全文获取类型
收费全文 | 1312篇 |
免费 | 96篇 |
国内免费 | 7篇 |
专业分类
化学 | 1079篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 132篇 |
物理学 | 192篇 |
出版年
2023年 | 14篇 |
2022年 | 45篇 |
2021年 | 47篇 |
2020年 | 42篇 |
2019年 | 49篇 |
2018年 | 30篇 |
2017年 | 22篇 |
2016年 | 59篇 |
2015年 | 65篇 |
2014年 | 46篇 |
2013年 | 76篇 |
2012年 | 105篇 |
2011年 | 132篇 |
2010年 | 81篇 |
2009年 | 34篇 |
2008年 | 75篇 |
2007年 | 82篇 |
2006年 | 74篇 |
2005年 | 64篇 |
2004年 | 35篇 |
2003年 | 42篇 |
2002年 | 33篇 |
2001年 | 18篇 |
2000年 | 6篇 |
1999年 | 7篇 |
1998年 | 6篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1990年 | 5篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1983年 | 9篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 8篇 |
1978年 | 8篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1971年 | 2篇 |
排序方式: 共有1415条查询结果,搜索用时 15 毫秒
1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
3.
B.J. Stoyanov R.A. Farrell J.F. Bird 《Journal of Computational and Applied Mathematics》1994,50(1-3):533-543
Asymptotic expansions of certain finite and infinite integrals involving products of two Bessel functions of the first kind are obtained by using the generalized hypergeometric and Meijer functions. The Bessel functions involved are of arbitrary (generally different) orders, but of the same argument containing a parameter which tends to infinity. These types of integrals arise in various contexts, including wave scattering and crystallography, and are of general mathematical interest being related to the Riemann—Liouville and Hankel integrals. The results complete the asymptotic expansions derived previously by two different methods — a straightforward approach and the Mellin-transform technique. These asymptotic expansions supply practical algorithms for computing the integrals. The leading terms explicitly provide valuable analytical insight into the high-frequency behavior of the solutions to the wave-scattering problems. 相似文献
4.
The Castelnuovo-Mumford regularity of a module gives a rough measure of its complexity. We bound the regularity of a module given a system of approximating modules whose regularities are known. Such approximations can arise naturally for modules constructed by inductive combinatorial means. We apply these methods to bound the regularity of ideals constructed as combinations of linear ideals and the module of derivations of a hyperplane arrangement as well as to give degree bounds for invariants of finite groups. 相似文献
5.
Jessica Strömbro Peter Gudmundson 《International Journal of Solids and Structures》2008,45(22-23):5765-5787
In this paper a simplified network model for mechano-sorptive creep is presented, which is a further development of an earlier paper [Strömbro, J., Gudmundson, P., 2008. Mechano-sorptive creep under compressive loading – a micromechanical model. International Journal of Solids and Structures 45 (9), 2420–2450.]. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive effects in compression than in tension. Moisture dependent material parameters and anisotropy in the fibre distribution have been introduced. Theoretical predictions based on the model are compared to experimental results for an anisotropic paper both under tensile and compressive loading at varying moisture content and it is found that the important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined. 相似文献
6.
Colin J. Thompson Keith M. Briggs Peter Farrell Anthony Fleming Bruce Hocking Kenneth Joyner Vitas Anderson Andrew W. Wood 《Physica A》1995,220(3-4):471-484
A nonlinear Lorenz model describing interactions between charged particles and combined ac-dc electromagnetic fields is studied for various combinations of frequencies, field strengths and relative angle (θ) between the ac and dc magnetic fields. Strong directional effects on the magnitude and location of resonant particle motion are observed when θ is varied and the regular resonance windows in the aligned field (θ = 0) and linear version of the model studied previously by Durney etaal., break up to form irregular and less well pronounced regions of large and small particle displacements when nonlinearities are taken into account. The length of time takne to achieve resonant behaviour also becomes larger and more variable when nonlinearities are present. The possible relevance of these effects to interactions between electromagnetic fields and biological media is briefly discussed. 相似文献
7.
We have investigated variations in molecularly thin rotaxane films deposited by solvent evaporation, using atomic force microscopy (AFM). Small changes in rotaxane structure result in significant differences in film morphology. The addition of exo-pyridyl moietes to the rotaxane macrocycle results in uniform domains having orientations corresponding to the underlying substrate lattice, while a larger, less symmetric molecule results in a greater lattice mismatch and smaller domain sizes. We have measured differences in film heights both as a function of the solvent of deposition and as a function of surface coverage of rotaxanes. Based on these observations we describe how the use of solvents with higher hydrogen-bond basicity results in films which are more likely to favour sub-molecular motion. 相似文献
8.
This paper introduces a method of combining open and closed microchannels in a single component in a novel way which couples the benefits of both open and closed microfluidic systems and introduces interesting on-chip microfluidic behaviour. Fluid behaviour in such a component, based on continuous pressure driven flow and surface tension, is discussed in terms of cross sectional flow behaviour, robustness, flow-pressure performance, and its application to microfluidic interfacing. The closed-open-closed microchannel possesses the versatility of upstream and downstream closed microfluidics along with open fluidic direct access. The device has the advantage of eliminating gas bubbles present upstream when these enter the open channel section. The unique behaviour of this device opens the door to applications including direct liquid sample interfacing without the need for additional and bulky sample tubing. 相似文献
9.
Charge-transfer, crystalline complexes of 1,3,5-trinitrobenzene (TNB), 2,4,7- trinitro-9-fluorenone (TNF). and 2,4,5,7-tetranitro-9-fluorenone (TENF) with eleven polynuclear aromatic hydrocarbons were compared for thermal stability, ΔH and ΔS of melting. Factors possibly influencing the above parameters are discussed.Melting does not induce separation of the components; these complexes can be repeatedly crystallized and melted without variation of the ΔH of melting, thereby indicating high thermal stability.With a few exceptions, melting temperatures of the complexes increase in the order TNB<TNF<TENF: so do ΔH and ΔS of melting. A number of crystal transitions were observed. 相似文献
10.
Merkx M Kopp DA Sazinsky MH Blazyk JL Müller J Lippard SJ 《Angewandte Chemie (International ed. in English)》2001,40(15):2725
The cover picture shows in the background the whole cell of a methanotrophic bacterium on which are superimposed components of methane monooxygenase (the structure of the hydroxylase component (top), one of the two four-helix bundles that house the catalytic diiron centers (left)) and a schematic diagram of the catalytic cycle by which the enzyme converts dioxygen and methane into methanol and water. More about this unusual enzyme system is reported by Lippard et al. on p. 2782 ff. 相似文献