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91.
García Ruano JL Alonso de Diego SA Martín MR Torrente E Martín Castro AM 《Organic letters》2004,6(26):4945-4948
[reaction: see text] Thermolysis of enantiopure sulfonyl pyrazolines 4 and 5, easily obtained from (Z)-3-p-tolylsulfinylacrylonitriles (1), afforded sulfonyl cyclopropanes (6, 7) in a completely stereoselective manner in almost quantitative yields. Both cyclopropanes and alkylidenecyclopropanes, containing one or two chiral carbon atoms, one of them being quaternary, were obtained by hydrogenolysis of the C-S bonding and under the conditions reported by Julia, respectively. The highly stereoselective extrusion of nitrogen suggests a concerted mechanism. 相似文献
92.
We argue that the recently introduced statefinder parameters (Sahni et al., JETP Lett. 77, 201 (2003)), that include the third derivative of the cosmic scale factor, are useful tools to characterize interacting quintessence models. We specify the statefinder parameters for two classes of models that solve, or at least alleviate, the coincidence problem. 相似文献
93.
Cerdeiriña CA González-Salgado D Romani L Delgado Mdel C Torres LA Costas M 《The Journal of chemical physics》2004,120(14):6648-6659
A model for the temperature dependence of the isobaric heat capacity of associated pure liquids C(p,m)(o)(T) is proposed. Taking the ideal gas as a reference state, the residual heat capacity is divided into nonspecific C(p) (res,ns) and associational C(p) (res,ass) contributions. Statistical mechanics is used to obtain C(p)(res,ass) by means of a two-state model. All the experimentally observed C(p,m)(o)(T) types of curves in the literature are qualitatively described from the combination of the ideal gas heat capacity C(p)(id)(T) and C(p)(res,ass)(T). The existence of C(p,m)(o)(T) curves with a maximum is predicted and experimentally observed, for the first time, through the measurement of C(p,m)(o)(T) for highly sterically hindered alcohols. A detailed quantitative analysis of C(p,m)(o)(T) for several series of substances (n-alkanes, linear and branched alcohols, and thiols) is made. All the basic features of C(p,m)(o)(T) at atmospheric and high pressures are successfully described, the model parameters being physically meaningful. In particular, the molecular association energies and the C(p)(res,ns) values from the proposed model are found to be in agreement with those obtained through quantum mechanical ab initio calculations and the Flory model, respectively. It is concluded that C(p,m)(o)(T) is governed by the association energy between molecules, their self-association capability and molecular size. 相似文献
94.
We show that with the help of a suitable coupling between dark energy and cold dark matter it is possible to reproduce any scaling solution
X
M
a
, where
X
and
M
are the densities of dark energy and dark matter, respectively. We demonstrate how the case = 1 alleviates the coincidence problem. Future observations of supernovae at high redshift as well as quasar pairs which are planned to discriminate between different cosmological models will also provide direct constraints on the coupling between dark matter and dark energy. 相似文献
95.
Mohd Mustapa MF Harris R Esposito D Chubb NA Mould J Schultz D Driscoll PC Tabor AB 《The Journal of organic chemistry》2003,68(21):8193-8198
Two diastereomeric analogues of ring C of nisin incorporating a novel norlanthionine residue have been synthesized via a triply orthogonal protecting group strategy. A full structural study was carried out by NMR, which elucidated the conformational properties of the two peptides and enabled the identity of each diastereoisomer to be proposed. 相似文献
96.
[RuCl2(PPh3)3] reacts with thallium(I) fluoride to give either [Tl(mu-F)3Ru(PPh3)3] (1) or [Tl(mu3-F)(mu2-Cl)2Ru2(mu2-Cl)(mu2-F)(PPh3)4] (2) depending on the excess of TlF used. Both 1 and 2 were fully characterized, including X-ray structure determinations. Complex 1 reacts with dihydrogen to form the known ruthenium hydride complex [Ru(H)2(H2)(PPh3)3] upon hydrogenolysis of the Ru-F bond. The reaction of 1 with activated alkyl bromides (R-Br) gives the corresponding alkyl fluorides and the trinuclear complex [Tl(mu3-F)(mu2-F)(mu2-X)Ru2(mu2-Br)(mu2-F)(PPh3)4] (X=Br, F) (3), whose structure closely resembles that of 2. However, 1 is not active as catalyst for the nucleophilic fluorination of R-Br in the presence of thallium fluoride. The effect of the bridging coordination mode of fluoride on the Ru-F bond is discussed in terms of the HSAB principle, which suggests a more general model for predicting the stability of d6 and d8 complexes containing hard ligands (such as fluoro, oxo, and amido). 相似文献
97.
Martín-Matute B Cárdenas DJ Echavarren AM 《Angewandte Chemie (International ed. in English)》2001,40(24):4754-4757
98.
[reaction: see text] The dipolarophilic reactivity of enantiopure (Z)-3-p-tolylsulfinylacrylonitriles (1) has been evaluated with diazoalkanes. 3-Cyanopyrazoles are obtained when R = H, but with R = alkyl (Bn, n-Bu, and t-Bu) only one cycloadduct (4 or 5) is formed in high yield under mild conditions, therefore evidencing a complete control of the regioselectivity and the endo/exo and pi-facial selectivities. These reactions are a new straightforward entry to the synthesis of pyrazolines and related structures and reveal the excellent dipolarophilic features of (Z)-sulfinylacrylonitriles. 相似文献
99.
We reveal unifying thermodynamic aspects of so different phenomena as the cosmological electron-positron annihilation, the evaporation of primordial black holes with a narrow mass range, and the "deflationary" transition from an initial de Sitter phase to a subsequent standard Friedmann–Lemaître–Robertson–Walker (FLRW) behavior. 相似文献
100.
Considerable advances in automatic speech recognition have been made in the last decades, thanks specially to the use of hidden Markov models. In the field of speech signal analysis, different techniques have been developed. However, deterioration in the performance of the speech recognizers has been observed when they are trained with clean signal and tested with noisy signals. This is still an open problem in this field. Continuous multiresolution entropy has been shown to be robust to additive noise in applications to different physiological signals. In previous works we have included Shannon and Tsallis entropies, and their corresponding divergences, in different speech analysis and recognition systems. In this paper we present an extension of the continuous multiresolution entropy to different divergences and we propose them as new dimensions for the pre-processing stage of a speech recognition system. This approach takes into account information about changes in the dynamics of speech signal at different scales. The methods proposed here are tested with speech signals corrupted with babble and white noise. Their performance is compared with classical mel cepstral parametrization. The results suggest that these continuous multiresolution entropy related measures provide valuable information to the speech recognition system and that they could be considered to be included as an extra component in the pre-processing stage. 相似文献