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11.
12.
A new approach to the total, asymmetric synthesis of D -threo-L -talo-octose ((?)- 1 ) and its derivatives is presented. It is based on the chemoselective Wittig-Horner monoolefination of a 5-deoxy-D -ribo-hexodialdose derivative 4 obtained by selective reduction of (?)-5-deoxy-2.3-O-isopropylidene-/β-D -ribo-hexofuranurono-6,1-lactone ((?)- 3 ). Allylic bromination of the resulting methyl (E)-oct-6-enofuranuronate (+)- 5 followed by intramolecular nucleophilic displacement of the so-obtained bromides gave a 13.3:1 mixture of (?)-methyl (E)-l,4-anhydro-6,7-dideoxy-2,3-O-isopropylidene-β-L -talo-oct-6-enopyranuronate ((?)- 8 ) and methyl (E)-l,4-anhydro-6,7-dideoxy-2,3-O-isopropylidene-α-D -allo-oct-6-enopyranuronate ( 9 ). The double hydroxylation of the enoate (?)- 8 followed Kishi's rule and gave the corresponding D -threo-β-L -talo-octopyranuronate derivative (?)- 11 with a good diastereoselectivity. Reduction of ester (?)- 11 and deprotection led to pure (?)- 1 . 相似文献
13.
J. Monnier S. Réguer D. Vantelon P. Dillmann D. Neff I. Guillot 《Applied Physics A: Materials Science & Processing》2010,99(2):399-406
The study and prediction of very long-term atmospheric corrosion behaviour of ferrous alloys is of great importance in different
fields. First the conservation of metallic artefacts in museum and the corrosion diagnosis on ferrous reinforcement used in
ancient monuments since medieval times needs reliable data to understand the mechanisms. Second, in the frame of the interim
storage of nuclear waste in France, it is necessary to model the long-term corrosion of low alloy steel overcontainer. The
nature of phases and elements constituting the corrosion layers can greatly influence the corrosion mechanisms. On the one
hand, it is crucial to precisely determine the nature of microscopic phases that can be highly reactive. On the other hand,
some elements as P and S could modify this reactivity. To clarify this point and complementary to other studies using Raman
micro spectroscopy technique, X-rays Absorption Spectroscopy (XAS) under synchrotron radiation plays a crucial role. It allows
one to precisely identify the reactive phases in the corrosion layers. Micro-XAS was required in order to refine the spatial
variation, at micrometer scale, of the predominant Fe oxidation state and to characterise the corresponding corrosion products.
Moreover, the role of minor elements on phase’s stability and the chemical form of these elements in the rust layer, especially
phosphorus and sulphur, was investigated. 相似文献
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15.
Alexandrou C de Forcrand P Neff H Negele JW Schroers W Tsapalis A 《Physical review letters》2005,94(2):021601
The magnetic dipole (M1), the electric quadrupole (E2), and the Coulomb quadrupole (C2) amplitudes for gammaN-->Delta are calculated in quenched lattice QCD. Using a new method, which combines an optimal choice of interpolating fields for the Delta and an overconstrained analysis, we obtain statistically accurate results for the dipole form factor and for the ratios R(EM)=E2/M1 and R(SM)=C2/M1, up to momentum transfer squared 1.5 GeV2. We show for the first time, using lattice QCD, that both R(EM) and R(SM) are nonzero and negative, in qualitative agreement with experiment and indicating the presence of deformation in the N/Delta system. 相似文献
16.
A silicon-on-insulator (SOI) based thin film resistor is employed for the label-free determination of enzymatic activity. We demonstrate that enzymes, which cleave biological polyelectrolyte substrates, can be detected by the sensor. As an application, we consider the serine endopeptidase trypsin, which cleaves poly-L-lysine (PLL). We show that PLL adsorbs quasi-irreversibly to the sensor and is digested by trypsin directly at the sensor surface. The created PLL fragments are released into the bulk solution due to kinetic reasons. This results in a measurable change of the surface potential allowing for the determination of trypsin concentrations down to 50 ng mL(-1). Chymotrypsin is a similar endopeptidase with a different specificity, which cleaves PLL with a lower efficiency as compared to trypsin. The activity of trypsin is analyzed quantitatively employing a kinetic model for enzyme-catalyzed surface reactions. Moreover, we have demonstrated the specific inactivation of trypsin by a serine protease inhibitor, which covalently binds to the active site of the enzyme. 相似文献
17.
A parallel-plate rheomete was constructed and used to study the development of dynamic shear modulus and cell opening under forced adiabatic conditions for a series of flexible slabstock polyurethane foams. Typical industrial formulations were used. The plates were heated to follow the adiabatic temperature profile of a real foam bun during foaming. The rheometer overcomes difficulties encountered in other methods such as heat loss and bubble damage caused by the probe.A four-stage modulus development profile was observed: initial bubble growth, bubble network, polymer stiffening and final curing. Chemical structure development was also studied under forced adiabatic conditions, using Fourier transform infrared spectroscopy. Polymer stiffening coincided with bidentate (hydrogen-bonded) urea formation.The normal force exerted by the expanding foam on the plates was found to be a function of the rate of foam expansion and the foam modulus. A sudden drop in the normal force typically coincides with the visually observed blow-off in the reacting foam bun, thus the normal force profile is a new and accurate indicator of cell opening. The normal force profile clearly shows that cell opening occurs just after the onset of polymer stiffening, thus illustrating the role of polymer rheology in the cell opening mechanism.Dedicated to the memory of Professor Tasos C. PapanastasiouPortions presented at the SPI Polyurethanes Technical/Marketing Conference, October 9–12, 1994, Boston, massachusetts, USA (Best paper award) and at the XIIth International Congress on Rheology, August 18–23, 1996, Québec City, Québec, Canada. 相似文献
18.
We investigate a family of isotropic volumetric-isochorically decoupled strain energies based on the Hencky-logarithmic (true, natural) strain tensor log U. The main result of this note is that for n = 2 the considered energies are rank-one convex for suitable values of two material parameters. We also conjecture that there are values of the material parameters such that the corresponding energies are polyconvex. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
19.
20.
The linear Reissner-Mindlin membrane-bending plate model is the rigorous Γ-limit for zero thickness of a linear isotropic Cosserat bulk model with symmetric curvature. For this result we use the natural nonlinear scaling for the displacements u and the linear scaling for the infinitesimal microrotations Ā ∈ so(3) affecting the in-plane drill rotations. No boundary conditions on the microrotations are prescribed. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献