全文获取类型
收费全文 | 461篇 |
免费 | 28篇 |
国内免费 | 4篇 |
专业分类
化学 | 374篇 |
晶体学 | 5篇 |
力学 | 7篇 |
数学 | 43篇 |
物理学 | 64篇 |
出版年
2023年 | 3篇 |
2022年 | 1篇 |
2021年 | 5篇 |
2020年 | 13篇 |
2019年 | 12篇 |
2018年 | 11篇 |
2017年 | 3篇 |
2016年 | 18篇 |
2015年 | 22篇 |
2014年 | 15篇 |
2013年 | 12篇 |
2012年 | 25篇 |
2011年 | 36篇 |
2010年 | 30篇 |
2009年 | 14篇 |
2008年 | 34篇 |
2007年 | 27篇 |
2006年 | 26篇 |
2005年 | 29篇 |
2004年 | 31篇 |
2003年 | 19篇 |
2002年 | 21篇 |
2001年 | 4篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有493条查询结果,搜索用时 9 毫秒
81.
Mansikkamäki H Busi S Nissinen M Ahman A Rissanen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(16):4289-4296
The assembly of C-methyl resorcinarene into a tubular supramolecular solid-state structure, its thermal stability, and its hosting properties are reported. Careful control of the crystallisation conditions of C-methyl resorcinarene and 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane (1,4-dimethyl DABCO) dibromide leads to a formation of two crystallographically different, but structurally very similar, solid-state nanotube structures. These structures undergo a remarkable variety of supramolecular interactions, which lead to the formation of 0.5 nm diameter nonpolar tubes through the crystal lattice. The formation of these tubes is templated by suitably sized small alcohols, namely, n-propanol, 2-propanol, or n-butanol. The self-assembly involves close pi...pi interactions between the adjacent resorcinarenes, and C--H...pi and cation...pi interactions between the resorcinarenes and the guest 1,4-dimethyl DABCO dications. The crystals of these supramolecular tube structures are thermally very stable and the included solvent alcohol can be removed from the tubes without breaking the single-crystalline structure of the assembly. After removal of the solvent molecules the tubes can be filled with other small, less polar solvent molecules such as dichloromethane. 相似文献
82.
13C NMR chemical shifts delta(C)(C=N) were measured in CDCl3 for a wide set of mesogenic molecule model compounds, viz. the substituted benzylidene anilines p-X-C6H4CH=NC6H4-p-Y (X = NO2, CN, CF3, F, Cl, H, Me, MeO, or NMe2; Y = NO2, CN, F, Cl, H, Me, MeO, or NMe2). The substituent dependence of delta(C)(C=N) was used as a tool to study electronic substituent effects on the azomethine unit. The benzylidene substituents X have a reverse effect on delta(C)(C=N): electron-withdrawing substituents cause shielding, while electron-donating ones behave oppositely, the inductive effects clearly predominating over the resonance effects. In contrast, the aniline substituents Y exert normal effects: electron-withdrawing substituents cause deshielding, while electron-donating ones cause shielding of the C=N carbon, the strengths of the inductive and resonance effects being closely similar. Additionally, the presence of a specific cross-interaction between X and Y could be verified. The electronic effects of the neighboring aromatic ring substituents systematically modify the sensitivity of the C=N group to the electronic effects of the benzylidene or aniline ring substituents. Electron-withdrawing substituents on the aniline ring decrease the sensitivity of delta(C)(C=N) to the substitution on the benzylidine ring, while electron-donating substituents have the opposite effect. In contrast, electron-withdrawing substituents on the benzylidene ring increase the sensitivity of delta(C)(C=N) to the substituent on the aniline ring, while electron-donating substituents act in the opposite way. These results can be rationalized in terms of the substituent-sensitive balance of the electron delocalization (mesomeric effects). The present NMR characteristics are discussed as regards the computational literature data. Valuable information has been obtained on the effects of the substituents on the molecular core of the mesogenic model compounds. 相似文献
83.
