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101.
The self-assembly of molecular components into complex superstructures involves the subtle interplay of various noncovalent forces. Charged species are often utilised in self-assembly processes as a result of the favorable π-π, cation-π, electrostatic, and hydrogen bonding interactions that form between these species. Although the counterions associated with these charged species can exert significant effects on the synthesis, stability, and operation of superstructures in solution, rarely are the counterions considered, leading to misinterpretations and misunderstandings of the studied systems. In this tutorial review, we discuss a variety of solution-phase counterion effects, from the fundamental origins to innovative ways in which these effects are exploited for useful functions. 相似文献
102.
Li H Zhao YL Fahrenbach AC Kim SY Paxton WF Stoddart JF 《Organic & biomolecular chemistry》2011,9(7):2240-2250
A synthetic approach to the preparation of [2]rotaxanes (1-5·6PF(6)) incorporating bispyridinium derivatives and two 1,5-dioxynaphthalene (DNP) units situated in the rod portions of their dumbbell components that are encircled by a single cyclobis(paraquat-p-phenylene) tetracationic (CBPQT(4+)) ring has been developed. Since the π-electron-deficient bispyridinium units are introduced into the dumbbell components of the [2]rotaxanes 1-5·6PF(6), there are Coulombic charge-charge repulsions between these dicationic units and the CBPQT(4+) ring in the [2]rotaxanes. Thus, the CBPQT(4+) rings in the degenerate [2]rotaxanes exhibit slow shuttling between two DNP recognition sites on the (1)H NMR time-scale on account of the electrostatic barrier posed by the bispyridinium units, as demonstrated by variable-temperature (1)H NMR spectroscopy. Electrochemical experiments carried out on the [2]rotaxanes 1·6PF(6) and 2·6PF(6) indicate that the one-electron reduced bipyridinium radical cation in the dumbbell components of the [2]rotaxanes serves as an additional recognition site for the two-electron reduced CBPQT(2(˙+)) diradical cationic ring. Under appropriate conditions, the ring components in the degenerate rotaxanes 1·6PF(6) and 2·6PF(6) can shuttle along the recognition sites--two DNP units and one-electron reduced bipyridinium radical cation--under redox control. 相似文献
103.
Using TMPZnCl·LiCl as a kinetically highly active base, nitriles and esters undergo a Pd-catalyzed α-arylation under mild conditions. Remarkably, in the case of α,β- or β,γ-unsaturated nitriles, a regioselective γ-arylation or a γ-alkenylation is observed. 相似文献
104.
Harrison S Fraser K Lane G Hughes D Villas-Boas S Rasmussen S 《Analytical and bioanalytical chemistry》2011,401(9):2955-2963
The main water-soluble carbohydrates in temperate forage grasses are polymeric fructans. Fructans consist of fructose chains
of various chain lengths attached to sucrose as a core molecule. In grasses, fructans are a complex mixture of a large number
of isomeric oligomers with a degree of polymerisation ranging from 3 to >100. Accurate monitoring and unambiguous peak identification
requires chromatographic separation coupled to mass spectrometry. The mass range of ion trap mass spectrometers is limited,
and we show here how monitoring selected multiply charged ions can be used for the detection and quantification of individual
isomers and oligomers of high mass, particularly those of high degree of polymerization (DP > 20) in complex plant extracts.
Previously reported methods using linear ion traps with low mass resolution have been shown to be useful for the detection
of fructans with a DP up to 49. Here, we report a method using high-resolution mass spectrometry (MS) using an Exactive Orbitrap
MS which greatly improves the signal-to-noise ratio and allows the detection of fructans up to DP = 100. High-sugar (HS) Lolium perenne cultivars with high concentrations of these fructans have been shown to be of benefit to the pastoral agricultural industry
because they improve rumen nitrogen use efficiency and reduce nitrous oxide emissions from pastures. We demonstrate with our
method that these HS grasses not only contain increased amounts of fructans in leaf blades but also accumulate fructans with
much higher DP compared to cultivars with normal sugar levels. 相似文献
105.
Hydrolysis of a Pacman-shaped binuclear magnesium complex of a polypyrrolic Schiff base macrocycle results in the formation of a new magnesium hydroxide cubane that is encapsulated by the macrocyclic framework through both coordinative and hydrogen-bonding interactions. 相似文献
106.
