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941.
Venkatnathan A Szilva AB Walter D Gdanitz RJ Carter EA 《The Journal of chemical physics》2004,120(4):1693-1704
We recently developed a reduced scaling multireference configuration interaction (MRCI) method based on local correlation in the internal (occupied) and external (virtual) orbital spaces. This technique can be used, e.g., to predict bond dissociation energies in large molecules with reasonable accuracy. However, the inherent lack of size extensivity of truncated CI is a disadvantage that in principle worsens as the system size grows. Here we implement an a priori size-extensive modification of local MRCI known as the averaged coupled pair functional (ACPF) method. We demonstrate that local MR-ACPF recovers more correlation energy than local MRCI, in keeping with trends observed previously for nonlocal ACPF. We test the size extensivity of local ACPF on noninteracting He atoms and a series of hydrocarbons. Basis set and core correlation effects are explored, as well as bond breaking in a variety of organic molecules. The local MR-ACPF method proves to be a useful tool for investigating large molecules and represents a further improvement in predictive accuracy over local MRCI. 相似文献
942.
Zirconium is quantitatively precipitated by 2,5-dihydroxy-1,4-benzoquinone and is separated from scandium in 1 N hydrochloric acid solution. Thorium is separated at pH 0.5 from uranium(VI), cerium(IV), lanthanum, yttrium and scandium. Scandium is quantitatively precipitated by this reagent in the pH range 1.4–2.0 and at pH 1.5 equivalent amounts of lanthanum do not interfere; small amounts of yttrium cause interference. 相似文献
943.
Snyder CA Selegue JP Tice NC Wallace CE Blankenbuehler MT Parkin S Allen KD Beck RT 《Journal of the American Chemical Society》2005,127(43):15010-15011
1,3-Diaryl-4H-cyclopenta[c]thiophenes are efficiently prepared from 1,2-diaroylcyclopentadienes by use of Lawesson's reagent. eta5-Cyclopenta[c]thienyl complexes, [Mn(eta5-SC7H3-1,3-R2)(CO)3] (R = Me, Ph), are prepared in high yield by ligand substitution reactions of [MnBr(CO)5] with [SnMe3(SC7H3-1,3-R2)]. Alternatively, thiation with P4S10/NaHCO3 converts [Mn{eta5-1,2-C5H3(COR)2)(CO)3] to [Mn(eta5-SC7H3-1,3-R2)(CO)3] (R = Ph, 4-tolyl, 4-MeOC6H4, benzo[2,3-b]thienyl). The molecular structures of complexes with R = Me, Ph show planar eta5-cyclopenta[c]thienyl ligands, with the manganese atom slightly displaced away from the ring-fusion bond. 相似文献
944.
Uranium is preconcentrated from sea water, tap water, and solutions obtained by digestion of biological samples, by coprecipitation with 1-(2-pyridylazo)-2-naphthol (PAN). Coprecipitation is most effective at pH 4.5–6.5 with a recovery of 85–94%. In the presence of 0.1 M 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) as a masking agent, the method is highly selective for uranium. After neutron activation of the precipitate, uranium can be quantified via the 239U nuclide with a relatively low background in the region of interest (74 keV). Detection limits are 3–4 ng kg?1 for 500-ml water samples and 5 μg kg?1 for 0.5-g biological samples (after digestion). The method can be applied to most environmental samples, as shown by the results for sea water and three standard reference materials. 相似文献
945.
Jellen EE Chappell AM Ryzhov V 《Rapid communications in mass spectrometry : RCM》2002,16(19):1799-1804
The size-dependent stability of noncovalent complexes under collision-induced dissociation (CID) conditions was studied on a quadrupole ion trap mass spectrometer. Complexes of heme, tetraphenylporphyrin iron(III) (TPP-Fe), and tetraphenylporphyrin manganese(III) (TPP-Mn) with several histidine-containing peptides and model compounds were formed by electrospray ionization (ESI) and their stability was probed by variable-energy CID. It was found that the stability of complexes with the same (or nearly the same) binding energy has a linear dependence on the complex size (or total number of degrees of freedom). This approach will allow comparisons of variable-energy CID data for noncovalent complexes with different binding energies and could be used to help in structural elucidation of some complexes formed by multidentate ligands. The linearity of size effects on the stability of the complexes was also tested in three crown ether/protonated primary amine systems. 相似文献
946.
