全文获取类型
收费全文 | 3250篇 |
免费 | 481篇 |
国内免费 | 97篇 |
专业分类
化学 | 3477篇 |
晶体学 | 81篇 |
力学 | 9篇 |
综合类 | 6篇 |
数学 | 80篇 |
物理学 | 175篇 |
出版年
2024年 | 8篇 |
2023年 | 39篇 |
2022年 | 55篇 |
2021年 | 79篇 |
2020年 | 141篇 |
2019年 | 99篇 |
2018年 | 90篇 |
2017年 | 61篇 |
2016年 | 182篇 |
2015年 | 153篇 |
2014年 | 200篇 |
2013年 | 246篇 |
2012年 | 221篇 |
2011年 | 177篇 |
2010年 | 153篇 |
2009年 | 197篇 |
2008年 | 236篇 |
2007年 | 258篇 |
2006年 | 204篇 |
2005年 | 221篇 |
2004年 | 205篇 |
2003年 | 111篇 |
2002年 | 56篇 |
2001年 | 49篇 |
2000年 | 54篇 |
1999年 | 64篇 |
1998年 | 50篇 |
1997年 | 48篇 |
1996年 | 42篇 |
1995年 | 37篇 |
1994年 | 18篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有3828条查询结果,搜索用时 15 毫秒
1.
Thomas Marmin Prof. Yves L. Dory 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6707-6711
Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C3-symmetric rings incorporating conjugated alkenes and dienes. All three C3-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals. 相似文献
2.
New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers 下载免费PDF全文
Prof. Dr. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
3.
Michiel Janssen Prof. Dirk E. De Vos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(45):10724-10734
The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing PtIV with a more economically viable oxidant, particularly O2. We report the potential of employing FeCl2 as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O2 in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O2 in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt0 was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N2 in the gaseous atmosphere. Finally, stability tests revealed the involvement of PtII and FeCl2 in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O2 is presented. 相似文献
4.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(9):2399-2399
5.
Alain Estve Adeline Bail Georges Landa Ahmed Dkhissi Marie Brut Mehdi Djafari Rouhani Jan Sudor Anne-Marie Gu 《Chemical physics》2007,340(1-3):12-16
Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior. 相似文献
6.
一类广义Bent型S-Box的构造 总被引:1,自引:0,他引:1
王章雄 《数学的实践与认识》2002,32(6):999-1002
S-box是密码理论与实践中十分重要的一种装置 ,它的密码性能由其分量函数所决定 .于是 ,选择适当的分量函数来构造 S-box就成了一个重要的研究课题 .在一定意义上 ,Bent函数是最优良的密码函数 .本文通过函数序列半群和置换群来构造其任何非零线性组合为 Bent函数与线性函数之和的函数组 ,从而可由 Bent函数构造出具有高度非线性度和其他良好性状的 S-box 相似文献
7.
8.
In this paper, we give a construction of RDS in Galois ring by using some bent function, and obtain the equivalent relationship between RDS and a kind of bent function. At the same time, its existence is demonstrated. 相似文献
9.
10.
Michael C. W. Chan Dr. 《化学:亚洲杂志》2008,3(1):18-27
The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???Hβ ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis. 相似文献