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131.
Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B2(pin)2). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity. 相似文献
132.
The scope of this paper is to present a nonlinear error estimation and correction for Navier-Stokes and Reynolds-averaged Navier-Stokes equations. This nonlinear corrector enables better solution or functional output predictions at fixed mesh complexity and can be considered in a mesh adaptation process. After solving the problem at hand, a corrected solution is obtained by solving again the problem with an added source term. This source term is deduced from the evaluation of the residual of the numerical solution interpolated on the h/2 mesh. To avoid the generation of the h/2 mesh (which is prohibitive for realistic applications), the residual at each vertex is computed by local refinement only in the neighborhood of the considered vertex. One of the main feature of this approach is that it automatically takes into account all the properties of the considered numerical method. The numerical examples point out that it successfully improves solution predictions and yields a sharp estimate of the numerical error. Moreover, we demonstrate the superiority of the nonlinear corrector with respect to linear corrector that can be found in the literature. 相似文献
133.
134.
Jia Zhang Florence Vermeire Ruben Van de Vijver Olivier Herbinet Frédérique Battin-Leclerc Marie-Françoise Reyniers Kevin M. Van Geem 《国际化学动力学杂志》2020,52(11):785-795
3-Carene is an important potential biofuel with properties similar to the jet-propellant JP-10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3-carene. The pyrolysis of 3-carene was investigated in a jet-stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3-carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3-carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara-2,4-diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS-QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3-carene. Both the conversion of 3-carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3-carene are hydrogen elimination reaction and radical chemistry. 相似文献
135.
Dr. Jean-Noël Rebilly Wenli Zhang Dr. Christian Herrero Dr. Hachem Dridi Dr. Katell Sénéchal-David Dr. Régis Guillot Prof. Frédéric Banse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):659-668
Rieske dioxygenases are metalloenzymes capable of achieving cis-dihydroxylation of aromatics under mild conditions using O2 and a source of electrons. The intermediate responsible for this reactivity is proposed to be a cis-FeV(O)(OH) moiety. Molecular models allow the generation of a FeIII(OOH) species with H2O2, to yield a FeV(O)(OH) species with tetradentate ligands, or {FeIV(O); OH.} pairs with pentadentate ones. We have designed a new pentadentate ligand, mtL42, bearing a labile triazole, to generate an “in-between” situation. Two iron complexes, [(mtL42)FeCl](PF6) and [(mtL42)Fe(OTf)2]), were obtained and their reactivity towards aromatic substrates was studied in the presence of H2O2. Spectroscopic and kinetic studies reflect that triazole is bound at the FeII state, but decoordinates in the FeIII(OOH). The resulting [(mtL42)FeIII(OOH)(MeCN)]2+ then lies on a bifurcated decay pathway (end-on homolytic vs. side-on heterolytic) depending on the addition of aromatic substrate: in the absence of substrate, it is proposed to follow a side-on pathway leading to a putative (N4)FeV(O)(OH), while in the presence of aromatics it switches to an end-on homolytic pathway yielding a {(N5)FeIV(O); OH.} reactive species, through recoordination of triazole. This switch significantly impacts the reaction regioselectivity. 相似文献
136.
Olivier Herbinet Benoit Husson Hervé Le Gall Frédérique Battin-Leclerc 《国际化学动力学杂志》2020,52(12):1006-1021
In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C7 diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C8 fuels and of 19 products for the C10 one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities. 相似文献
137.
Manon Catherin Olatz Uranga-Barandiaran Arnaud Brosseau Dr. Rémi Métivier Dr. Gabriel Canard Dr. Anthony D'Aléo Dr. David Casanova Prof. Frédéric Castet Dr. Elena Zaborova Prof. Frédéric Fages 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3818-3828
We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF2 dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional 1H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore. 相似文献
138.
Piotr Frąckiewicz 《Physics letters. A》2018,382(48):3463-3469
The Li–Du–Massar quantum duopoly model is one of the generally accepted quantum game schemes. It has applications in a wide range of duopoly problems. Our purpose is to study Stackelberg's duopoly with incomplete information in the quantum domain. The result of Lo and Kiang has shown that the correlation of players' quantities caused by the quantum entanglement enhances the first-mover advantage in the game. Our work demonstrates that there is no first-mover advantage if the players' actions are maximally correlated. Furthermore, we proved that the second mover gains a higher equilibrium payoff than the first one. 相似文献
139.
140.
We consider graphs with prescribed mean curvature and flat normal bundle. Using techniques of Schoen et al. (Acta Math 134:275–288, 1975) and
Ecker and Huisken (Ann Inst H Poincaré Anal Non Linèaire 6:251–260, 1989), we derive the interior curvature estimate
up to dimension n ≤ 5, where C is a constant depending on natural geometric data of Σ only. This generalizes previous results of Smoczyk et al. (Calc Var
Partial Differ Equs 2006) and Wang (Preprint, 2004) for minimal graphs with flat normal bundle. 相似文献