首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1799篇
  免费   78篇
  国内免费   6篇
化学   1345篇
晶体学   21篇
力学   39篇
数学   280篇
物理学   198篇
  2023年   19篇
  2022年   17篇
  2021年   46篇
  2020年   55篇
  2019年   41篇
  2018年   26篇
  2017年   32篇
  2016年   59篇
  2015年   45篇
  2014年   55篇
  2013年   118篇
  2012年   104篇
  2011年   119篇
  2010年   66篇
  2009年   69篇
  2008年   104篇
  2007年   74篇
  2006年   76篇
  2005年   84篇
  2004年   63篇
  2003年   58篇
  2002年   50篇
  2001年   28篇
  2000年   22篇
  1999年   17篇
  1998年   23篇
  1997年   26篇
  1996年   12篇
  1995年   15篇
  1994年   12篇
  1993年   16篇
  1992年   19篇
  1991年   18篇
  1990年   16篇
  1988年   9篇
  1987年   5篇
  1985年   12篇
  1984年   13篇
  1983年   16篇
  1982年   13篇
  1981年   26篇
  1980年   22篇
  1979年   11篇
  1978年   16篇
  1977年   11篇
  1976年   15篇
  1975年   16篇
  1974年   15篇
  1973年   14篇
  1968年   6篇
排序方式: 共有1883条查询结果,搜索用时 15 毫秒
201.
Catalytic hydrogenation of carboxylic acid esters is essential for the green production of pharmaceuticals, fragrances, and fine chemicals. Herein, we report the efficient hydrogenation of esters with manganese catalysts based on simple bidentate aminophosphine ligands. Monoligated Mn PN complexes are particularly active for the conversion of esters into the corresponding alcohols at Mn concentrations as low as 0.2 mol % in the presence of sub-stoichiometric amounts of KOtBu base.  相似文献   
202.
203.
A classical tensor product \({A \otimes B}\) of complete lattices A and B, consisting of all down-sets in \({A \times B}\) that are join-closed in either coordinate, is isomorphic to the complete lattice Gal(A,B) of Galois maps from A to B, turning arbitrary joins into meets. We introduce more general kinds of tensor products for closure spaces and for posets. They have the expected universal property for bimorphisms (separately continuous maps or maps preserving restricted joins in the two components) into complete lattices. The appropriate ingredient for quantale constructions is here distributivity at the bottom, a generalization of pseudocomplementedness. We show that the truncated tensor product of a complete lattice B with itself becomes a quantale with the closure of the relation product as multiplication iff B is pseudocomplemented, and that the tensor product has a unit element iff B is atomistic. The pseudocomplemented complete lattices form a semicategory in which the hom-set between two objects is their tensor product. The largest subcategory of that semicategory has as objects the atomic boolean complete lattices, which is equivalent to the category of sets and relations. More general results are obtained for closure spaces and posets.  相似文献   
204.
Lovász theta function and the related theta body of graphs have been in the center of the intersection of four research areas: combinatorial optimization, graph theory, information theory, and semidefinite optimization. In this paper, utilizing a modern convex optimization viewpoint, we provide a set of minimal conditions (axioms) under which certain key, desired properties are generalized, including the main equivalent characterizations of the theta function, the theta body of graphs, and the corresponding antiblocking duality relations. Our framework describes several semidefinite and polyhedral relaxations of the stable set polytope of a graph as generalized theta bodies. As a by-product of our approach, we introduce the notion of “Schur Lifting” of cones which is dual to PSD Lifting (more commonly used in SDP relaxations of combinatorial optimization problems) in our axiomatic generalization. We also generalize the notion of complements of graphs to diagonally scaling-invariant polyhedral cones. Finally, we provide a weighted generalization of the copositive formulation of the fractional chromatic number by Dukanovic and Rendl from 2010.  相似文献   
205.
