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991.
992.
A series of silica-based tetracycline (TC)-imprinted xerogel sorbents were prepared by sol-gel processing and were characterized for TC binding. Molecularly imprinted xerogels (MIXs) formed from allyltriethoxysilane (AtEOS) and tetraethoxysilane (TEOS) and end capped with trimethylchlorosilane exhibited the best analytical performance (imprinting factor, IF, of 7.46±0.13). Computational modeling was used to estimate the interaction energy (IE) between TC and each type of silane to evaluate our ability to predict the analytical performance of a given MIX. Rankings from the computations agreed with the experimental data showing the AtEOS having the highest IE in comparison to the other formulations. Together, these results demonstrate the potential and limitations of using theoretical calculations to guide the development of analyte selective MIXs in comparison to arbitrary trial and error approaches traditionally used to produce MIXs as sorbents for solid phase extraction. 相似文献
993.
Building on [BB1] we prove a general criterion for convergence of (possibly singular) Bergman measures towards pluripotential-theoretic
equilibrium measures on complex manifolds. The criterion may be formulated in terms of the growth properties of the unit-balls
of certain norms on holomorphic sections, or equivalently as an asymptotic minimization property for generalized Donaldson
L-functionals. Our result settles in particular a well-known conjecture in pluripotential theory concerning the equidistribution
of Fekete points and it gives the convergence of Bergman measures towards the equilibrium measure for Bernstein-Markov measures.
Applications to interpolation of holomorphic sections are also discussed. 相似文献
994.
Thakur M Weng A Bachran D Riese SB Böttger S Melzig MF Fuchs H 《Electrophoresis》2011,32(21):3085-3089
Saponinum album (SA) is a commercial mixture of saponins isolated from Gypsophila species. In the previously published work, we reported that SA dramatically improves the inhibition of tumor growth by targeted toxins in mice in a synergistic way. Here we report a simplified electrophoretic method for the isolation of a highly effective fraction of SA with a relative electrophoretic mobility to the dye front (R(f) ) of 0.63 from the mixture. In total, four different fractions were separated at a preparative scale, and evaluated by ESI-MS, HPLC and TLC analysis. Electrophoretic mobility and electrochemical properties of the different fractions of saponins from SA were set into relation to their ability to enhance the cytotoxicity of epidermal growth factor (EGF)-based targeted toxins. We here treated HER-14 cells, which are NIH-3T3 Swiss mouse embryo cells transfected with the human EGF receptor. Untransfected NIH-3T3 cells served as control. The major bulk of SA (72.3%) (R(f) =0.78) migrated the farthest and was found to be significantly ineffective (p<0.05) in enhancing the cytotoxicity of the targeted toxin, while the second fraction (R(f) =0.63) showed an enhancement of 9800-fold. The third (R(f) =0.56) had an enhancement factor of 3200, the fourth (R(f) =0.08) was again significantly ineffective (p<0.05) in exhibiting any enhancement of cytotoxicity. 相似文献
995.
Diana Wischang Oliver Brücher Jens Hartung 《Coordination chemistry reviews》2011,255(19-20):2204-2217
The discovery of enzymes that utilize hydrogen peroxide to oxidize bromide under physiological conditions provided a strong stimulus to the field of oxidative bromination. A synthetically useful enzyme, to catalyze the oxidation of bromide, for bromofunctionalization of donor-substituted arenes in solutions of hydrogen peroxide and sodium bromide, is a vanadate(V)-dependent bromoperoxidase from the brown alga Ascophyllum nodosum. This enzyme operates in homogeneous solutions of buffered aqueous tert-butanol (pH 6.2), or, to simplify repetitive use, in a two-phase system after immobilization onto magnetic beads. Synthesis of cyclic bromohydrin ethers (tetrahydrofurans and tetrahydropyrans) and vicinal dibromides from unsaturated hydrocarbons, on the other hand, occurs more effectively in polar aprotic solvents. Under such conditions the more lipophilic tert-butyl hydroperoxide serves as oxidant, which is activated by oxovanadium(V) complexes (functional bromoperoxidase mimics). Protons and bromide ions, which are consumed for in situ generation of bromine, are supplied in organic solution by fragmentation of 3-bromopropionic acids. The structure-reactivity data obtained from oxidations catalyzed by bromoperoxidases and functional enzyme mimics pose a valuable guideline for predicting selectivity in biomimetic synthesis of organobromines from terpenes, acetogenins, and pyrrole alkaloids. 相似文献
996.
