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81.
82.
Itaru Hataue 《Journal of Computational and Applied Mathematics》2009,232(1):82-89
In the present paper, the dependencies of the numerical results of fluid simulations on forcibly added randomness are discussed. The incompressible Navier-Stokes equations and the continuity equation are solved numerically by using the MAC (Maker-And-Cell) method and implicit temporal scheme. The model adopted in the present study is a flow around a two-dimensional circular cylinder and the Reynolds number is 1500. The randomness which is given by using the pseudo-random number is forcibly added in the time marching step of the discretized Navier-Stokes equations. Dependencies of the averaged structure of asymptotic numerical solutions on the randomness are discussed. Furthermore, the dependence of the qualitative structure of the asymptotic solution of each sample calculation on the amplitude of randomness is also studied. It is clarified that forcibly added random errors may cover the nonlinear errors which make the system unstable. 相似文献
83.
Fukuta Y Mita T Fukuda N Kanai M Shibasaki M 《Journal of the American Chemical Society》2006,128(19):6312-6313
An asymmetric ring-opening reaction of meso-aziridines with TMSN3 was developed using a catalyst prepared from Y(OiPr)3 and chiral ligand 2 in a 1:2 ratio. Excellent enantioselectivity was realized from a wide range of substrates with a practical catalyst loading. The products were efficiently converted to enantiomerically enriched 1,2-diamines, which are versatile chiral building blocks for pharmaceuticals and chiral ligands. This reaction was applied to a catalytic asymmetric synthesis of Tamiflu, a very important anti-influenza drug containing a chiral 1,2-diamino functionality. 相似文献
84.
Fujimori I Mita T Maki K Shiro M Sato A Furusho S Kanai M Shibasaki M 《Journal of the American Chemical Society》2006,128(51):16438-16439
New chiral ligands for asymmetric polymetallic catalysts were designed on the basis of the assumption that the higher-order assembly structure is stabilized by modifying the modular unit. The designed ligands 6 and 7 contained a scaffolding cyclohexane ring with a Lewis base phosphine oxide directly attached to the scaffold. A module in the polymetallic complex contains two metals per ligand, and a stable 6-, 5-, 5-membered fused chelation ring system should be generated. Synthesis of these ligands is simple and high yielding, using a catalytic dynamic kinetic resolution promoted by the Trost catalyst as a key step. Ligand function was assessed in a catalytic asymmetric ring-opening reaction of meso-aziridines with TMSCN, a useful reaction for the synthesis of optically active beta-amino acids. The Gd complex generated from Gd(OiPr)3 and the ligand was a highly active and enantioselective catalyst in this reaction. Enantioselectivity was reversed compared to the previously reported d-glucose-derived catalyst containing the same chirality of the individual module. ESI-MS analysis and X-ray crystallographic studies indicate that the assembly state of the modules in the polymetallic catalysts differs depending on the chiral ligand. The difference in the higher-order structure stems from a subtle change (one carbon) in the position of the Lewis base relative to the Gd metal. The change in the higher-order structure of the polymetallic complex led to a dramatic reversal of the enantioselectivity and increased catalyst activity. 相似文献
85.
Ojida A Inoue MA Mito-oka Y Tsutsumi H Sada K Hamachi I 《Journal of the American Chemical Society》2006,128(6):2052-2058
Protein phosphorylation is ubiquitously involved in living cells, and it is one of the key events controlling protein-protein surface interactions, which are essential in signal transduction cascades. We now report that the small molecular receptors bearing binuclear Zn(II)-Dpa can strongly bind to a bis-phosphorylated peptide in a cross-linking manner under neutral aqueous conditions when the distance between the two Zn(II) centers can appropriately fit in that of the two phosphate groups of the phosphorylated peptide. The binding property was quantitatively determined by ITC (isothermal titration calorimetry), induced CD (circular dichroism), and NMR. On the basis of these findings, we demonstrated that these types of small molecules were able to effectively disrupt the phosphoprotein-protein interaction in a phosphorylated CTD peptide and the Pin1 WW domain, a phosphoprotein binding domain, at a micromolar level. The strategy based on a small molecular disruptor that directly interacts with phosphoprotein is unique and should be promising in developing a designer inhibitor for phosphoprotein-protein interaction. 相似文献
86.
One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO(2) gas, an inexpensive and ubiquitous C1 source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO(2) was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products. 相似文献
87.
Takahashi M Kawamura A Kato N Nishi T Hamachi I Ohkanda J 《Angewandte Chemie (International ed. in English)》2012,51(2):509-512
Fluorescent combination: Cell-penetrating probes derived from the diterpene fusicoccin can form ternary complexes with 14-3-3 proteins and phosphopeptide ligands, whereupon the probes site-specifically attach a fluorescent tag onto the surface of the 14-3-3 proteins. 相似文献
88.
Visualization of tumor-specific protein biomarkers on cell membranes has the potential to contribute greatly to basic biological research and therapeutic applications. We recently reported a unique supramolecular strategy for specific protein detection using self-assembling fluorescent nanoprobes consisting of a hydrophilic protein ligand and a hydrophobic BODIPY fluorophore in test tube settings. This method is based on recognition-driven disassembly of the nanoprobes, which induces a clear turn-on fluorescent signal. In the present study, we have successfully extended the range of applicable fluorophores to the more hydrophilic ones such as fluorescein or rhodamine by introducing a hydrophobic module near the fluorophore. Increasing the range of available fluorophores allowed selective imaging of membrane-bound proteins under live cell conditions. That is, overexpressed folate receptor (FR) or hypoxia-inducible membrane-bound carbonic anhydrases (CA) on live cell surfaces as cancer-specific biomarkers were fluorescently visualized using the designed supramolecular nanoprobes in the turn-on manner. Moreover, a cell-based inhibitor-assay platform for CA on a live cell surface was constructed, highlighting the potential applicability of the self-assembling turn-on probes. 相似文献
89.
Ikeda M Fukuda K Tanida T Yoshii T Hamachi I 《Chemical communications (Cambridge, England)》2012,48(21):2716-2718
A boronic acid-appended fluorescent receptor was incorporated into self-assembled nanofibers containing a hydrophobic FRET-paired dye to develop a gel-based fluorocolorimetric sensor for polyols. We demonstrated that the gel-based sensor is capable of detecting polyols such as catechol and dopamine not only under semi-wet conditions, but also under dry conditions using a paper platform. 相似文献
90.
Okamoto I Ono T Sameshima R Ono A 《Chemical communications (Cambridge, England)》2012,48(36):4347-4349
Thiopyrimidine pairs in DNA duplexes were unexpectedly largely stabilized by complexation with two equivalents of Ag(I) ions and their binding properties were evaluated. The metal ion-binding properties of the thiopyrimidine base pairs differed significantly from those of unpaired bases. 相似文献