Guy Crundwell James Sullivan Ryan Pelto Katherine Kantardjieff 《Journal of chemical crystallography》2003,33(4):239-244
2,2-Thenil crystallizes in P21/c with a = 7.2501(12) Å, b = 4.7846(8) Å, c = 13.9867(23) Å, = 96.897(3), V = 481.67(14) Å3, and Z = 2. The molecule resides on an inversion center and is planar. 3,3-Thenil also crystallizes in P21/c with a = 3.9904(8) Å, b = 21.310(4) Å, c = 11.618(2) Å, = 101.83(3), V = 966.9(3) Å3, and Z = 4. Refinement of 3,3-thenil data indicated that 10.3(2)% of both thienyl rings are flip-disordered in this nonplanar molecule. A brief discussion of disorder in molecules containing terminal, unsubstituted 2- and 3-thienyl rings is presented. 相似文献
947.
The focus of this review is to present the current advances in Loop Heat Pipes (LHP) with flat evaporators, which address the current challenges to the wide implementation of the technology. A recent advance in LHP is the design of flat-shaped evaporators, which is better suited to the geometry of discretely mounted electronics components (microprocessors) and therefore negate the need for an additional transfer surface (saddle) between component and evaporator. However, various challenges exist in the implementation of flat-evaporator, including (1) deformation of the evaporator due to high internal pressure and uneven stress distribution in the non-circular casing; (2) heat leak from evaporator heating zone and sidewall into the compensation chamber; (3) poor performance at start-up; (4) reverse flow through the wick; or (5) difficulties in sealing, and hence frequent leakage. This paper presents and reviews state-of-the-art LHP technologies; this includes an (a) review of novel manufacturing methods; (b) LHP evaporator designs; (c) working fluids; and (d) construction materials. The work presents solutions that are used to develop or improve the LHP construction, overall thermal performance, heat transfer distance, start-up time (especially at low heat loads), manufacturing cost, weight, possibilities of miniaturization and how they affect the solution on the above-presented problems and challenges in flat shape LHP development to take advantage in the passive cooling systems for electronic devices in multiple applications. 相似文献
948.
Raf, a threonine/serine kinase in the Raf/MEK/ERK pathway, regulates cell proliferation. Raf''s full activation requires dimerization. Aberrant activation through dimerization is an important therapeutic target. Despite its clinical importance, fundamental questions, such as how the side-to-side dimerization promotes the OFF-to-ON transition of Raf''s kinase domain and how the fully activated ON-state kinase domain is stabilized in the dimer for Raf signaling, remain unanswered. Herein, we decipher an atomic-level mechanism of Raf activation through dimerization, clarifying this enigma. The mechanism reveals that the replacement of intramolecular π–π stacking by intermolecular π–π stacking at the dimer interface releases the structural constraint of the αC-helix, promoting the OFF-to-ON transition. During the transition, the inhibitory hydrophobic interactions were disrupted, making the phosphorylation sites in A-loop approach the HRD motif for cis-autophosphorylation. Once fully activated, the ON-state kinase domain can be stabilized by a newly identified functional N-terminal basic (NtB) motif in the dimer for Raf signaling. This work provides atomic level insight into critical steps in Raf activation and outlines a new venue for drug discovery against Raf dimerization.We decipher an atomic-level mechanism of Raf activation through dimerization, revealing that the disruption of intramolecular π–π stacking at the dimer interface promotes the OFF-to-ON transition. 相似文献
949.
John Ryan 《Mathematical Methods in the Applied Sciences》1997,20(18):1617-1624
We develop aspects of Clifford analysis over the sphere and hyperbolae. We focus primarily on the hyperbola lying in the Minkowski type space ℝn,1. We show that in order to give a proper extension of basic results on Clifford analysis in Euclidean space to this context one needs to consider both hyperbolae lying in ℝn,1. We also introduce Bergman spaces of Lp left monogenic sections in this context and consider the decomposition of square integrable sections over suitable bundles constructed over subdomains of spheres and hyperbolae. The results presented here cover the necessary background to enable one to set up and solve boundary value problems for field-type equations over hyperbolae. In particular, one can study analogues of the Dirichlet problem for analogues of the Laplacian over hyperbolae and spheres. © 1997 B. G. Teubner Stuttgart–John Wiley & Sons Ltd. 相似文献
950.
Frankie P. Anderson John F. Gallagher Peter T. M. Kenny Clodagh Ryan David Savage 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(1):m13-m15
The title compounds, [Fe(C5H5)(C14H13O2)] and [Fe(C5H5)(C15H15O2)], respectively, contain the ferrocenyl η5(C5H4) and phenylene –C6H4– rings in a nearly coplanar arrangement, with interplanar angles of 6.88 (12) and 10.5 (2)°, respectively. Molecules of the ethyl ester form dimers through η5(C5H5)C—H⋯O=C hydrogen bonds, with graph set R(20), and, together with Csp3—H⋯π(C5H5) interactions, generate a one‐dimensional column (irregular ladder). Molecules of the isopropyl ester aggregate through η5(C5H5)C—H⋯π(C6H4) interactions. 相似文献