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781.
Vicinelli V Ceroni P Maestri M Balzani V Gorka M Vögtle F 《Journal of the American Chemical Society》2002,124(22):6461-6468
We have investigated the complexation of the luminescent Nd(3+), Eu(3+), Gd(3+), Tb(3+), Er(3+), and Yb(3+) ions by a polylysin dendrimer containing 21 amide groups in the interior and, in the periphery, 24 chromophoric dansyl units which show an intense fluorescence band in the visible region. Most of the experiments were performed in 5:1 acetonitrile/dichloromethane solution at 298 K. On addition of the lanthanide ions to dendrimer solutions, the fluorescence of the dansyl units is quenched; in Nd(3+), Er(3+), and Yb(3+), a sensitized near-infrared emission of the lanthanide ion is observed. At low metal ion concentrations, each dendrimer hosts only one metal ion and when the hosted metal ion is Nd(3+) or Eu(3+), the fluorescence of all the 24 dansyl units of the dendrimer is quenched with unitary efficiency. Quantitative measurements were performed in a variety of experimental conditions, including protonation of the dansyl units and measurements in rigid matrix at 77 K where a sensitized Eu(3+) emission could also be observed. The results obtained have been interpreted on the basis of the energy levels and redox potentials of dendrimer and metal ions. 相似文献
782.
Slootweg JC de Kanter FJ Schakel M Lutz M Spek AL Kozhushkov SI de Meijere A Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):6982-6993
Novel, highly stable, linear and branched mono- and diphospha[n]triangulanes were synthesized in high yields by the CuCl-catalyzed phosphinidene addition to spirocyclopropanated methylenecyclopropanes and bicyclopropylidenes. The effect of spirofusion on the electronic properties of these esthetically attractive phosphacycles is apparent from X-ray single crystal structure analyses, which reveals a tightening of the phosphirane ring on additional spirocyclopropanation, and from the NMR features that show deshielded chemical shifts for the ring-phosphorus and -carbon atoms. Steric factors play a role in the addition reaction when the substrate alkene carries a second sphere of spirocyclopropane rings and causes the formation of 2-phosphabicyclo[3.2.0]heptenes in small amounts. These by-products most probably result from addition of the [PhP(Cl)W(CO)(5)]-Cu-L (L=alkene or solvent) reagent to the spirocyclopropanated bicyclopropylidene to give an intermediate sigma-complex, which subsequently, facilitated by steric factors, undergoes a cyclopropylcarbinyl to cyclobutyl ring expansion followed by a [1,3]-sigmatropic shift. 相似文献
783.
Saudan C Balzani V Gorka M Lee SK Maestri M Vicinelli V Vögtle F 《Journal of the American Chemical Society》2003,125(15):4424-4425
We have investigated the formation of metal complexes between Zn2+ and two derivatives, 1 and 2, of the well-known 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand. Compound 1 is 1,4,8,11-tetrakis(naphthylmethyl) cyclam, and compound 2 is a dendrimer consisting of a cyclam core with appended 12 dimethoxybenzene and 16 naphthyl units. Compound 1 exhibits an emission band with a maximum around 480 nm, assigned to the formation of exciplexes between amine and excited naphthyl units. Dendrimer 2 exhibits three types of weak emission bands, assigned to naphthyl localized excited states (lambdamax = 337 nm), naphthyl excimers (lambdamax ca. 390 nm), and naphthyl-amine exciplexes (lambdamax = 480 nm). In CH3CN-CH2Cl2 1:1 v/v, titration of ligand 1 with Zn2+ causes the disappearance of the exciplex emission and the appearance of a strong naphthyl localized fluorescence; the titration plot is linear and reaches a plateau for a 1:1 stoichiometry, showing that a highly stable [Zn(1)]2+ complex is formed. In the case of 2, titration with Zn2+ causes the disappearance of the exciplex band, with a concomitant increase in the excimer and naphthyl localized emissions; the titration plot is again linear, but in this case it reaches a plateau for a 2:1 stoichiometric ratio, showing the unexpected formation of a [Zn(2)2]2+ complex. Such an unexpected stoichiometry for the complex of the dendritic ligand has been fully confirmed by 1H NMR titrations. The results obtained show that the dendrimer branches not only do not hinder, but in fact favor coordination of cyclam to Zn2+. 相似文献
784.
