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排序方式: 共有284条查询结果,搜索用时 15 毫秒
61.
Francesco Mallamace Carmelo Corsaro Domenico Mallamace Sow-Hsin Chen Emiliano Fratini Piero Baglioni 《中国科学:物理学 力学 天文学(英文版)》2019,(10)
We study the evolution of the Boson peak for water confined in cement paste obtained by means of Inelastic Neutron Scattering from room temperature to the deep supercooled regime. We analyze the data in terms of a universal-like model, developed for glass forming liquids in the frame of the energy landscape. In such a way it is possible to discriminate between the fragile and strong glass forming character of supercooled liquids and the dynamical crossover, fragile to strong, between them. Hence, we confirm the link between the Boson peak and the water polymorphism. In particular, the main result is represented by a crossover from a local energetic minima configuration to that characteristic of saddle points on going towards the deep supercooled regime up to the dynamical arrest. 相似文献
62.
Carmelo Sgarlata Valeria Zito Giuseppe Arena Grazia Maria Letizia Consoli Eva Galante Corrada Geraci 《Polyhedron》2009
The binding affinity for Pb2+, Cd2+ and Hg2+ of the sinapic acid–calix[4]arene hybrid 2, having four sinapyl pendants at the upper rim, has been investigated via an UV–Vis study. Compound 2 has better complexing ability than the monomeric p-phenetidine derivative 1. This highlights that the clustering of sinapyl units in a basket-like structure, dictated by the calixarene scaffold, greatly enhances the complexing properties. Ligand 2 forms complexes even with Hg2+, which is not complexed by 1 at all; the complexes formed by 2 with Pb2+ and Cd2+ are much stronger than the analogous complexes formed by 1. The UV–Vis investigation shows that the hybrid 2 markedly favors Pb2+ over Cd2+ and Hg2+. Information on the structural properties of the complex species was obtained by 1H NMR spectroscopy. NMR data show that all three metal ions are placed into the cavity consisting of the calixarene scaffold and the sinapyl pendants, though their binding affects the coordinating regions to a different extent. 相似文献
63.
The mechanisms that trigger the phototoxic response to 2-chlorophenothiazine derivatives are still unknown. To better understand the relationship between the molecular structure of halogenated phenothiazines and their phototoxic activity, their photophysics and photochemistry were studied in several alcohols. The photodestruction quantum yields were determined under anaerobic conditions using monochromatic light (313 nm). Absorption- and emission-spectroscopy, 1 H- and 13 C-NMR and GC-MS were used to characterize the photoproducts and reference compounds. An electron transfer mechanism had been previously proposed by Bunce et al . ( J. Med. Chem . 22 , 202–204) to explain the large difference between the photodestruction quantum yield of 2-chlorpromazine (φ = 0.46) and 2-chlorphenothiazine (φ = 0.20). According to these authors, the alkylamino chain transfers an electron to the phenothiazine moiety. Our results demonstrate that this mechanism is incorrect, because the photodestruction quantum yields of all chlorinated derivatives of this study are the same under the same conditions of solvent and irradiation wavelength. The quantum yield has no dependence on the 10-substituent, but it depends on the solvent. The percentage of each photoproduct, on the other hand, strongly depends on that substituent, but not very much on the solvent. Finally, it is demonstrated that the phototoxic effect of chlorinated phenothiazines is not related to the photodechlorination, although both processes share the same transient. 相似文献
64.
Ignacio Martínez-Lpez Isabel María Ortiz-Rodríguez Carmelo Rodríguez-Torreblanca 《Applied Mathematics Letters》2009,22(12):1892-1895
This paper is concerned with constructing optimal designs for rational models which are used for modeling problems in Agriculture and other disciplines. Homoscedastic and weighted models are considered. An analytical characterization of these designs is obtained as zeros of a polynomial solution of a second order differential equation. 相似文献
65.
