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131.
Naotake Nakamura Kenjiro Uno Yoshihiro Ogawa 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(11):1389-1390
In the molecular structure of the title compound, C21H44O2, the hydrocarbon skeleton has an all‐trans conformation. One of the terminal hydroxyl groups is also trans with respect to the skeleton, while the other is gauche. In the crystal structure, the molecules lie parallel to the b axis, forming layers with a thickness of b/2. The packing is similar to that in the smectic A phase of liquid crystals. These features are similar to those of the homologues with an odd number of C atoms, but different from those with an even number. 相似文献
132.
Dr. Randa K. Gabr Prof. Dr. Takuji Hatakeyama Prof. Dr. Kazuhiro Takenaka Prof. Dr. Shinobu Takizawa Yoshihiro Okada Prof. Dr. Masaharu Nakamura Prof. Dr. Hiroaki Sasai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9518-9525
The reaction pathway of an enantioselective 5‐endo‐trig‐type cyclization of 3‐alkenoic acids catalyzed by a chiral palladium–spiro‐bis(isoxazoline) complex, Pd–SPRIX, has been studied by density functional theory calculations. The most plausible pathway involves intramolecular nucleophilic attack of the carboxylate moiety on the C?C double bond activated by Pd–SPRIX and β‐H elimination from the resulting organopalladium intermediate. The enantioselectivity was determined in the cyclization step through the formation of a π‐olefin complex, in which one of the two enantiofaces of the olefin moiety was selected. The β‐H elimination occurs via a seven‐membered cyclic structure in which the acetate ligand plays a key role in lowering the activation barrier of the transition state. In the elimination step, the SPRIX ligand was found to behave as a monodentate ligand due to the hemilability of one of the isoxazoline units thereby facilitating the elimination. Natural population analysis of this pathway showed that the more weakly electron‐donating SPRIX ligand, compared with the bis(oxazoline) ligand, BOX, facilitated the formation of the π‐olefin complex intermediate, leading to a smaller overall activation energy and a higher reactivity of the Pd–SPRIX catalyst. 相似文献
133.
Let f : U → X be a map from a connected nilpotent space U to a connected rational space X. The evaluation subgroup G
*(U, X; f), which is a generalization of the Gottlieb group of X, is investigated. The key device for the study is an explicit Sullivan model for the connected component containing f of the function space of maps from U to X, which is derived from the general theory of such a model due to Brown and Szczarba (Trans Am Math Soc 349, 4931–4951, 1997).
In particular, we show that non Gottlieb elements are detected by analyzing a Sullivan model for the map f and by looking at non-triviality of higher order Whitehead products in the homotopy group of X. The Gottlieb triviality of a fibration in the sense of Lupton and Smith (The evaluation subgroup of a fibre inclusion, 2006)
is also discussed from the function space model point of view. Moreover, we proceed to consideration of the evaluation subgroup
of the fundamental group of a nilpotent space. In consequence, the first Gottlieb group of the total space of each S
1-bundle over the n-dimensional torus is determined explicitly in the non-rational case.
相似文献
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137.
Yoshihiro Takebayashi Hiroyuki Hotta Atsushi Shono Katsuto Otake Kiwamu Sue Satoshi Yoda Takeshi Furuya 《Journal of solution chemistry》2009,38(5):545-555
Acid-base equilibria between 2,5-dichlorophenol (DCP) and various bases (LiOH, NaOH, and KOH) were studied in ambient to supercritical
methanol, by measuring the absorption spectrum of DCP at alkali metal hydroxide molalities ranging up to 10 mmol⋅kg−1, at temperatures up to 250 °C and a pressure of 25.0 MPa. The spectrum was deconvoluted into contributions for the acidic
(HA) and basic (A−) forms of DCP, taking into account a blue shift of the phenolate (A−) spectrum due to the effect of ion pairing with an alkali metal cation. Degrees of dissociation of DCP determined from the
spectra suggested that the dissociation constant of DCP has a maximum around 150 °C, whereas that of KOH decreases with temperature.
The phenolate-alkali metal ion pairing was examined from the peak shift of the phenolate spectrum in the presence of Li+, Na+, and K+. A smaller cation radius and higher temperature (thus a lower dielectric constant for methanol) give rise to stronger electrostatic
interaction in the ion pair. The basicities of the alkali metal hydroxides in supercritical methanol were compared using DCP
as an indicator, and were shown to follow the order LiOH < NaOH ≤ KOH. This order is the same as that for the catalytic effect
of alkali metal hydroxides on the methylation of phenol in supercritical methanol (Takebayashi et al.: Ind. Eng. Chem. Res.
47:704–709, 2008).
Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
138.
Matthias Röger Yoshihiro Tonegawa 《Calculus of Variations and Partial Differential Equations》2008,32(1):111-136
We prove the convergence of phase-field approximations of the Gibbs–Thomson law. This establishes a relation between the first
variation of the Van der Waals–Cahn–Hilliard energy and the first variation of the area functional. We allow for folding of
diffuse interfaces in the limit and the occurrence of higher-multiplicities of the limit energy measures. We show that the
multiplicity does not affect the Gibbs–Thomson law and that the mean curvature vanishes where diffuse interfaces have collided.
We apply our results to prove the convergence of stationary points of the Cahn–Hilliard equation to constant mean curvature
surfaces and the convergence of stationary points of an energy functional that was proposed by Ohta–Kawasaki as a model for
micro-phase separation in block-copolymers. 相似文献
139.
John E. Hutchinson Yoshihiro Tonegawa 《Calculus of Variations and Partial Differential Equations》2000,10(1):49-84
We study the general asymptotic behavior of critical points, including those of non-minimal energy type, of the functional
for the van der Waals-Cahn-Hilliard theory of phase transitions. We prove that the interface is close to a hypersurface with
mean curvature zero when no Lagrange multiplier is present, and with locally constant mean curvature in general. The energy
density of the limiting measure has integer multiplicity almost everywhere modulo division by a surface energy constant.
Received March 16, 1999 / Accepted June 11, 1999 相似文献
140.
Yuya Ikeuchi Dr. Hiroshi Takatsu Dr. Cédric Tassel Yoshihiro Goto Taito Murakami Prof. Hiroshi Kageyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5864-5867
A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K3W5O15 (K0.6WO3). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of RW=3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze KxWO3-K0.6−yBayWO3 phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO3 phase was also identified as a line phase—in marked contrast to NaxWO3 and LixWO3 with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended. 相似文献