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991.
Yuri I. Gorlov Ivan I. Ukrainsky Vladimir V. Penkovsky 《Theoretical chemistry accounts》1974,34(1):31-38
The UHF-CNDO/2 calculations have been performed for several radicals containing C, Si or P. The equilibrium geometries found by the minimization of the total energies and calculated spin densities are compared with results from ESR experiments and INDO calculations. The electronic structure of the radicals is discussed for their equilibrium geometries. 相似文献
992.
Marine toxins targeting the actin cytoskeleton represent a new and promising class of anti-cancer compounds. Here we present a 2.0 A resolution structure of swinholide A, a marine macrolide, bound to two actin molecules. The structure demonstrates that the actin dimer in the complex does not represent a physiologically relevant entity, for the two actin molecules do not interact with each other. The swinholide A actin binding site is the same as that targeted by toxins of the trisoxazole family and numerous actin binding proteins, highlighting the importance of this site in actin polymerization. The observed structure reveals the mechanism of action of swinholide A and provides a structural framework about which to design new agents directed at the cytoskeleton. 相似文献
993.
Motional heterogeneity and phase separation of functionalized polyester polyurethanes 总被引:1,自引:0,他引:1
The polyester polyurethanes, PU based on isophoronediisocyanate, polycaprolactone, and 1,4-butanediol with different amounts of functional groups introduced into the hard segments via second chain extender, 2,2′-bis-(hydroxymethyl) propionic acid, were investigated by electron spin resonance, ESR, spin label method, wide-angle X-ray diffraction, WAXD, optical microscopy and differential scanning calorimetry, DSC. The objective of this study is to clarify the effect of functional groups on the motional heterogeneity, microphase separation and crystallisation of the polyurethanes. The concentration of carboxylic groups varied from 0 to 0.45 mmol g−1. The temperature-dependent ESR spectra of spin labelled PU hard segments chain ends with stable nitroxide radical 2,2,6,6-tetramethyl-4-aminopiperidin-1-yloxyl are sensitive to the amount of functional groups attached to the hard segments. Composite ESR spectra of functionalized PU, with fast and slow component, suggest that PU hard segments are partitioned in two motionally different environments. According to the ratio of fast and slow component motional heterogeneity increases with an increase of functional groups up to 0.35 mmol g−1 and above this concentration slow component decreases indicating higher degree of phase mixing and stronger effect of soft segments. Polarized micrographs and the extent of ordering from WAXD measurements reveal the changes of phase morphology with the carboxylic groups content in a similar way as shown from the motional behaviour of spin label on the segmental level. The degree of crystallinity and the separation of spherulitic rings are decreasing above a certain concentration of functional groups. The effect of functional groups in PU on the hard and soft segment mixing is discussed in terms of additional noncovalent interactions and chain structure which at critical level of interactions lead to a formation of more open hard segment structure accessible to interaction with the soft segment. 相似文献
994.
Boltzmann-like distributions appear in many properties and energy-related quantities of proteins. A few examples are hydrophobicity, various types of side-chain/side-chain interactions, proline isomerization, hydrogen bonds, internal cavities, interactions at the level of specific atom types, and the propensity of the phi/'phi' ratio. Here, we conjecture that the Boltzmann hypothesis also holds for the intra-residue energy distribution. We confirm the conjecture by calculating the energies of 41,672 residues of the structures of highly resolved proteins, where at least 12 out of 20 naturally occurring amino acids follow Boltzmann's law. We further examine the entire set of all residue energies and find that the convolution of the individual distributions gives a Poisson function, which is followed by approximately 50% of individual proteins' structures. 相似文献
995.
An analytical method is presented based on reverse isotope dilution single detector inductively coupled plasma magnetic sector mass spectrometry (ID-ICP-SMS) and applied to the specific case of the certification of a (111)Cd enriched candidate Cd spike calibration material (nominal mass fraction 10 mg kg(-1) in 5% HNO3 solution). Uncertainty propagation was used as a tool for both determining the analytical approach and validating it. The robustness of close to "exact matching" reverse IDMS to correction of measured isotope intensities for multiplicative (mass discrimination) and (semi)additive effects (dead time, instrumental background, and isobaric interference) is discussed. The very low experimental relative standard deviation of the mean (0.08%) of eight replicate determinations indicated that all significant sources of uncertainty had probably been taken into account for the estimation of the final combined uncertainty statement (U(c) = 0.17%, k = 1). IRMM-621 was used as comparator. Uncertainties on IUPAC isotopic abundances of 111Cd and 112Cd, for the natural Cd solution involved between the two enriched materials, formed nearly 60% of U(c). The repeatability of the isotope ratio measurements contributed less than 10%. Correction for procedural blank necessitated somewhat unusual calculations (potential contamination of an enriched material with natural Cd). The procedure also involved a quadrupole based ICP-MS judged to be appropriate for the characterization of the isotopic composition. For comparison purposes, direct IDMS results are simulated using identical experimental input data. Finally, a significant background signal in the 106-116 mass region, observed only with the magnetic sector instrument, was attributed to argon based isobaric interferences. 相似文献
996.
Optimal design with respect to the variable thickness of an elastic beam with unilateral supports under the criterion of minimal value of the maximal stress is presented in Part I. A dual formulation of the state problem (in terms of bending moments) is used and the convergence of some approximations proved.In Part III the variable thickness of an elastic or elasto-plastic plate unilaterally supported on a part of its edge is optimized. For elastic plates with parallel edges a primal finite element model is applied and a convergence result obtained. 相似文献
997.
A natural supersymmetric extension
is defined of the current (= affine Kac-Moody Lie) algebra
; it corresponds to a superconformal and chiral invariant 2-dimensional quantum field theory (QFT), and hence appears as an ingredient in superstring models. All unitary irreducible positive energy representations of
are constructed. They extend to unitary representations of the semidirect sumS
(G) of
with the superconformal algebra of Neveu-Schwarz, for
, or of Ramond, for =0.On leave of absence from the Institute for Nuclear Research and Nuclear Energy of the Bulgarian Academy of Sciences, BG-1184 Sofia, Bulgaria 相似文献
998.
999.
Mirjam S. Studer Roland Künzli Reto Maier Michael W. I. Schmidt Rolf T. W. Siegwolf Ivan Woodhatch 《Isotopes in environmental and health studies》2017,53(3):286-297
Plant–soil interactions are recognized to play a crucial role in the ecosystem response to climate change. We developed a facility to disentangle the complex interactions behind the plant–soil C feedback mechanisms. The MICE (‘Multi-Isotope labelling in a Controlled Environment’) facility consists of two climate chambers with independent control of the atmospheric conditions (light, CO2, temperature, humidity) and the soil environment (temperature, moisture). Each chamber holds 15 plant–soil systems with hermetical separation of the shared above ground (shoots) from the individual belowground compartments (roots, rhizosphere, soil). Stable isotopes (e.g. 13C, 15N, 2H, 18O) can be added to either compartment and traced within the whole system. The soil CO2 efflux rate is monitored, and plant material, leached soil water and gas samples are taken frequently. The facility is a powerful tool to improve our mechanistic understanding of plant–soil interactions that drive the C cycle feedback to climate change. 相似文献
1000.