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61.
Victor?de?FreitasEmail author Nuno?Mateus 《Analytical and bioanalytical chemistry》2011,401(5):1463-1464
Pyranoanthocyanins constitute one of the most important classes of anthocyanin-derived pigments occurring naturally in red wine. Nonetheless, correct assignment of their structures and pathways of formation in red wine has been relatively recent—less than two decades. Study of these newly discovered pigments is progressively unfolding the chemical pathways that drive the evolution of red wine colour during ageing. The objective of this paper is to review current knowledge regarding the pathway of formation in red wine of a great variety of pyranoanthocyanin structures, namely carboxypyranoanthocyanins, methylpyranoanthocyanins, pyranoanthocyanin-flavanols, pyranoanthocyanin-phenols, portisins, oxovitisins, and pyranoanthocyanin dimers. The chromatic features of some of the compounds, for example their colour expression and acid–base equilibria in aqueous media, are also discussed. 相似文献
62.
Oliveira EF Cerqueira NM Fernandes PA Ramos MJ 《Journal of the American Chemical Society》2011,133(39):15496-15505
In this paper we studied the mechanism of formation of the internal aldimine, a common intermediate to most pyridoxal 5'-phosphate (PLP)-dependent enzymes. A large model based on the crystal structure from the human ornithine decarboxylase (ODC) enzyme was constructed and in total accounts for 504 atoms. The reaction mechanism was investigated using the ONIOM methodology (B3LYP/6-31G(d)//AM1), and the final energies were calculated with the M06/6-311++G(2d,2p)//B3LYP/6-31G(d) level of theory. It was demonstrated that the reaction is accomplished in three sequential steps: (i) the nucleophilic attack of Lysine69 to PLP, (ii) the carbinolamine formation, and (iii) a final dehydration step. For the carbinolamine formation, several mechanistic hypotheses were explored, and the preferred pathway assigns a key role for the conserved active site Cys360. The overall reaction is exergonic in -9.1 kcal/mol, and the rate-limiting step is the dehydration step (E(a) = 13.5 kcal/mol). For the first time, we provide an atomistic portrait of this mechanism in an enzymatic environment. Moreover, we were able to assign a novel role to Cys360 in the ODC reaction mechanism that was never proposed. 相似文献
63.
64.
Yeast cell wall particles: a promising class of nature-inspired microcarriers for multimodal imaging
Figueiredo S Moreira JN Geraldes CF Rizzitelli S Aime S Terreno E 《Chemical communications (Cambridge, England)》2011,47(38):10635-10637
This communication demonstrates that yeast cell wall particles (YCWPs) are a promising class of nature-inspired biocompatible microcarriers for the delivery of amphipathic/lipophilic imaging reporters. When a paramagnetic MRI agent is loaded, the longitudinal relaxivity per particle at 0.5 T is the highest ever reported for Gd-based systems. 相似文献
65.
66.
We study iteration of polynomials on symmetric stochastic matrices. In particular, we focus on a certain one-parameter family
of quadratic maps which exhibits chaotic behavior for a wide range of the parameters. The well-known dynamical behavior of
the quadratic family on the interval, and its dependence on the parameter, is reproduced on the spectrum of the stochastic
matrices. For certain subclasses of stochastic matrices the referred dynamical behavior is also obtained in the matrix entries.
Since a stochastic matrix characterizes a Markov chain, we obtain a discrete dynamical system on the space of reversible Markov
chains. Therefore, depending on the parameter, there are initial conditions for which the corresponding reversible Markov
chains will lead under iteration to a fixed point, to a periodic point, or to an aperiodic point. Moreover, there are sensitivity
to initial conditions and the coexistence of infinite repulsive periodic orbits, both features of chaos. 相似文献
67.
Polymer films containing dispersions of liquid crystal microdroplets have considerable potential for use in displays and other light control devices. These polymer-dispersed liquid crystal (PDLC) films operate by electric field control of light scattering, rather than by polarization control as in the case of twisted nematic systems. The scattering characteristics of the PDLC films are determined by the refractive indices of the polymer and liquid crystal and by the size of the microdroplets. We have found that it is possible to regulate the microdroplet size by controlling the droplet formation rate (i.e. the cure kinetics of the film). Using calorimetry and scanning electron microscopy, we determined the influence of cure kinetics on microdroplet size for epoxy-based PDLCs. We found that droplet size increased with increasing cure time constant. However, the relationship changed as cure temperature was varied, perhaps as a result of competing cure processes. We also determined the phase behaviour of the epoxy-based PDLCs. The liquid crystal acted as a plasticizer, depressing the glass transition temperature of the PDLC samples slightly below that of the pure epoxy. The temperature and enthalpy of the nematic to isotropic transition of the liquid crystal material in the microdroplets were both functions of cure temperature. From the transition enthalpy it was possible to estimate a, the fraction of liquid crystal contained in the droplets; we found that a decreased with increasing cure temperature, presumably as a result of greater liquid crystal solubility in the epoxy matrix at higher temperatures. 相似文献
68.
The skeletal rearrangement of bicyclo[2.2.2]lactones, involving a mild and chemoselective palladium-catalysed translocation key-step, provides an efficient and diastereoselective access to synthetically useful bicyclo[3.3.0]lactones. 相似文献
69.
Several specific synthetic protocols were developed for the preparation from cyanuric chloride of a range of symmetric and non-symmetric di- and tri-substituted 1,3,5-triazines containing alkyl, aromatic, hindered, chiral and achiral hydroxyalkyl, ester and imidazole groups via sequential nucleophilic substitution of the C-Cl bond by C-O, C-N and C-S bonds. 相似文献
70.
We describe the Williams zeta-functions and the twist zeta-functions of sub-Lorenz templates generated by renormalizable Lorenz maps, in terms of the corresponding zeta-functions of the sub-Lorenz templates generated by the renormalized map and by the map that determines the renormalization type. 相似文献