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91.
Mialane P Duboc C Marrot J Rivière E Dolbecq A Sécheresse F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):1950-1959
Two new azido-bridged polyoxometalate compounds were synthesized in acetonitrile/methanol media and their molecular structures have been determined by X-ray crystallography. The [[(gamma-SiW10O36)Mn2(OH)2(N3)(0.5)(H2O)(0.5)]2(mu-1,3-N3)](10-) (1 a) tetranuclear Mn(III) complex, in which an end-to-end N3- ligand acts as a linker between two [(gamma-SiW10O36)Mn2(OH)2]4- units, represents the first manganese-azido polyoxometalate. The magnetic properties have been studied considering the spin Hamiltonian H = -J1(S1S2+S1*S2*)-J2(S1S1*), showing that antiferromagnetic interactions between the paramagnetic centers (g = 1.98) occur both through the di-(mu-OH) bridge (J1 = -25.5 cm(-1)) and the mu-1,3-azido bridge (J2 = -19.6 cm(-1)). The [(gamma-SiW10O36)2Cu4(mu-1,1,1-N3)2(mu-1,1-N3)2]12- (2 a) tetranuclear Cu(II) complex consists of two [gamma-SiW10O36Cu2(N3)2]6- subunits connected through the two mu-1,1,1-azido ligands, the four paramagnetic centers forming a lozenge. The magnetic susceptibility data have been fitted. This reveals ferromagnetic interactions between the four Cu(II) centers, leading to an S=2 ground state (H = -J1(S1S2+S1*S2*)-J2(S2S2*), J1 = +294.5 cm(-1), J2 = +1.6 cm(-1), g = 2.085). The ferromagnetic coupling between the Cu(II) centers in each subunit is the strongest ever observed either in a polyoxometalate compound or in a diazido-bridged Cu(II) complex. Considering complex 2 a and the previously reported basal-basal di-(mu-1,1-N3)-bridged Cu(II) complexes in which the metallic centers are not connected by other magnetically coupling ligands, the linear correlation J1 = 2639.5-24.95*theta(av) between the theta(av) bridging angle and the J1 coupling parameter has been proposed. The electronic structure of complex 2 a has also been investigated by using multifrequency high-field electron paramagnetic resonance (HF-EPR) spectroscopy between 95 and 285 GHz. The spin Hamiltonian parameters of the S = 2 ground state (D = -0.135(2) cm(-1), E = -0.003(2) cm(-1), g(x) = 2.290(5), g(y) = 2.135(10), g(z) = 2.158(5)) as well as of the first excited spin state S = 1 (D = -0.960(4) cm(-1), E = -0.080(5) cm(-1), g(x) = 2.042(5), g(y) = 2.335(5), g(z) = 2.095(5)) have been determined, since the energy gap between these two spin states is very small (1.6 cm(-1)). 相似文献
92.
A new 3-D coordination polymer containing both 3d and 4f ions has been designed. Its chemical formula is La2[Cu(pba)]3(H2O)8 . 8H2O. It crystallizes in the quadratic system, space group I41/a with a = 42.4947(9) Angstrom, c = 16.3378(3) Angstrom, and Z = 16. Its crystal structure can be described as a 3-D molecular framework exhibiting a complex network of interconnected zigzaglike channels. Once crystallization water molecules are removed, this compound presents a high potential porosity and a low density. The porosity has been evaluated using Connolly's algorithm. 相似文献
93.
We use the Born approximation of the radiative transport equation to recover simultaneously the absorption and scattering coefficients in a single layer of a two-layer tissue sample from reflectance data. This method reduces the estimation of both optical properties to a single linear, least-squares problem. It is valid over length scales smaller than a transport mean free path and hence is useful for epithelial tissue layers. We demonstrate the accuracy of this method by using spatially resolved reflectance data computed with Monte Carlo simulations. 相似文献
94.
Müller WE Belikov SI Tremel W Perry CC Gieskes WW Boreiko A Schröder HC 《Micron (Oxford, England : 1993)》2006,37(2):107-120
All metazoan animals comprise a body plan of different complexity. Since--especially based on molecular and cell biological data--it is well established that all metazoan phyla, including the Porifera (sponges), evolved from a common ancestor the search for common, basic principles of pattern formation (body plan) in all phyla began. Common to all metazoan body plans is the formation of at least one axis that runs from the apical to the basal region; examples for this type of organization are the Porifera and the Cnidaria (diploblastic animals). It seems conceivable that the basis for the formation of the Bauplan in sponges is the construction of their skeleton by spicules. In Demospongiae (we use the model species Suberites domuncula) and Hexactinellida, the spicules consist of silica. The formation of the spicules as the building blocks of the skeleton, starts with the expression of an enzyme which was termed silicatein. Spicule growth begins intracellularly around an axial filament composed of silicatein. When the first layer of silica is made, the spicules are extruded from the cells and completed extracellularly to reach their the final form and size. While the first steps of spicule formation within the cells are becoming increasingly clear, it remains to be studied how the extracellularly present silicatein strings are formed. The understanding of especially this morphogenetic process will allow an insight into the construction of the amazingly diverse skeleton of the siliceous sponges; animals which evolved between two periods of glaciations, the Sturtian glaciation (710-680 MYA) and the Varanger-Marinoan ice ages (605-585 MYA). Sponges are--as living fossils--witnesses of evolutionary trends which remained unique in the metazoan kingdom. 相似文献
95.
