were characterized using light scattering and 1H NMR techniques. The hydrodynamic radius (Rh) of the C60‐bound polymer micelle increased with increasing temperature, which was ascribed to the hydrophobic association between dehydrated PNIPAM shells above lower critical solution temperature (LCST). 1H NMR data suggest that the motion of the PNIPAM block is restricted above LCST due to the dehydration of the PNIPAM shell in water. The generation of singlet oxygen by photosensitization by the C60‐bound polymer micelle was confirmed from photooxidation of 9,10‐anthracenedipropionic acid. Furthermore, DNA was found to be cleaved by visible light irradiation in the presence of the C60‐bound polymer micelle. Therefore, there may be a hope for a pharmaceutical application of the C60‐bound polymer micelle to cancer photodynamic therapy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献
85.
Alejandro R. Diaz Noboru Klkuchl Panos Papalambros John E. Taylor 《基于设计的结构力学与机械力学》2013,41(2):215-230
ABSTRACT Finite element solutions of improved quality are obtained by optimizing the location of nodes of the finite element grid, while keeping the number of degrees of freedom fixed. The formulation of the grid optimization problem is based on the reduction of error associated with interpolation of the exact solution, using functions from the finite element space. Element sizes are selected as design variables: length in R1 and area in R2. Analytically derived optimality conditions are presented and an approximation to these conditions is introduced to obtain a set of operationally useful equations that can be used as guidelines for construction of improved grids. Example problems are given for illustration. 相似文献
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Hiroki Uoyama Kil Suk Kim Dr. Kenji Kuroki Jae‐Yoon Shin Dr. Toshi Nagata Dr. Tetsuo Okujima Dr. Hiroko Yamada Dr. Noboru Ono Prof. Dongho Kim Prof. Hidemitsu Uno Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(13):4063-4074
Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ(2)) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways. 相似文献
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