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971.
Graham Smith 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(2):140-145
The Li, Rb and Cs complexes with the herbicide (2,4‐dichlorophenoxy)acetic acid (2,4‐D), namely poly[[aqua[μ3‐(2,4‐dichlorophenoxy)acetato‐κ3O1:O1:O1′]lithium(I)] dihydrate], {[Li(C8H5Cl2O3)(H2O)]·2H2O}n, (I), poly[μ‐aqua‐bis[μ3‐(2,4‐dichlorophenoxy)acetato‐κ4O1:O1′:O1′,Cl2]dirubidium(I)], [Rb2(C8H5Cl2O3)2(H2O)]n, (II), and poly[μ‐aqua‐bis[μ3‐(2,4‐dichlorophenoxy)acetato‐κ5O1:O1′:O1′,O2,Cl2]dicaesium(I)], [Cs2(C8H5Cl2O3)2(H2O)]n, (III), respectively, have been determined and their two‐dimensional polymeric structures are described. In (I), the slightly distorted tetrahedral LiO4 coordination involves three carboxylate O‐atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water molecules of solvation. Conjoined six‐membered ring systems generate a one‐dimensional coordination polymeric chain which extends along b and interspecies water O—H...O hydrogen‐bonding interactions give the overall two‐dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octahedral RbO5Cl coordination about Rb+ comprises a single bridging water molecule which lies on a twofold rotation axis, a bidentate Ocarboxy,Cl‐chelate interaction and three bridging carboxylate O‐atom bonding interactions from the 2,4‐D ligand. A two‐dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four‐membered Rb2O2 ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water molecule forms intralayer aqua–carboxylate O—H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z′ = 2) irregular CsO6Cl coordination centres, each comprising two O‐atom donors (carboxylate and phenoxy) and a ring‐substituted Cl‐atom donor from the 2,4‐D ligand species in a tridentate chelate mode, two O‐atom donors from bridging carboxylate groups and one from a bridging water molecule. However, the two 2,4‐D ligands are conformationally very dissimilar, with one phenoxyacetate side chain being synclinal and the other being antiperiplanar. The minimum Cs...Cs separation is 4.4463 (5) Å. Structure extension gives coordination polymeric layers which lie parallel to (001) and are stabilized by intralayer water–carboxylate O—H...O hydrogen bonds. 相似文献
972.
Graham Smith 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(6):499-505
4‐Nitrobenzoic acid (PNBA) has proved to be a useful ligand for the preparation of metal complexes but the known structures of the alkali metal salts of PNBA do not include the rubidium salt. The structures of the isomorphous potassium and rubidium polymeric coordination complexes with PNBA, namely poly[μ2‐aqua‐aqua‐μ3‐(4‐nitrobenzoato)‐potassium], [K(C7H4N2O2)(H2O)2]n, (I), and poly[μ3‐aqua‐aqua‐μ5‐(4‐nitrobenzoato)‐rubidium], [Rb(C7H4N2O2)(H2O)2]n, (II), have been determined. In (I), the very distorted KO6 coordination sphere about the K+ centres in the repeat unit comprise two bridging nitro O‐atom donors, a single bridging carboxylate O‐atom donor and two water molecules, one of which is bridging. In Rb complex (II), the same basic MO6 coordination is found in the repeat unit, but it is expanded to RbO9 through a slight increase in the accepted Rb—O bond‐length range and includes an additional Rb—Ocarboxylate bond, completing a bidentate O,O′‐chelate interaction, and additional bridging Rb—Onitro and Rb—Owater bonds. The comparative K—O and Rb—O bond‐length ranges are 2.7352 (14)–3.0051 (14) and 2.884 (2)–3.182 (2) Å, respectively. The structure of (II) is also isomorphous, as well as isostructural, with the known structure of the nine‐coordinate caesium 4‐nitrobenzoate analogue, (III), in which the Cs—O bond‐length range is 3.047 (4)–3.338 (4) Å. In all three complexes, common basic polymeric extensions are found, including two different centrosymmetric bridging interactions through both water and nitro groups, as well as extensions along c through the para‐related carboxylate group, giving a two‐dimensional structure in (I). In (II) and (III), three‐dimensional structures are generated through additional bridges involving the nitro and water O atoms. In all three structures, the two water molecules are involved in similar intra‐polymer O—H...O hydrogen‐bonding interactions to both carboxylate and water O‐atom acceptors. A comparison of the varied coordination behaviour of the full set of Li–Cs salts with 4‐nitrobenzoic acid is also made. 相似文献
973.