Harmonics-to-Noise Ratio: An Index of Vocal Aging 总被引:3,自引:0,他引:3
Distinguishing between vocal changes that occur with normal aging and those that are associated with disease is an important goal of research in voice. Several acoustic measures have been used in an attempt to illuminate the integrity of the vocal mechanism, including harmonics-to-noise ratio (HNR), jitter, and fundamental frequency (F0). HNR is a measure that quantifies the amount of additive noise in the voice signal; jitter reflects the periodicity of vocal fold vibration. In this study, measures of HNR, jitter and F0 were used to compare vocal function in three groups of normally speaking women: young adults, middle-aged adults, and elderly adults. Significant differences in HNR emerged between the elderly women and the other two groups. F0 differences were also apparent between the elderly group and the two younger groups; there were no significant differences in jitter between the three groups. HNR was found to be a more sensitive index of vocal function than jitter. The significant lowering of HNR evident in the elderly speakers may be attributable in part to medications taken by the majority of these elderly subjects. 相似文献
96.
X Yi K Bernot F Pointillart G Poneti G Calvez C Daiguebonne O Guillou R Sessoli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(36):11379-11387
The reaction of [Ln(hfac)(3) ]?2?H(2) O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3) (PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4?K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0) =(5.62±0.4)×10(-11) s and Δ=(167±1)?K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42?Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001)?cm(-1) ). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1?%, respectively. The thermal investigation of [Dy(hfac)(3) (PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods. 相似文献
97.
98.
S Shahzad-Ul-Hussan R Ghirlando CI Dogo-Isonagie Y Igarashi J Balzarini CA Bewley 《Journal of the American Chemical Society》2012,134(30):12346-12349
The pradimicin family of antibiotics is attracting attention due to its anti-infective properties and as a model for understanding the requirements for carbohydrate recognition by small molecules. Members of the pradimicin family are unique among natural products in their ability to bind sugars in a Ca(2+)-dependent manner, but the oligomerization to insoluble aggregates that occurs upon Ca(2+) binding has prevented detailed characterization of their carbohydrate specificity and biologically relevant form. Here we take advantage of the water solubility of pradimicin S (PRM-S), a sulfated glucose-containing analogue of pradimicin A (PRM-A), to show by NMR spectroscopy and analytical ultracentrifugation that at biologically relevant concentrations, PRM-S binds Ca(2+) to form a tetrameric species that selectively binds and engulfs the trisaccharide Manα1-3(Manα1-6)Man over mannose or mannobiose. In functional HIV-1 entry assays, IC(50) values of 2-4 μM for PRM-S corrrelate with the concentrations at which oligomerization occurs as well as the affinities with which PRM-S binds the HIV surface envelope glycoprotein gp120. Together these data reveal the biologically active form of PRM-S, provide an explanation for previous speculations that PRM-A may contain a second mannose binding site, and expand our understanding of the characteristics that can engender a small molecule with the ability to function as a carbohydrate receptor. 相似文献
99.
Bionanocomposites based on the association between biological polymers and inorganic colloids are an emerging class of materials, with main applications in biotechnology and biomedicine. They combine the chemical diversity, hierarchical structure, and biocompatibility of natural biomacromolecules with the robustness and functionality of mineral phases. In particular, biopolymer hydrogels can act as templates and/or host matrices for nanoparticles to design bionanocomposites with tailored optical, conductive, magnetic, mechanical, and bioactive properties. This review presents the key concepts on which such materials are currently designed, in terms of chemistry and physics. Specific examples are provided to illustrate the importance of the bio‐organic/inorganic interface on the final properties of the composite structures. It is finally suggested that bionanocomposites have a major role to play for the development of green materials and bio‐responsive devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
100.
A new bifunctional C-5' substituted cinchona alkaloid-based catalyst promotes the first highly enantioselective additions of alkyl thiols to nitrostyrenes. 相似文献