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71.
Alan K. Brisdon Abeer M. T. Muneer Robin G. Pritchard 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(10):900-902
Halogen bonding is an intermolecular interaction capable of being used to direct extended structures. Typical halogen‐bonding systems involve a noncovalent interaction between a Lewis base, such as an amine, as an acceptor and a halogen atom of a halofluorocarbon as a donor. Vapour‐phase diffusion of 1,4‐diazabicyclo[2.2.2]octane (DABCO) with 1,2‐dibromotetrafluoroethane results in crystals of the 1:1 adduct, C2Br2F4·C6H12N2, which crystallizes as an infinite one‐dimensional polymeric structure linked by intermolecular N...Br halogen bonds [2.829 (3) Å], which are 0.57 Å shorter than the sum of the van der Waals radii. 相似文献
72.
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
73.
Sergey G. Arkhipov Denis A. Rychkov Alexey M. Pugachev Elena V. Boldyreva 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):584-592
Crystals of maleates of three amino acids with hydrophobic side chains [L‐leucenium hydrogen maleate, C6H14NO2+·C4H3O4−, (I), L‐isoleucenium hydrogen maleate hemihydrate, C6H14NO2+·C4H3O4−·0.5H2O, (II), and L‐norvalinium hydrogen maleate–L‐norvaline (1/1), C5H11NO2+·C4H3O4−·C5H12NO2, (III)], were obtained. The new structures contain C22(12) chains, or variants thereof, that are a common feature in the crystal structures of amino acid maleates. The L‐leucenium salt is remarkable due to a large number of symmetrically non‐equivalent units (Z′ = 3). The L‐isoleucenium salt is a hydrate despite the fact that L‐isoleucine is a nonpolar hydrophobic amino acid (previously known amino acid maleates formed hydrates only with lysine and histidine, which are polar and hydrophilic). The L‐norvalinium salt provides the first example where the dimeric cation L‐Nva...L‐NvaH+ was observed. All three compounds have layered noncentrosymmetric structures. Preliminary tests have shown the presence of the second harmonic generation (SGH) effect for all three compounds. 相似文献
74.
Malliavin calculus is implemented in the context of Hairer (2014) [16]. This involves some constructions of independent interest, notably an extension of the structure which accommodates a robust, and purely deterministic, translation operator, in -directions, between “models”. In the concrete context of the generalized parabolic Anderson model in 2D – one of the singular SPDEs discussed in the afore-mentioned article – we establish existence of a density at positive times. 相似文献
75.
This paper investigates some properties of approximate efficiency in variable ordering structures where the variable ordering structure is given by a special set valued map. We characterize -minimal and - nondominated elements as approximate solutions of a multiobjective optimization problem with a variable ordering structure and give necessary and sufficient conditions for these solutions, via scalarization. 相似文献
76.
We consider a linear parabolic problem in a thick junction domain which is the union of a fixed domain and a collection of periodic branched trees of height of order 1 and small width connected on a part of the boundary. We consider a three‐branched structure, but the analysis can be extended to n‐branched structures. We use unfolding operator to study the asymptotic behavior of the solution of the problem. In the limit problem, we get a multi‐sheeted function in which each sheet is the limit of restriction of the solution to various branches of the domain. Homogenization of an optimal control problem posed on the above setting is also investigated. One of the novelty of the paper is the characterization of the optimal control via the appropriately defined unfolding operators. Finally, we obtain the limit of the optimal control problem. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
77.
《化学:亚洲杂志》2017,12(22):2942-2949
Hollow hybrid nanostructures have received significant attention because of their unique structural features. This study reports a facile ion adsorption–heating method to fabricate hollow PbS‐TiO2 hybrid particles. In this method, the TiO2 spheres used as a substrate material to grow PbS are aggregates of many small amorphous TiO2 particles, and each small particle is covered with thioglycolic acid ligands through Ti4+–carboxyl coordination. When Pb2+ ions are added to a colloidal solution of these TiO2 spheres, these ions are adsorbed by sulfhydryl (‐SH) groups to form metal thiolates, and the C−S bond is dissociated by heating to release S2−. The S2− ions react with Pb2+ ions to form PbS without additive sulfur sources. Additionally, the amorphous TiO2 spheres are transformed into the anatase phase during the heating process. As a result, the crystallization of TiO2 spheres along with the formation of PbS is simultaneously carried out by heating. During the heating process, owing to the Kirkendall effect of S2− diffusion and the Ostwald ripening effect of the crystallization of amorphous TiO2 spheres, PbS‐TiO2 hollow hybrid structures can be obtained. The XRD and XPS characterizations proved the formation of anatase TiO2 and PbS. The TEM characterization confirmed the formation of hollow structures in the PbS‐TiO2 hybrid sample. The photocatalytic activity of the hollow PbS‐TiO2 hybrid spheres have been investigated for the degradation of Cr6+ under visible light. The results show that hollow PbS‐TiO2 hybrid spheres exhibited the highest photocatalytic activity, in which almost all the Cr6+ was degraded after 140 min. 相似文献
78.
《化学:亚洲杂志》2017,12(1):36-40
N‐doped mesoporous carbon‐capped MoO2 nanobelts (designated as MoO2@NC) were synthesized and applied to lithium‐ion storage. Owing to the stable core–shell structural framework and conductive mesoporous carbon matrix, the as‐prepared MoO2@NC shows a high specific capacity of around 700 mA h g−1 at a current of 0.5 A g−1, excellent cycling stability up to 100 cycles, and superior rate performance. The N‐doped mesoporous carbon can greatly improve the conductivity and provide uninhibited conducting pathways for fast charge transfer and transport. Moreover, the core–shell structure improved the structural integrity, leading to a high stability during the cycling process. All of these merits make the MoO2@NC to be a suitable and promising material for lithium ion battery. 相似文献
79.
《Angewandte Chemie (International ed. in English)》2017,56(20):5475-5479
Gaining external control over self‐organization is of vital importance for future smart materials. Surfactants are extremely valuable for the synthesis of diverse nanomaterials. Their self‐assembly is dictated by microphase separation, the hydrophobic effect, and head‐group repulsion. It is desirable to supplement surfactants with an added mode of long‐range and directional interaction. Magnetic forces are ideal, as they are not shielded in water. We report on surfactants with heads containing tightly bound transition‐metal centers. The magnetic moment of the head was varied systematically while keeping shape and charge constant. Changes in the magnetic moment of the head led to notable differences in surface tension, aggregate size, and contact angle, which could also be altered by an external magnetic field. The most astonishing result was that the use of magnetic surfactants as structure‐directing agents enabled the formation of porous solids with 12‐fold rotational symmetry. 相似文献
80.
《Angewandte Chemie (International ed. in English)》2017,56(20):5512-5516
Hollow metal–organic frameworks (MOFs) are promising materials with sophisticated structures, such as multiple shells, that cannot only enhance the properties of MOFs but also endow them with new functions. Herein, we show a rational strategy to fabricate multi‐shelled hollow chromium (III) terephthalate MOFs (MIL‐101) with single‐crystalline shells through step‐by‐step crystal growth and subsequent etching processes. This strategy relies on the creation of inhomogeneous MOF crystals in which the outer layer is chemically more robust than the inner layer and can be selectively etched by acetic acid. The regulation of MOF nucleation and crystallization allows the tailoring of the cavity size and shell thickness of each layer. The resultant multi‐shelled hollow MIL‐101 crystals show significantly enhanced catalytic activity during styrene oxidation. The insight gained from this systematic study will aid in the rational design and synthesis of other multi‐shelled hollow structures and the further expansion of their applications. 相似文献