Open‐access microcavities are emerging as a new approach to confine and engineer light at mode volumes down to the λ3 regime. They offer direct access to a highly confined electromagnetic field while maintaining tunability of the system and flexibility for coupling to a range of matter systems. This article presents a study of coupled cavities, for which the substrates are produced using Focused Ion Beam milling. Based on experimental and theoretical investigation the engineering of the coupling between two microcavities with radius of curvature of 6 m is demonstrated. Details are provided by studying the evolution of spectral, spatial and polarisation properties through the transition from isolated to coupled cavities. Normal mode splittings up to 20 meV are observed for total mode volumes around . This work is of importance for future development of lab‐on‐a‐chip sensors and photonic open‐access devices ranging from polariton systems to quantum simulators.
974.
Surface and Structural Investigation of a MnOx Birnessite‐Type Water Oxidation Catalyst Formed under Photocatalytic Conditions 下载免费PDF全文
Benjamin J. Deibert Jingming Zhang Paul F. Smith Dr. Karena W. Chapman Dr. Sylvie Rangan Debasis Banerjee Kui Tan Hao Wang Nicholas Pasquale Prof. Feng Chen Prof. Ki‐Bum Lee Prof. G. Charles Dismukes Prof. Yves J. Chabal Prof. Jing Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):14218-14228
Catalytically active MnOx species have been reported to form in situ from various Mn‐complexes during electrocatalytic and solution‐based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnOx catalysts form without supports in situ under photocatalytic conditions. Our most active 4MnOx catalyst (~0.84 mmol O2 mol Mn?1 s?1) forms from a Mn4O4 bearing a metal–organic framework. 4MnOx is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR‐TEM as a disordered, layered Mn‐oxide with high surface area (216 m2g?1) and small regions of crystallinity and layer flexibility. In contrast, the SMnOx formed from Mn2+ salt gives an amorphous species of lower surface area (80 m2g?1) and lower activity (~0.15 mmol O2 mol Mn?1 s?1). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p3/2 core levels detects enriched Mn3+ and Mn2+ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria. 相似文献
975.
Vanessa C. Lussini Dr. James P. Blinco Dr. Kathryn E. Fairfull‐Smith Prof. Steven E. Bottle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18258-18268
Novel profluorescent mono‐ and bis‐isoindoline nitroxides linked to napthalimide and perylene diimide structural cores are described. These nitroxide‐fluorophore probes display strongly suppressed fluorescence in comparison to their corresponding non‐radical diamagnetic methoxyamine derivatives. The perylene‐based probe possessing two isoindoline systems tethered through ethynyl linkages was shown to be the most photostable in solution, demonstrating significantly enhanced longevity over the 9,10‐bis(phenylethynyl)anthracene fluorophore used in previous profluorescent nitroxide probes. 相似文献
976.
977.
Finding Alignment: The Perceptions and Integration of the Next Generation Science Standards Practices by Elementary Teachers 下载免费PDF全文
Preparing elementary‐level teachers to teach in alignment with the eight Next Generation Science Standards (NGSS) practices could prove to be a daunting endeavor. However, the process may be catalyzed by leveraging elements of teacher science instruction that inherently attend to the practice standards. In this study, we investigated the science instruction of three grade 3–5 elementary‐level teachers. We used observation, interviews, and surveys to determine the level to which the teachers perceived they taught and engaged in teaching science aligned with the eight NGSS practices. We found that the teachers were partially, and intrinsically implementing several of these practices in their instruction, and at the same time could not articulate the eight NGSS practices. Our results suggest there may be ample opportunity to build on the current science instruction of elementary‐level teachers to bring their instruction into alignment with the NGSS. We found that teachers’ perceive professional development, school culture, and access to additional instructional resources to be essential to their adoption of the NGSS practices. 相似文献
978.
C.W. Smith O. Olaosebikan J.S. Epstein 《Theoretical and Applied Fracture Mechanics》1984,2(2):157-169
The traction continuity condition is used to delineate the elastic linear zone (ELZ) for the extraction of the Mode I stress intensity factor (SIF) from photoelastic data. The procedure requires an estimation, with the aid of experimental data, of some non-dimensional quantities which are the ratios of unknown parameters of the LEFM equations and the corresponding ones for an infinite body problem. Furthermore, the crack tip nonlinear zone is assumed to admit of plastic deformation with small-scale yielding.The estimation of the ELZ thus obtained seems to predict well the experimentally observed one. 相似文献
979.
Global stability for infinite-delay,dispersive Lotka-Volterra systems: Weakly interacting populations in nearly identical patches 总被引:1,自引:0,他引:1
A Lotka-Volterra-like model ofm interacting species which can disperse amongn discrete habitats and where species interaction terms involve general unbounded delays is shown to possess a globally stable equilibrium when the undelayed intraspecific competition term dominates interspecific interactions as well as the delayed intraspecific competition effect and when then habitats are nearly identical. 相似文献
980.
Experimental results on the stability of circumferential growth of through-wall cracks in brass tubes, show that non-uniform bending can adversely affect the crack stability criterion. The results are relevant to the important technological problem of crack stability in 304 stainless steel pipes used in Boiling Water Reactors. 相似文献