全文获取类型
收费全文 | 6791篇 |
免费 | 831篇 |
国内免费 | 565篇 |
专业分类
化学 | 6347篇 |
晶体学 | 11篇 |
力学 | 122篇 |
综合类 | 45篇 |
数学 | 712篇 |
物理学 | 950篇 |
出版年
2024年 | 4篇 |
2023年 | 71篇 |
2022年 | 254篇 |
2021年 | 262篇 |
2020年 | 270篇 |
2019年 | 222篇 |
2018年 | 235篇 |
2017年 | 193篇 |
2016年 | 276篇 |
2015年 | 314篇 |
2014年 | 394篇 |
2013年 | 709篇 |
2012年 | 348篇 |
2011年 | 474篇 |
2010年 | 333篇 |
2009年 | 387篇 |
2008年 | 389篇 |
2007年 | 426篇 |
2006年 | 355篇 |
2005年 | 326篇 |
2004年 | 279篇 |
2003年 | 270篇 |
2002年 | 295篇 |
2001年 | 142篇 |
2000年 | 135篇 |
1999年 | 120篇 |
1998年 | 120篇 |
1997年 | 88篇 |
1996年 | 71篇 |
1995年 | 51篇 |
1994年 | 62篇 |
1993年 | 66篇 |
1992年 | 35篇 |
1991年 | 24篇 |
1990年 | 18篇 |
1989年 | 24篇 |
1988年 | 18篇 |
1987年 | 16篇 |
1986年 | 11篇 |
1985年 | 15篇 |
1984年 | 8篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1976年 | 3篇 |
1973年 | 7篇 |
1970年 | 5篇 |
1968年 | 2篇 |
排序方式: 共有8187条查询结果,搜索用时 15 毫秒
1.
Kento Nishikibe Keisuke Nishikawa Momochika Kumagai Matsumi Doe Yoshiki Morimoto 《化学:亚洲杂志》2022,17(1):e202101137
There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis. 相似文献
2.
Claudius Gros 《Entropy (Basel, Switzerland)》2021,23(2)
Human societies are characterized by three constituent features, besides others. (A) Options, as for jobs and societal positions, differ with respect to their associated monetary and non-monetary payoffs. (B) Competition leads to reduced payoffs when individuals compete for the same option as others. (C) People care about how they are doing relatively to others. The latter trait—the propensity to compare one’s own success with that of others—expresses itself as envy. It is shown that the combination of (A)–(C) leads to spontaneous class stratification. Societies of agents split endogenously into two social classes, an upper and a lower class, when envy becomes relevant. A comprehensive analysis of the Nash equilibria characterizing a basic reference game is presented. Class separation is due to the condensation of the strategies of lower-class agents, which play an identical mixed strategy. Upper-class agents do not condense, following individualist pure strategies. The model and results are size-consistent, holding for arbitrary large numbers of agents and options. Analytic results are confirmed by extensive numerical simulations. An analogy to interacting confined classical particles is discussed. 相似文献
3.
4.
Natural products with a variety of pharmacological effects are important sources for commercial drugs, and it is very crucial to develop effective techniques to selectively extract and isolate bioactive natural components from the plants against the background of sustainable development. Ionic liquids (ILs) are a kind of designable material with unique physicochemical properties, including good thermal stability, negligible vapor pressure, good solvation ability, etc. ILs have already been used in pharmaceuticals for extraction, purification, drug delivery, etc. It has been reported that multi-interactions, like hydrogen bonding, hydrophobic interactions, play important roles in the extraction of bioactive components from the plants. In this review, recent progress in the understanding of scientific essence of hydrogen bonding, the special interaction, in ILs was summarized. The extraction of various natural products, one important area in pharmaceutical, by conventional and functional ILs as well as the specific roles of multi-interactions in this process were also reviewed. Moreover, problems existing in bioactive compound extraction by ILs and the future developing trends of this area are given, which might be helpful for scientists, especially beginners, in this field. 相似文献
5.
Szabolcs Cserényi 《Journal of fluorine chemistry》2006,127(7):850-853
The Perkin reaction of the activated aromatic ketones (2,2,2-trifluoroacetophenone and its 4′-phenyl-derivative) with various condensing agents (acetic anhydride, propionic anhydride, phenylacetic acid/acetic anhydride) gives the title compounds in good or moderate yields, and high E-stereoselectivity. For some derivatives an appreciable amount of the Z isomer was also formed. Several of the resulting butenoic acids and their methyl esters are synthesised and characterised for the first time. 相似文献
6.
F. Gugumus 《Polymer Degradation and Stability》2006,91(11):2698-2714
Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 105 than to 6 × 105 (s−1) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical. 相似文献
7.
Laurent Gosse. 《Mathematics of Computation》2002,71(238):553-582
This paper investigates the behavior of numerical schemes for nonlinear conservation laws with source terms. We concentrate on two significant examples: relaxation approximations and genuinely nonhomogeneous scalar laws. The main tool in our analysis is the extensive use of weak limits and nonconservative products which allow us to describe accurately the operations achieved in practice when using Riemann-based numerical schemes. Some illustrative and relevant computational results are provided.
8.
We study a model of a queueing system with two complementary products/services. In our model, there is one M/M/1 system and another facility that provides instantaneous service. The two services are complementary and the customer has no benefit from obtaining just one of them. We investigate the model under various price structures and ownership assumptions.AMS subject classification: 90B22, 91A10The authors are equal in their contribution to this paper. This paper is submitted by the first author to the Tokyo Institute of Technology as partial fulfillment of the requirements for the Ph.D. program in the Department of Value and Decision Sciences, and the order of names was chosen in compliance with program conditions. This research was supported by the Israel Science Foundation (grant No. 237/02). 相似文献
9.
Ernesto Quesada 《Tetrahedron letters》2004,45(25):4877-4881
The first syntheses of newly isolated members of the Preussomerin family, Preussomerins K and L, are reported. Key steps include the functionalisation of a 2-arylacetal anion, one-pot Friedel-Crafts cyclisation-deprotection and reductive opening of epoxides. 相似文献
10.
Emmanuel DardennesÁrpád Kovács-Kulyassa Andrea RenzettiJanos Sapi Jean-Yves Laronze 《Tetrahedron letters》2003,44(2):221-223
Chiral pyrano- and pyrrolidino-fused tryptamines were prepared by a diasteroselective trimolecular condensation between indole, Garner's aldehyde and Meldrum's acid, followed by selective functional group transformations. 相似文献