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111.
Quentin Michaudel Guillaume Journot Alicia Regueiro‐Ren Animesh Goswami Zhiwei Guo Thomas P. Tully Lufeng Zou Raghunath O. Ramabhadran Kendall N. Houk Phil S. Baran 《Angewandte Chemie (International ed. in English)》2014,53(45):12091-12096
Physicochemical properties constitute a key factor for the success of a drug candidate. Whereas many strategies to improve the physicochemical properties of small heterocycle‐type leads exist, complex hydrocarbon skeletons are more challenging to derivatize because of the absence of functional groups. A variety of C H oxidation methods have been explored on the betulin skeleton to improve the solubility of this very bioactive, yet poorly water‐soluble, natural product. Capitalizing on the innate reactivity of the molecule, as well as the few molecular handles present on the core, allowed oxidations at different positions across the pentacyclic structure. Enzymatic oxidations afforded several orthogonal oxidations to chemical methods. Solubility measurements showed an enhancement for many of the synthesized compounds. 相似文献
112.
Free radicals are observed in γ-irradiated single crystals of 5-nitrouracil with the unpaired electron showing hyperfine interaction with one nitrogen atom. The principal values of hyperfine coupling are Ax = 22·5 g, Ay = 25·2 g, and Az = 40·0 g, and the principal values of the spectroscopic splitting factor are gu = 2·0117, gv = 2·0064 and gw = 2·0027. The relationship of the directions of the corresponding principal axes to the molecular orientations show that the unpaired electron must be located in an sp 2 orbital on either N(1) or N(5). Considerations of the mechanism of radical formation and comparison to radiation damage in other molecules make the N(1) location seem more probable. The π interaction of the nitro group on C(5) evidently prevents the formulation of free radicals with the unpaired electron on C(5). That carbon atom is the most common location of unpaired electron density in other pyrimidine free radicals. 相似文献
113.
Harold P. Benson 《Journal of Global Optimization》1993,3(1):95-111
The algorithms and algorithmic ideas currently available for globally optimizing linear functions over the efficient sets of multiple objective linear programs either use nonstandard subroutines or cannot yet be implemented for lack of sufficient development. In this paper a Bisection-Extreme Point Search Algorithm is presented for globally solving a large class of such problems. The algorithm finds an exact, globally-optimal solution after a finite number of iterations. It can be implemented by using only well-known pivoting and optimization subroutines, and it is adaptable to large scale problems or to problems with many local optima. 相似文献
114.
Vijay Janyani Ana Vukovic John D. Paul Phillip Sewell Trevor M. Benson 《Optical and Quantum Electronics》2005,37(1-3):3-24
The paper investigates and compares a range of different models currently used for modelling nonlinear optical phenomena. The models are implemented in the numerical time domain Transmission Line Modelling (TLM) method and include a Kerr model and different formulations of the Duffing model. The models are used to simulate an all-optical limiter for a CW input and results compared with ones available in the literature. This enables a comparison to be made between the different models, from which it is concluded that the Duffing model has some advantages, when modelling materials and phenomena involving more than one frequency, arising from its ability to describe dispersive effects. These conclusions are further supported by the simulation results obtained for a pulse input. 相似文献
115.
Advection and dispersion in time and space 总被引:2,自引:0,他引:2
Previous work showed how moving particles that rest along their trajectory lead to time-nonlocal advection–dispersion equations. If the waiting times have infinite mean, the model equation contains a fractional time derivative of order between 0 and 1. In this article, we develop a new advection–dispersion equation with an additional fractional time derivative of order between 1 and 2. Solutions to the equation are obtained by subordination. The form of the time derivative is related to the probability distribution of particle waiting times and the subordinator is given as the first passage time density of the waiting time process which is computed explicitly. 相似文献
116.
The equivalence between the propagation of dispersive modal fields in two-dimensional waveguides, and plane waves in a one-dimensional plasma is presented. Exploitation of this equivalence allows a time domain variant of the effective index approach to be used to model dispersive waveguides problems very efficiently. A time domain integral equation is developed for this important practical case and the stability of a computer algorithm based upon it is improved by means of both a semi-implicit formulation and the use of a modified space–time mesh. 相似文献
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119.
H. F. Arrand T. M. Benson A. Loni R. Arens-Fischer M. G. Krueger M. Thoenissen H. Lueth S. Kershaw N. N. Vorozov 《Journal of luminescence》1998,80(1-4):119-123
Since the first report on the use of porous silicon as an optical waveguide medium in 1995, significant development has been made towards the understanding and applicability of such material. Here, the introduction of solvents (acetone, methanol, and propan-2-ol) into the pores is shown to dramatically reduce the loss of the waveguides, in a reversible manner. Both the magnitude and duration of this effect are sensitive to the solvent introduced. In some waveguides, for example, the measured loss (at 0.633 μm) falls by as much as 34 dB cm−1 on the introduction of acetone. Theoretical estimates of the effect of solvents on the interfacial scattering loss confirm this as the origin of the observed reductions. These results, combined with the fact that a substantial portion of the guided-mode field interacts with the solvent, indicate an enhanced sensitivity for sensor applications may be achievable. 相似文献
120.
Pyrolysis of cis-butene-2 under conditions of very low pressure (VLPP) has been studied in the range of 1100–1300°K. The principal products are butadiene and H2, obtained in a unimolecular reaction. A competing reaction to form butene-l accounts for from 10% to 40% of the overall decomposition over the range. Using a «tight» model for the transition state and RRKM theory yields a high-pressure, unimolecular rate constant for the 1,4-H2 elimination of where θ = 2.303RT in kcal/mol. There is some surface reaction of butadiene at these temperatures to yield H2 + nonvolatile residue. Butene-l proceeds to decompose irreversibly to allyl + methyl radicals which have been observed directly. Comparison with related reactions leads to the conclusion that orbital symmetry-forbidden, 1,2-H2 elimination from saturated organic compounds will have activation energies too high to observe. 相似文献