Arbuse A Mandal S Maji S Martínez MA Fontrodona X Utz D Heinemann FW Kisslinger S Schindler S Sala X Llobet A 《Inorganic chemistry》2011,50(15):6878-6889
The preparation and characterization of three new macrocyclic ligands with pendant arms based on the [2+2] condensation of isophthalaldehyde and the corresponding triamine substituted at the central N-atom is reported. None of these new macrocyclic ligands undergo any equilibrium reaction, based on imine hydrolysis to generate [1+1] macrocyclic formation or higher oligomeric compounds, such as [3+3], [4+4], etc., at least within the time scale of days. This indicates the stability of the newly generated imine bond. In sharp contrast, the reaction of the [2+2] macrocyclic Schiff bases with Cu(I) generates the corresponding dinuclear Cu(I) complexes [Cu(2)(L(1))](2+), 1(2+); [Cu(2)(L(2))(CH(3)CN)(2)](2+), 2(2+); and [Cu(2)(L(3))(CH(3)CN)(2)](2+), 3(2+), together with their trinuclear Cu(I) homologues [Cu(3)(L(4))](3+), 4(3+); [Cu(3)(L(5))(CH(3)CN)(3)](3+), 5(3+); and [Cu(3)(L(6))(CH(3)CN)(3)](3+), 6(3+), where the [2+2] ligand has undergone an expansion to the corresponding [3+3] Schiff base that is denoted as L(4), L(5), or L(6). The conditions under which the dinuclear and trinuclear complexes are formed were analyzed in terms of solvent dependence and synthetic pathways. The new complexes are characterized in solution by NMR, UV-vis, and MS spectroscopy and in the solid state by X-ray diffraction analysis and IR spectroscopy. For the particular case of the L(2) ligand, MS spectroscopy is also used to monitor the metal assisted transformation where the dinuclear complex 2(2+) is transformed into the trinuclear complex 5(3+). The Cu(I) complexes described here, in general, react slowly (within the time scale of days) with molecular oxygen, except for the ones containing the phenolic ligands 2(2+) and 5(3+) that react a bit faster. 相似文献
997.
The strength of the interaction between a pesticide and the soil organic matter is a key parameter to assess the risk of it reaching to groundwater with potentially harmful effects to human health. In this work, a new approach that allows measuring such interactions in a few minutes using a purified fraction of the soil organic matter (humic substances) is detailed. The strength of sorption is assessed via the normalised difference of elution (retention factor, k′) between the chemical of interest and a neutral marker transported via electroosmotic flow through an open tubular column supporting the immobilised humic substances (open tubular capillary electrochromatography). The immobilisation was achieved by incubating a capillary, pre-coated with a monolayer of humic acid, with an acidic solution of humic substances. This induces the formation of a supramolecular structure of humic substances as it occurs in soils. This aggregate can easily be removed using alkaline solutions, and a new structure assembled using other humic substances (HS) or different incubations conditions. The whole procedure takes 2 h. This approach has been tested using five triazines and three types of humic substances. The order of the strength of sorption of the triazines as expected from relevant literature and the relative standard deviation of k′ was between 1 and 6%. Good repeatability was also observed after long period of wash, between re-coating and repeating of the full coating with a new capillary. 相似文献
998.
Absolute pitch, the rare ability to identify or produce a musical tone without a reference tone, has been shown to be advantageous in some musical tasks; however, its relevance in musical contexts primarily involving relative pitch has been questioned. To explore this issue, 36 trained musicians-18 absolute pitch possessors and 18 non-possessors with equivalent age of onset and duration of musical training-were tested on interval naming tasks requiring only relative pitch. The intervals to be named were either ascending or descending with separation ranging from 1 to 12 semitones and equally involved all 12 pitch classes. Three different conditions were employed; these used brief sine waves, piano tones, and piano tones preceded by a V7-I chord cadence so as to establish a tonal context. The possession of absolute pitch was strongly correlated with enhanced performance on all these tests of relative pitch. Furthermore, no evidence was found that this absolute pitch avantage depended on key, interval size, or musical context. 相似文献
999.
We introduce a direct wavefront sensing method using structures labeled with fluorescent proteins in tissues as guide stars. An adaptive optics confocal microscope using this method is demonstrated for imaging of mouse brain tissue. A dendrite and a cell body of a neuron labeled with yellow fluorescent protein are tested as guide stars without injection of other fluorescent labels. Photobleaching effects are also analyzed. The results shows increased image contrast and 3× improvement in the signal intensity for fixed mouse tissues at depths of 70?μm. 相似文献
1000.
Zhou Z Wang X Klahr NJ Liu W Arias D Liu H von Deneen KM Wen Y Lu Z Xu D Liu Y 《Magnetic resonance imaging》2011,29(3):418-433
Granger causality model (GCM) derived from multivariate vector autoregressive models of data has been employed to identify effective connectivity in the human brain with functional magnetic resonance imaging (fMRI) and to reveal complex temporal and spatial dynamics underlying a variety of cognitive processes. In the most recent fMRI effective connectivity measures, pair-wise GCM has commonly been applied based on single-voxel values or average values from special brain areas at the group level. Although a few novel conditional GCM methods have been proposed to quantify the connections between brain areas, our study is the first to propose a viable standardized approach for group analysis of fMRI data with GCM. To compare the effectiveness of our approach with traditional pair-wise GCM models, we applied a well-established conditional GCM to preselected time series of brain regions resulting from general linear model (GLM) and group spatial kernel independent component analysis of an fMRI data set in the temporal domain. Data sets consisting of one task-related and one resting-state fMRI were used to investigate connections among brain areas with the conditional GCM method. With the GLM-detected brain activation regions in the emotion-related cortex during the block design paradigm, the conditional GCM method was proposed to study the causality of the habituation between the left amygdala and pregenual cingulate cortex during emotion processing. For the resting-state data set, it is possible to calculate not only the effective connectivity between networks but also the heterogeneity within a single network. Our results have further shown a particular interacting pattern of default mode network that can be characterized as both afferent and efferent influences on the medial prefrontal cortex and posterior cingulate cortex. These results suggest that the conditional GCM approach based on a linear multivariate vector autoregressive model can achieve greater accuracy in detecting network connectivity than the widely used pair-wise GCM, and this group analysis methodology can be quite useful to extend the information obtainable in fMRI. 相似文献