Fraser MG Clark CA Horvath R Lind SJ Blackman AG Sun XZ George MW Gordon KC 《Inorganic chemistry》2011,50(13):6093-6106
The syn and anti isomers of the bi- and trinuclear Re(CO)(3)Cl complexes of 2,3,8,9,14,15-hexamethyl-5,6,11,12,17,18-hexaazatrinapthalene (HATN-Me(6)) are reported. The isomers are characterized by (1)H NMR spectroscopy and X-ray crystallography. The formation of the binuclear complex from the reaction of HATN-Me(6) with 2 equiv of Re(CO)(5)Cl in chloroform results in a 1:1 ratio of the syn and anti isomers. However, synthesis of the trinuclear complex from the reaction of HATN-Me(6) with 3 equiv of Re(CO)(5)Cl in chloroform produces only the anti isomer. syn-{(Re(CO)(3)Cl)(3)(μ-HATN-Me(6))} can be synthesized by reacting 1 equiv of Re(CO)(5)Cl with syn-{(Re(CO)(3)Cl)(2)(μ-HATN-Me(6))} in refluxing toluene. The product is isolated by subsequent chromatography. The X-ray crystal structures of syn-{(Re(CO)(3)Cl)(2)(μ-HATN-Me(6))} and anti-{(Re(CO)(3)Cl)(3)(μ-HATN-Me(6))} are presented both showing severe distortions of the HATN ligand unit and intermolecular π stacking. The complexes show intense absorptions in the visible region, comprising strong π → π* and metal-to-ligand charge-transfer (MLCT) transitions, which are modeled using time-dependent density functional theory (TD-DFT). The energy of the MLCT absorption decreases from mono- to bi- to trinuclear complexes. The first reduction potentials of the complexes become more positive upon binding of subsequent Re(CO)(3)Cl fragments, consistent with changes in the energy of the MLCT bands and lowering of the energy of relevant lowest unoccupied molecular orbitals, and this is supported by TD-DFT. The nature of the excited states of all of the complexes is also studied using both resonance Raman and picosecond time-resolved IR spectroscopy, where it is shown that MLCT excitation results in the oxidation of one rhenium center. The patterns of the shifts in the carbonyl bands upon excitation reveal that the MLCT state is localized on one rhenium center on the IR time scale. 相似文献
107.
Fleming FF Liu W Yao L Pitta B Purzycki M Ravikumar PC 《European journal of organic chemistry》2011,2011(34):6843-6846
Grignard reagents trigger an addition-elimination with α'-hydroxy acrylonitriles to selectively generate Z-alkenenitriles. The modular assembly of Z-alkenenitriles from a Grignard reagent, acrylonitrile, and an aldehyde is ideal for stereoselectively synthesizing alkenes as illustrated in the synthesis of the putative lignan "morinol I." 相似文献
108.
109.
We consider the relationship of the geometry of compact Riemannian manifolds with boundary to the first nonzero eigenvalue σ1 of the Dirichlet-to-Neumann map (Steklov eigenvalue). For surfaces Σ with genus γ and k boundary components we obtain the upper bound σ1L(∂Σ)?2(γ+k)π. For γ=0 and k=1 this result was obtained by Weinstock in 1954, and is sharp. We attempt to find the best constant in this inequality for annular surfaces (γ=0 and k=2). For rotationally symmetric metrics we show that the best constant is achieved by the induced metric on the portion of the catenoid centered at the origin which meets a sphere orthogonally and hence is a solution of the free boundary problem for the area functional in the ball. For a general class of (not necessarily rotationally symmetric) metrics on the annulus, which we call supercritical, we prove that σ1(Σ)L(∂Σ) is dominated by that of the critical catenoid with equality if and only if the annulus is conformally equivalent to the critical catenoid by a conformal transformation which is an isometry on the boundary. Motivated by the annulus case, we show that a proper submanifold of the ball is immersed by Steklov eigenfunctions if and only if it is a free boundary solution. We then prove general upper bounds for conformal metrics on manifolds of any dimension which can be properly conformally immersed into the unit ball in terms of certain conformal volume quantities. We show that these bounds are only achieved when the manifold is minimally immersed by first Steklov eigenfunctions. We also use these ideas to show that any free boundary solution in two dimensions has area at least π, and we observe that this implies the sharp isoperimetric inequality for free boundary solutions in the two-dimensional case. 相似文献
110.