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101.
102.
In recent work, we constructed a new near octagon \(\mathcal {G}\) from certain involutions of the finite simple group \(G_2(4)\) and showed a correspondence between the Suzuki tower of finite simple groups, \(L_3(2)< U_3(3)< J_2< G_2(4) < Suz\), and the tower of near polygons, \(\mathrm {H}(2,1) \subset \mathrm {H}(2)^D \subset \mathsf {HJ} \subset \mathcal {G}\). Here we characterize each of these near polygons (except for the first one) as the unique near polygon of the given order and diameter containing an isometrically embedded copy of the previous near polygon of the tower. In particular, our characterization of the Hall–Janko near octagon \(\mathsf {HJ}\) is similar to an earlier characterization due to Cohen and Tits who proved that it is the unique regular near octagon with parameters (2, 4; 0, 3), but instead of regularity we assume existence of an isometrically embedded dual split Cayley hexagon, \(\mathrm {H}(2)^D\). We also give a complete classification of near hexagons of order (2, 2) and use it to prove the uniqueness result for \(\mathrm {H}(2)^D\). 相似文献
103.
We define two transforms of non‐conformal harmonic maps from a surface into the 3‐sphere. With these transforms one can construct, from one such harmonic map, a sequence of harmonic maps. We show that there is a correspondence between harmonic maps into the 3‐sphere, H‐surfaces in Euclidean 3‐space and almost complex surfaces in the nearly Kähler manifold . As a consequence we can construct sequences of H‐surfaces and almost complex surfaces. 相似文献
104.
Huang C Soenen SJ Rejman J Lucas B Braeckmans K Demeester J De Smedt SC 《Chemical Society reviews》2011,40(5):2417-2434
Stimuli-responsive electrospun nanofibers are gaining considerable attention as highly versatile tools which offer great potential in the biomedical field. In this critical review, an overview is given on recent advances made in the development and application of stimuli-responsive fibers. The specific features of these electrospun fibers are highlighted and discussed in view of the properties required for the diverse applications. Furthermore, several novel biomedical applications are discussed and the respective advantages and shortcomings inherent to stimuli-responsive electrospun fibers are addressed (136 references). 相似文献
105.
Scheres L Rijksen B Giesbers M Zuilhof H 《Langmuir : the ACS journal of surfaces and colloids》2011,27(3):972-980
On H-Si(111) surfaces monolayer formation with 1-alkenes results in alkyl monolayers with a Si-C-C linkage, while 1-alkynes yield alkenyl monolayers with a Si-C═C linkage. Recently, considerable structural differences between both types of monolayers were observed, including an increased thickness, improved packing, and higher surface coverage for the alkenyl monolayers. The precise origin thereof could experimentally not be clarified yet. Therefore, octadecyl and octadecenyl monolayers on Si(111) were studied in detail by molecular modeling via PCFF molecular mechanics calculations on periodically repeated slabs of modified surfaces. After energy minimization the packing energies, structural properties, close contacts, and deformations of the Si surfaces of monolayers structures with various substitution percentages and substitution patterns were analyzed. For the octadecyl monolayers all data pointed to a substitution percentage close to 50-55%, which is due the size of the CH(2) groups near the Si surface. This agrees with literature and the experimentally determined coverage of octadecyl monolayers. For the octadecenyl monolayers the minimum in packing energy per chain is calculated around 60% coverage, i.e., close to the experimentally observed value of 65% [Scheres et al. Langmuir 2010, 26, 4790], and this packing energy is less dependent on the substitution percentage than calculated for alkyl layers. Analysis of the chain conformations, close contacts, and Si surface deformation clarifies this, since even at coverages above 60% a relatively low number of close contacts and a negligible deformation of the Si was observed. In order to evaluate the thermodynamic feasibility of the monolayer structures, we estimated the binding energies of 1-alkenes and 1-alkynes to the hydrogen-terminated Si surface at a range of surface coverages by composite high-quality G3 calculations and determined the total energy of monolayer formation by adding the packing energies and the binding energies. It was shown that due to the significantly larger reaction exothermicity of the 1-alkynes, thermodynamically even a substitution percentage as high as 75% is possible for octadecenyl chains. However, because sterically (based on the van der Waals footprint) a coverage of 69% is the maximum for alkyl and alkenyl monolayers, the optimal substitution percentage of octadecenyl monolayers will be presumably close to this latter value, and the experimentally observed 65% is likely close to what is experimentally maximally obtainable with alkenyl monolayers. 相似文献
106.
