全文获取类型
收费全文 | 4609篇 |
免费 | 756篇 |
国内免费 | 301篇 |
专业分类
化学 | 3036篇 |
晶体学 | 21篇 |
力学 | 126篇 |
综合类 | 74篇 |
数学 | 1917篇 |
物理学 | 492篇 |
出版年
2024年 | 3篇 |
2023年 | 49篇 |
2022年 | 76篇 |
2021年 | 85篇 |
2020年 | 183篇 |
2019年 | 148篇 |
2018年 | 127篇 |
2017年 | 117篇 |
2016年 | 244篇 |
2015年 | 234篇 |
2014年 | 257篇 |
2013年 | 405篇 |
2012年 | 293篇 |
2011年 | 338篇 |
2010年 | 300篇 |
2009年 | 337篇 |
2008年 | 360篇 |
2007年 | 291篇 |
2006年 | 284篇 |
2005年 | 210篇 |
2004年 | 221篇 |
2003年 | 222篇 |
2002年 | 149篇 |
2001年 | 98篇 |
2000年 | 98篇 |
1999年 | 87篇 |
1998年 | 75篇 |
1997年 | 94篇 |
1996年 | 49篇 |
1995年 | 35篇 |
1994年 | 32篇 |
1993年 | 23篇 |
1992年 | 20篇 |
1991年 | 17篇 |
1990年 | 16篇 |
1989年 | 9篇 |
1988年 | 3篇 |
1987年 | 8篇 |
1986年 | 14篇 |
1985年 | 8篇 |
1984年 | 9篇 |
1983年 | 3篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1973年 | 2篇 |
1969年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有5666条查询结果,搜索用时 187 毫秒
81.
82.
Slowly time-varying delays are seldom, but do need to be, considered in the context of discrete-time systems. This paper addresses the exponential stability issue of discrete-time systems with slowly time-varying delays. The basic idea is to transform, by utilizing the switching transformation approach, the original system with slowly time-varying delays into an equivalent switched system with special switching signal. Different types of delays correspond to different types of switching signals, and the stability issue of the original system is converted into that of a switched system. It is the first time that the method of switched homogeneous polynomial Lyapunov function is applied to general delayed systems. Some sufficient exponential stability conditions for the original system are proposed in several situations. It is numerically shown that the conservativeness of the proposed conditions reduces as the degree of the switched homogeneous polynomial Lyapunov function increases. 相似文献
83.
Friedbert Prü fer Franco Tricerri Lieven Vanhecke 《Transactions of the American Mathematical Society》1996,348(11):4643-4652
We first prove that a Riemannian manifold with globally constant additive Weyl invariants is locally homogeneous. Then we use this result to show that a manifold whose Laplacian commutes with all invariant differential operators is a locally homogeneous space.
84.
Arie Tamir 《Mathematical Programming》1993,62(1-3):475-496
In the classicalp-center location model on a network there is a set of customers, and the primary objective is to selectp service centers that will minimize the maximum distance of a customer to a closest center. Suppose that thep centers receive their supplies from an existing central depot on the network, e.g. a warehouse. Thus, a secondary objective is to locate the centers that optimize the primary objective as close as possible to the central depot. We consider tree networks and twop-center models. We show that the set of optimal solutions to the primary objective has a semilattice structure with respect to some natural ordering. Using this property we prove that there is ap-center solution to the primary objective that simultaneously minimizes every secondary objective function which is monotone nondecreasing in the distances of thep centers from the existing central depot.Restricting the location models to a rooted path network (real line) we prove that the above results hold for the respective classicalp-median problems as well. 相似文献
85.
86.
In this B3 LYP model study, homoleptic nickel(0) ethyne complexes have been predicted as the catalyst resting state for the title reaction. Ethyne ligand coupling of Ni(C(2)H(2))(3) yields monoethyne nickelacyclopentadiene in the rate-determining step. Ethyne coordination is followed by insertion of an ethyne ligand into the Ni--C sigma bond. A highly strained monoethyne trans-nickelacycloheptatriene is formed. This trans intermediate is unable to reductively eliminate benzene without prior isomerization to a cis-structure. Instead, it rapidly collapses to a nickelacyclononatetraene. Ethyne coordination induces reductive elimination to the cyclooctatetraene complex Ni(eta(2)-C(2)H(2))(eta(2)-C(8)H(8)), followed by facile ligand exchange. Other ethyne coupling pathways have been computed to be less favored. The cyclooctatetraene ligand binds significantly weaker to nickel(0) than ethyne, both for mononuclear, and for dinuclear species. For this reason, C--C bond formation steps at Ni(2)(micro-cot) fragments have been predicted to feature prohibitively high overall reaction barriers. 相似文献
87.
