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71.
Jian Dong Zhihao Zhuang Feng Song Debra Dunaway‐Mariano Paul R. Carey 《Journal of Raman spectroscopy : JRS》2012,43(1):65-71
4‐Hydroxybenzoyl‐CoA (4‐HB‐CoA) thioesterase from Arthrobacter is the final enzyme catalyzing the hydrolysis of 4‐HB‐CoA to produce coenzyme A and 4‐hydroxybenzoic acid in the bacterial 4‐chlorobenzoate dehalogenation pathway. Using a mutation E73A that blocks catalysis, stable complexes of the enzyme and its substrate can be analyzed by Raman difference spectroscopy. Here we have used Raman difference spectroscopy, in the non‐resonance regime, to characterize 4‐HB‐CoA bound in the active site of the E73A thioesterase. In addition, we have characterized complexes of the wild‐type enzyme complexed with the unreactive substrate analog 4‐hydroxyphenacyl‐CoA (4‐HP‐CoA). Both sets of complexes show evidence for two forms of the ligand in the active site: one population has the 4‐hydroxy group protonated, 4‐OH; while the second has the group as the hydroxide, 4‐O−. For bound 4‐HP‐CoA, X‐ray data show that glutamate 78 is close to the 4‐OH in the complex and it is likely that this is the proton acceptor for the 4‐OH proton. Although the pKa of the 4‐OH group on the free substrate in aqueous solution is 8.6, the relative populations of ionized and neutral 4‐HB‐CoA bound to E73A remain invariant between pH 7.3 and 9.8. The invariance with pH suggests that the 4‐OH and the ‐COO− of E78 constitute a tightly coupled pair where their separate pKa ‘s lose their individual qualities. Narrow band profiles are seen in the CO double bond and C‐S regions, suggesting that the hydrolyzable thioester group is rigidly bound in the active site in a syn gauche conformation. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
72.
Carey T Corma A Rey F Tang CC Hriljac JA Anderson PA 《Chemical communications (Cambridge, England)》2012,48(47):5829-5831
X-Ray powder diffraction studies have been used to measure the thermal expansion properties of three zeolites with the LTA topology and provide details of the underlying structural changes. Siliceous ITQ-29 and dehydrated and hydrated silver zeolite A have large negative, moderate negative and positive thermal expansion coefficients, respectively. 相似文献
73.
The positive energy representations of the loop group of U(1) are used to construct a boson-anyon correspondence. We compute
all the correlation functions of our anyon fields and study an anyonic W-algebra of unbounded operators with a common dense domain. This algebra contains an operator with peculiar exchange relations
with the anyon fields. This operator can be interpreted as a second quantized Calogero–Sutherland (CS) Hamiltonian and may
be used to solve the CS model. In particular, we inductively construct all eigenfunctions of the CS model from anyon correlation
functions, for all particle numbers and positive couplings.
Received: 12 May 1998 / Accepted: 4 August 1998 相似文献
74.
75.
The standard two-dimensional shallow water equation formulation assumes a mild bed slope and no curvature effect. These assumptions limit the applicability of these equations for some important classes of problems. In particular, flow over a spillway is affected by the bed curvature via a decidedly non-hydrostatic pressure distribution. A detailed derivation of a more general equation set is given here in Part I. The method relies upon a perturbation expansion to simplify a bed-fitted co-ordinate configuration of the three-dimensional Euler equations. The resulting equations are essentially the equivalent of the two-dimensional shallow water equations but with curvature included and without the mild slope assumption. A finite element analysis and flume result are given in Part II. © 1998 John Wiley & Sons, Ltd. 相似文献
76.
A mathematical model and adaptive finite element scheme are developed for describing the distribution of proppant in a propagating hydraulic fracture. The governing equation for proppant concentration is derived by applying the conservation law of mass to the proppant and to the proppant-laden fluid. Shah's empirical equation, which relates the proppant concentration and the indices of the non-Newtonian fluid, is used to describe the proppant-laden fluid. The proppant distribution inside a hydraulic fracture can then be obtained by solving the proppant concentration equation together with the governing equations of fluid and elasticity for a hydraulic fracturing. A novel moving grid scheme is developed that combines grid point insertion with redistribution. Four examples corresponding to different in situ stress distributions are computed to demonstrate the scheme. © 1997 by John Wiley & Sons, Ltd. 相似文献
77.
AlanL.CAREY BaiLingWANG 《数学学报(英文版)》2003,19(2):245-296
This paper gives a detailed construction of Seiberg-Witten-Floer homology for a closed oriented 3-manifold with a non-torsion Spin^C structure.Gluing formulae for certain 4-dimensional manifolds splitting along an embedded 3-manifold are obtained. 相似文献
78.
The concept of a holonomy term in a Lagrangian is introduced. It unifies the idea of the interaction term in the Dirac monopole and the Wess-Zumino term. In particular, it provides a dynamical interpretation of the Kac-Moody cocycle on a loop group. 相似文献
79.
Viscoelastic flows remain a demanding class of problems for approximate analysis, particularly at increasing Weissenberg numbers. Part of the difficulty stems from the convective behavior and in the treatment of the stress field as a primary unknown. This latter aspect has led to the use of higher-order piecewise approximations for the stress approximation spaces in recent finite element research. The computational complexity of the discretized problem is increased significantly by this approach but at present it appears the most viable technique for solving these problems. Motivated by recent success in treating mixed systems and convective problems, we formulate here a least squares finite element method for the viscoelastic flow problem. Numerical experiments are conducted to test the method and examine its strengths and limitations. Some difficulties and open issues are identified through the numerical experiments. We consider the use of high degree elements (p refinement) to improve performance and accuracy. 相似文献
80.