The goal of this work is to determine the proton affinities of (deoxy)nucleoside 5'- and 3'-monophosphates (mononucleotides) using the kinetic method with fast atom bombardment mass spectrometry. The proton affinities of the (deoxy)nucleoside 5'- and 3'-monophosphates yielded the following trend: (deoxy)adenosine monophosphates > (deoxy)guanosine monophosphates > (deoxy)cytidine monophosphates > deoxythymidine/uridine monophosphates. In all cases the proton affinity decreases or remains the same with the addition of the phosphate group from those values reported for nucleosides. The proton affinity is dependent on the location of the phosphate backbone (5'-vs. 3'-phosphates): the 3'-monophosphates have lower proton affinities than the 5'-monophosphates except for the thymidine/uridine monophosphates where the trend is reversed. Molecular modeling was utilized to determine if multiple protonation sites and intramolecular hydrogen bond formation would influence the proton affinity measurements. Semiempirical calculations of the proton affinities at various locations on each mononucleotide were performed and compared to the experimental results. The possible influence of intramolecular hydrogen bonding between the nucleobases and the phosphate group on the measured and calculated proton affinities is discussed. 相似文献
84.
85.
The magnitude of the -effects on13C chemical shifts was studied as function of theN-substitution [Me, Et, Bu, CH2C6H5, CH2CH2C6H5, Pri, But, Bus, c-C6H11, CH(CH3)C6H5, But, or Ph] for several benzylamines,o-aminomethylphenols and 3,4-dihydro-2H-1,3-benzoxazines. A correlation between the c-values and the steric substituent constants (E
s
) of theN-substituents proved useful in characterizing the variation of the -effects along with the conformational factors. The diastereospecificity of the -effects is discussed for purposes of configurational assignments.For part 2, see Ref. 1. This paper is also Part 5 in the series Studies on the Benzoxazine Series. 相似文献
86.
Asymmetric Synthesis of Spirocyclic β‐Lactams through Copper‐Catalyzed Kinugasa/Michael Domino Reactions 下载免费PDF全文
Tao Shu Long Zhao Sun Li Dr. Xiang‐Yu Chen Dr. Carolina von Essen Prof. Dr. Kari Rissanen Prof. Dr. Dieter Enders 《Angewandte Chemie (International ed. in English)》2018,57(34):10985-10988
The first copper‐catalyzed highly chemo‐, regio‐, diastereo‐, and enantioselective Kinugasa/Michael domino reaction for the desymmetrization of prochiral cyclohexadienones is described. In the presence of a chiral copper catalyst, alkyne‐tethered cyclohexadienones couple with nitrones to generate the chiral spirocyclic lactams with excellent stereoselectivity (up to 97 % ee, >20:1 dr). The new method provides direct access to versatile highly functionalized spirocyclic β‐lactams possessing four contiguous stereocenters, including one quaternary and one tetra‐substituted stereocenter. 相似文献
87.
Sara Busi Manu Lahtinen Reijo Sillanp Kari Rissanen 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):m458-m460
The title compound, (C16H20N)2[Fe2Br6O], crystallizes with one dibenzyldimethylammonium cation and one half of a μ‐oxo‐bis[tribromoferrate(III)] anion in the asymmetric unit. The bridging oxo group is situated on an inversion centre, resulting in a linear conformation for the Fe—O—Fe unit. The iron(III) cations have tetrahedral geometry, with bond angles in the range 106.8 (1)–112.2 (1)°. The ion pairs are held together by Coulombic forces and C—H⋯Br hydrogen bonds. Each Br− anion forms one hydrogen bond. No C—H⋯O hydrogen bonds are found between the O atom in the Fe—O—Fe unit and surrounding counter‐cations, consistent with the linear configuration of the Fe—O—Fe unit. 相似文献
88.
p-(1H-phenanthro[9,10-d]imidazol-2-yl)- substituted calix[4]arene, a deep cavity for guest inclusion
The reaction of tetra-p-formyltetra-O-propylcalix[4]arene with phenanthrenequinone in the presence of NH(4)OAc affords compound 2, a new class of calixarene with an expanded aromatic cavity, that could be stabilized by hydrogen-bonded bridges and/or ion pairing, thus preventing collapse into fully stacked pinched cone conformations as depicted. Two partially protonated calixarenes interdigitate in the solid state to give rise to a self-assembled face-to-face dimer, stabilized by pi-pi stacking interactions. 相似文献
89.
The Banach spaces with the bounded compact approximation property are characterized by the completeness of measures of noncompactness. Applications to the theory of semi-Fredholm operators and to the algebraic properties of their canonical images in the Calkin algebra are discussed. 相似文献