We propose a new approach for the discretization of diffusive flux on a non orthogonal mesh based on the Deferred correction introduced by Peric. This new method is applied successfully to the solution of a Poisson problem in quadrangular domains meshed with very distorted control volumes. The interest of this approach lies in the fact that the precision of the used schemes is conserved despite meshes distortion level. The comparative study of the value of the spectral radius of iteration matrix enables us to explain why our Deferred correction approach is better than that of Peric, which diverges on highly skewed meshes. To cite this article: Y.M. Ahipo, Ph. Traore, C. R. Mecanique 334 (2006).  相似文献   
206.
A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications.  相似文献   
207.
We report on the synthesis and scanning tunneling microscopy (STM) studies of a series of linear molecular rods (1-5) comprising different numbers and/or spatial arrangements of perfluorinated benzene and benzene subunits interlinked with diacetylenes in the para position and decorated with or without terminal dodecyl chains. The molecules organize themselves into well-ordered 2D crystal structures at the liquid/solid interface through intermolecular and molecule-substrate interactions. Whereas the molecules substituted by dodecyl chains form the lamellar structures with alternating rigid core rows and alkyl chain rows, the unsubstituted ones change the orientation of the rigid backbones with respect to the lamellar axis. The molecular arrangement is not influenced by fluoro substituents on any phenyl ring of the backbone, which suggests that the interactions between the π-conjugated backbones are dominated by close packing rather than by the dipole moments of the rods or fluorine-based intermolecular interactions.  相似文献   
208.
Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance.  相似文献   
209.
On H-Si(111) surfaces monolayer formation with 1-alkenes results in alkyl monolayers with a Si-C-C linkage, while 1-alkynes yield alkenyl monolayers with a Si-C═C linkage. Recently, considerable structural differences between both types of monolayers were observed, including an increased thickness, improved packing, and higher surface coverage for the alkenyl monolayers. The precise origin thereof could experimentally not be clarified yet. Therefore, octadecyl and octadecenyl monolayers on Si(111) were studied in detail by molecular modeling via PCFF molecular mechanics calculations on periodically repeated slabs of modified surfaces. After energy minimization the packing energies, structural properties, close contacts, and deformations of the Si surfaces of monolayers structures with various substitution percentages and substitution patterns were analyzed. For the octadecyl monolayers all data pointed to a substitution percentage close to 50-55%, which is due the size of the CH(2) groups near the Si surface. This agrees with literature and the experimentally determined coverage of octadecyl monolayers. For the octadecenyl monolayers the minimum in packing energy per chain is calculated around 60% coverage, i.e., close to the experimentally observed value of 65% [Scheres et al. Langmuir 2010, 26, 4790], and this packing energy is less dependent on the substitution percentage than calculated for alkyl layers. Analysis of the chain conformations, close contacts, and Si surface deformation clarifies this, since even at coverages above 60% a relatively low number of close contacts and a negligible deformation of the Si was observed. In order to evaluate the thermodynamic feasibility of the monolayer structures, we estimated the binding energies of 1-alkenes and 1-alkynes to the hydrogen-terminated Si surface at a range of surface coverages by composite high-quality G3 calculations and determined the total energy of monolayer formation by adding the packing energies and the binding energies. It was shown that due to the significantly larger reaction exothermicity of the 1-alkynes, thermodynamically even a substitution percentage as high as 75% is possible for octadecenyl chains. However, because sterically (based on the van der Waals footprint) a coverage of 69% is the maximum for alkyl and alkenyl monolayers, the optimal substitution percentage of octadecenyl monolayers will be presumably close to this latter value, and the experimentally observed 65% is likely close to what is experimentally maximally obtainable with alkenyl monolayers.  相似文献   
210.
The preparation and characterization of self-assembled monolayers on copper with n-alkyl and functional thiols was investigated. Well-ordered monolayers were obtained, while the copper remained oxide-free. Direct attachment of N-succinimidyl mercaptoundecanoate (NHS-MUA) onto the copper surface allowed for the successful attachment of biomolecules, such as β-d-glucosamine, the tripeptide glutathione, and biotin. Notably, the copper surfaces remained oxide-free even after two reaction steps. All monolayers were characterized by static water contact angle measurements, X-ray photoelectron spectroscopy, and infrared reflection absorption spectroscopy. In addition, the biotinylated copper surfaces were employed in the immobilization of biomolecules such as streptavidin.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号