A simple and reliable method for docking protein-protein complexes using (1)H(N)/(15)N chemical shift mapping and backbone (15)N-(1)H residual dipolar couplings is presented and illustrated with three complexes (EIN-HPr, IIA(Glc)-HPr, and IIA(Mtl)-HPr) of known structure. The (1)H(N)/(15)N chemical shift mapping data are transformed into a set of highly ambiguous, intermolecular distance restraints (comprising between 400 and 3000 individual distances) with translational and some degree of orientational information content, while the dipolar couplings provide information on relative protein-protein orientation. The optimization protocol employs conjoined rigid body/torsion angle dynamics in simulated annealing calculations. The target function also comprises three nonbonded interactions terms: a van der Waals repulsion term to prevent atomic overlap, a radius of gyration term (E(rgyr)) to avoid expansion at the protein-protein interface, and a torsion angle database potential of mean force to bias interfacial side chain conformations toward physically allowed rotamers. For the EIN-HPr and IIA(Glc)-HPr complexes, all structures satisfying the experimental restraints (i.e., both the ambiguous intermolecular distance restraints and the dipolar couplings) converge to a single cluster with mean backbone coordinate accuracies of 0.7-1.5 A. For the IIA(Mtl)-HPr complex, twofold degeneracy remains, and the structures cluster into two distinct solutions differing by a 180 degrees rotation about the z axis of the alignment tensor. The correct and incorrect solutions which have mean backbone coordinate accuracies of approximately 0.5 and approximately 10.5 A, respectively, can readily be distinguished using a variety of criteria: (a) examination of the overall (1)H(N)/(15)N chemical shift perturbation map (because the incorrect cluster predicts the presence of residues at the interface that experience only minimal chemical shift perturbations; this information is readily incorporated into the calculations in the form of ambiguous intermolecular repulsion restraints); (b) back-calculation of dipolar couplings on the basis of molecular shape; or (c) the E(rgyr) distribution which, because of its global nature, directly reflects the interfacial packing quality. This methodology should be particularly useful for high throughput, NMR-based, structural proteomics. 相似文献
785.
786.
Eugen A. Preoteasa Elena Preoteasa Constantin Ciortea Daniel D. Marin Dan Gurban Marius Gugiu Adela Scafes 《X射线光谱测定》2009,38(6):548-556
Simultaneous particle‐induced x‐ray emission (PIXE) and particle‐induced gamma‐ray emission (PIGE) measurements in the 0–270 keV range with a low‐energy hyperpure Ge detector have been performed on the outer surface and on an inner section of a dental composite filling extracted from a patient. The biomaterial has been identified as the fluorine‐releasing Tetric Ceram dental composite. Compared to the native material, the dental filling evidenced changes occurring during the in vivo oral use. These included mainly Cl and K accumulation and loss of Zr, Ba, Yb (by PIXE), and F (in the PIGE region). The changes were similar at the surface and inside of the dental filling for most of the above elements, indicating an unexpectedly high permeability of the material, maybe due to microscopic bulk fracture of the dental composite filling throughout its use. The PIGE spectra detected also Al and traces of Hf and Sm possibly associated with Zr and Yb. Changes in the ratio of the L lines of Yb and in the ratio of the 110‐ and 197‐keV lines of F evidenced alterations in the matrix physical properties of the composite, associated with factors such as surface roughening by wear, grain size decrease by slow dissolution, and compositional variations. Further studies are needed to gain a deeper insight into the complex changes taking place in a dental composite filling. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
787.
788.
The present paper is dedicated to the study of the global existence for the inviscid two-dimensional Boussinesq system. We
focus on finite energy data with bounded vorticity and we find out that, under quite a natural additional assumption on the
initial temperature, there exists a global unique solution. No smallness conditions are imposed on the data. The global existence
issues for infinite energy initial velocity, and for the Bénard system are also discussed. 相似文献
789.
We study the regularity of the Navier-Stokes equations in arbitrary Lipschitz domains. 相似文献
790.
To determine the dynamic response of a structure under the influence of the fluid flow one must solve a coupled computational fluid dynamics (CFD) and computational structural dynamics (CSD) mathematical problem. This paper presents the comparison of two methods for the calculation of the fluid-structure interaction. The first one is of explicit-implicit type and uses a staggered time advancement of the fluid and structure problems. The second uses a fully implicit discretization in the physical time of the fluid-structure equations and an explicit advancement in the dual-time. The physical fluid-structure problem is accompanied by the equations of the mesh motion, which are written as for a pseudo-structural system with its own dynamics. Representative numerical results are presented for the two degrees of freedom tipical section in unsteady transonic flow. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献