Carmelo Rodríguez-Álvarez 《International Journal of Game Theory》2009,38(3):431-452
We analyze coalition formation problems in which a group of agents is partitioned into coalitions and agents’ preferences
only depend on the coalition to which they belong. We study rules that associate to each profile of preferences a partition
of the society. We focus on strategy-proof rules on restricted domains of preferences, as the domains of additively representable
or separable preferences. In such domains, the only strategy-proof and individually rational rules that satisfy either a weak
version of efficiency or non-bossiness and flexibility are single-lapping rules. Single-lapping rules are characterized by
severe restrictions on the set of feasible coalitions that are consistent with hierarchical organizations. These restrictions
are necessary and sufficient for the existence of a unique core-stable partition. In fact, single-lapping rules always select
the associated unique core-stable partition. Thus, our results highlight the relation between the non-cooperative concept
of strategy-proofness and the cooperative concept of uniqueness of core-stable partitions. 相似文献
66.
Wang F DeMuro NE Elmquist CE Stover JS Rizzo CJ Stone MP 《Journal of the American Chemical Society》2006,128(31):10085-10095
The solution structure of the oligodeoxynucleotide 5'-d(CTCGGCXCCATC)-3'.5'-d(GATGGCGCCGAG)-3' containing the heterocyclic amine 8-[(3-methyl-3H-imidazo[4,5-f]quinolin-2-yl)amino]-2'-deoxyguanosine adduct (IQ) at the third guanine in the NarI restriction sequence, a hot spot for -2 bp frameshifts, is reported. Molecular dynamics calculations restrained by distances derived from 24 (1)H NOEs between IQ and DNA, and torsion angles derived from (3)J couplings, yielded ensembles of structures in which the adducted guanine was displaced into the major groove with its glycosyl torsion angle in the syn conformation. One proton of its exocyclic amine was approximately 2.8 A from an oxygen of the 5' phosphodiester linkage, suggesting formation of a hydrogen bond. The carcinogen-guanine linkage was defined by torsion angles alpha' [N9-C8-N(IQ)-C2(IQ)] of 159 +/- 7 degrees and beta' [C8-N(IQ)-C2(IQ)-N3(IQ)] of -23 +/- 8 degrees . The complementary cytosine was also displaced into the major groove. This allowed IQ to intercalate between the flanking C.G base pairs. The disruption of Watson-Crick hydrogen bonding was corroborated by chemical-shift perturbations for base aromatic protons in the complementary strand opposite to the modified guanine. Chemical-shift perturbations were also observed for (31)P resonances corresponding to phosphodiester linkages flanking the adduct. The results confirmed that IQ adopted a base-displaced intercalated conformation in this sequence context but did not corroborate the formation of a hydrogen bond between the IQ quinoline nitrogen and the complementary dC [Elmquist, C. E.; Stover, J. S.; Wang, Z.; Rizzo, C. J. J. Am. Chem. Soc. 2004, 126, 11189-11201]. 相似文献
67.
Pérez Pavón JL del Nogal Sánchez M Fernández Laespada ME García Pinto C Moreno Cordero B 《Analytica chimica acta》2006,576(2):156-162
A high-speed determination of benzene in gasoline samples using a non-separative method based on direct injection into the mass spectrometer is proposed. The results obtained are very similar to those provided with fast GC-MS.The calibration set was made up of gasoline samples in which the benzene was determined chromatographically and samples of gasoline subjected to a process of evaporation - until the complete disappearance of the original benzene - to which known concentrations of this compound had been added. A PLS1 multivariate calibration model was constructed. Cross-validation was used to select the optimum number of PLS components. The prediction capacity of the model was checked with an additional group of gasoline samples that had not been used either in the construction or in the validation of the model.With the direct injection method proposed here it was possible to analyse 24 samples over a period of 1 h. The direct injection method is rapid, simple and - in view of the results - highly suitable for the determination of benzene in gasoline samples. 相似文献
68.
69.
70.
Francesco Mallamace Carmelo Corsaro Enza Fazio Sow-Hsin Chen Domenico Mallamace 《中国科学:物理学 力学 天文学(英文版)》2019,(10)
We study the hydrogen bonds effect on the water density as a function of temperature and pressure from the supercritical region to the metastable supercooled and amorphous phases. We identify two important thermodynamic thresholds, that is P~*2■kbar and T~*■315 K, that separate two different water behaviors in terms of hydrogen bonding capability. For T T~* and P P~* the formation and stability of hydrogen bonded local structures are enhanced. The additional analyses of the proton NMR chemical shift and of the relaxation time confirm this evidence and highlight the structure breaking effects of the pressure. The investigation of both structural and dynamical quantities allow us to draw a complete picture of the water properties in terms of the temperaturepressure dependence of hydrogen bonding. 相似文献