Bonnet S Limburg B Meeldijk JD Gebbink RJ Killian JA 《Journal of the American Chemical Society》2011,133(2):252-261
Electrostatic forces play an important role in the interaction between large transition metal complexes and lipid bilayers. In this work, a thioether-cholestanol hybrid ligand (4) was synthesized, which coordinates to ruthenium(II) via its sulfur atom and intercalates into lipid bilayers via its apolar tail. By mixing its ruthenium complex [Ru(terpy)(bpy)(4)](2+) (terpy = 2,2';6',2'-terpyridine; bpy = 2,2'-bipyridine) with either the negatively charged lipid dimyristoylphosphatidylglycerol (DMPG) or with the zwitterionic lipid dimyristoylphosphatidylcholine (DMPC), large unilamellar vesicles decorated with ruthenium polypyridyl complexes are formed. Upon visible light irradiation the ruthenium-sulfur coordination bond is selectively broken, releasing the ruthenium fragment as the free aqua complex [Ru(terpy)(bpy)(OH(2))](2+). The photochemical quantum yield under blue light irradiation (452 nm) is 0.0074(8) for DMPG vesicles and 0.0073(8) for DMPC vesicles (at 25 °C), which is not significantly different from similar homogeneous systems. Dynamic light scattering and cryo-TEM pictures show that the size and shape of the vesicles are not perturbed by light irradiation. Depending on the charge of the lipids, the cationic aqua complex either strongly interacts with the membrane (DMPG) or diffuses away from it (DMPC). Back coordination of [Ru(terpy)(bpy)(OH(2))](2+) to the thioether-decorated vesicles takes place only at DMPG bilayers with high ligand concentrations (25 mol %) and elevated temperatures (70 °C). During this process, partial vesicle fusion was also observed. We discuss the potential of such ruthenium-decorated vesicles in the context of light-controlled molecular motion and light-triggered drug delivery. 相似文献
107.
The circular birefringence of polycrystalline polymers is invariably obscured by strong linear birefringence. To parse the two mechanisms of light retardation, polycrystalline spherulites of polylactide enantiomers were analyzed by Mueller matrix microscopy. Polymer films are barely optically active in normal incidence, but if illuminated obliquely they become strongly optically active. Opposite hemispheres have oppositely signed circular birefringence. The sign is independent of the enantiomer but dependent on the sense of the sample's tilt. These observations are consistent with light path inhomogeneities resulting from stacked, mis-oriented lamellae. Chiroptical commonalities based on symmetry arguments are discussed among polylactide, a single oriented water molecule, and microfabricated metamaterial arrays, as well as the first physical model of optical activity, Reusch's pile of mica plates. The latter model provides the best explanation of the circular birefringence of polylactide spherulites. The only data on the optical rotation of crystalline polymers to date come from ostensible single crystals of polylactide. The enormous, anisotropic optical rotations observed previously are in quantitative agreement with misoriented lamellae observed here. Limitations of parsing circularly birefringent systems into those showing 'natural optical activity' and those others, somehow 'unnatural', are discussed. 相似文献
108.
Calcium selective electrodes with various membrane formulations were studied in solutions containing CaCl2 and sodium dodecylsulfate (NaDS). It is shown that electrodes based on neutral ionophores ETH 1001 and ETH 129 cannot be used as Ca2+ ion sensors in these solutions because of strong anion interference from DS? anion. Among other formulations, that based on calcium bis(tetramethylbutylphenyl)phosphate in tri(2‐ethylhexyl)phosphate appear the most promising. The interpretation of the ISE response in solutions under study relied on a novel approach which considers three forms of calcium: Ca2+ free ions, Ca in Ca(DS)2 precipitate, and Ca2+ bound by the DS? micelles. Data needed for the respective calculations were obtained by DS? selective electrode based on tetradecylammonium, and Na+ selective glass electrode. 相似文献
109.
Kádár Z Kovács D Frank É Schneider G Huber J Zupkó I Bartók T Wölfling J 《Molecules (Basel, Switzerland)》2011,16(6):4786-4806
A straightforward and reliable method for the regioselective synthesis of steroidal 1,4-disubstituted triazoles and 1,5-disubstituted tetrazoles via copper(I)-catalyzed cycloadditions is reported. Heterocycle moieties were efficiently introduced onto the starting azide compound 3β-acetoxy-16β-azidomethylandrost-5-en-17β-ol through use of the "click" chemistry approach. The antiproliferative activities of the newly-synthesized triazoles were determined in vitro on three human gynecological cell lines (HeLa, MCF7 and A2780) using the microculture tetrazolium assay. 相似文献
110.
Kádár Z Baji Á Zupkó I Bartók T Wölfling J Frank É 《Organic & biomolecular chemistry》2011,9(23):8051-8057
Stereoselective 1,4-Michael addition of azoimide to 17β-acetoxy-5α-adrost-1-en-3-one was carried out to furnish a 1α-azido-3-ketone, which was reduced to give the 3β- and 3α-hydroxy epimers in a ratio of 5 : 2. The Cu(I)-catalyzed 1,3-dipolar cycloaddition of the major isomer to terminal alkynes afforded 1α-triazolyl derivatives, which were deacetylated to the corresponding 3β,17β-diols or oxidized to the analogous 3-ketones. However, the ability of the minor 1α,3α-azidoalcohol to undergo similar cyclization was found to be affected significantly by the steric bulk of the substituents on the alkyne reaction partner. All triazolyl compounds were tested in vitro on three malignant gynecological cell lines (HeLa, MCF7 and A2780). 相似文献