Effect of molecular orientation distribution and crystallinity on the measurement of the crystal lattice modulus of nylon 6 by x-ray diffraction 总被引:1,自引:0,他引:1
The crystal lattice modulus of nylon 6 (-type) was measured by x-ray diffraction using nylon 6 films drawn up to five times. The measured crystal lattice modulus was 173–175 GPa for all specimens whose crystallinity and the Young's modulus were beyond 46% and 3.75 GPa, respectively. These results indicate that a state of homogenous stress can be achieved. In contrast, the values were scattered for the speciments whose crystallinity and Young's modulus are less than the above values. To study the origin, a numerical calculation of the crystal lattice modulus, as measured by x-ray diffraction, was carried out by considering effects on the orientation factors of molecular chains and crystallinity. In this calculation, a previously introduced model was employed, in which oriented crystalline layers are surrounded by oriented amorphous phases so that the strains of the two phases at the boundary are identical. The theoretical results calculated by the introduced model indicated that the crystal lattice modulus by x-ray diffraction is almost equal to the intrinsic crystal modulus if the morphology of the test specimen can be represented as a series model. In contrast, if a parallel model is more appropriate, the difference between the measured modulus and the intrinsic value can be pronounced. Such morphological dependence was found to be less pronounced with increasing high degree of molecular orientation and crystallinity. 相似文献
88.
Takaya Matsumoto 《Catalysis Surveys from Asia》2007,11(1-2):31-48
In this article, two kinds of our transition metal-catalyzed olefin arylations are summarized and discussed. The first one
is Ir-catalyzed novel anti-Markovnikov hydroarylation of olefins with benzene. Using this reaction catalyzed by [Ir(μ-acac-O,O′,C3)(acac-O,O′)(acac-C3)]2 (acac = acetylacetonato), 1, straight-chain alkylarenes, which were not obtainable by the conventional Friedel-Crafts aromatic alkylation with olefins,
were able to be successfully synthesized directly from arenes and olefins with the higher selectivity than that of branched
alkylarenes. This is the first efficient catalyst which shows the desirable high regioselectivity. The reaction of benzene
with propylene gave n-propylbenzene and cumene in 61% and 39% selectivities, respectively, and the reaction of benzene and styrene afforded 1,2-diphenylethane
in 98% selectivity. The reaction of alkylarene and olefin showed meta and para orientations. A wide range of olefins and arenes
can be employed for the synthesis of alkylarenes. The mechanism of the reaction involves C–H bond activation of benzene by
Ir center to form Ir–phenyl species. The second reaction is Rh-catalyzed oxidative arylation of ethylene with benzene to directly
produce styrene, namely one-step synthesis of styrene. The reaction of benzene with ethylene catalyzed by Rh(ppy)2(OAc) (ppyH = 2-phenylpyridine, OAc = acetate), 3 with Cu oxidizing agent gave styrene and vinyl acetate in 77% and 23% selectivities, respectively, in contrast to those by
Pd(OAc)2, 47% of styrene and 53% of vinyl acetate. The mechanism of the reaction involves Rh-mediated C–H bond activation of benzene,
which appears to be a rate-determining step. Furthermore, Rh complexes in a Rh(I) oxidation state at the beginning of the
reaction work as catalysts for the reaction by addition of acacH and O2 without any oxidizing agent, like Cu salt. 相似文献
89.
在电极袭面反应物浓度均匀的近似假设下,得到了微圆盘电极上暂态可逆反应的一般解.然后利用该一般解得到了微圆盘电极上耦合一级均相反应的可逆电极反应CE、EC、EC′和ECE 的稳态电流计算公式. 相似文献
90.
Kumar K Michalik D Garcia Castro I Tillack A Zapf A Arlt M Heinrich T Böttcher H Beller M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):746-757
A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals. 相似文献