全文获取类型
收费全文 | 526篇 |
免费 | 43篇 |
国内免费 | 2篇 |
专业分类
化学 | 404篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 29篇 |
物理学 | 128篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 21篇 |
2021年 | 33篇 |
2020年 | 25篇 |
2019年 | 25篇 |
2018年 | 33篇 |
2017年 | 12篇 |
2016年 | 30篇 |
2015年 | 17篇 |
2014年 | 25篇 |
2013年 | 22篇 |
2012年 | 32篇 |
2011年 | 35篇 |
2010年 | 37篇 |
2009年 | 16篇 |
2008年 | 43篇 |
2007年 | 32篇 |
2006年 | 36篇 |
2005年 | 25篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1991年 | 1篇 |
1988年 | 1篇 |
1984年 | 1篇 |
排序方式: 共有571条查询结果,搜索用时 15 毫秒
501.
502.
We present a method for fabricating anchored polymers with a gradual variation of grafting densities on solid substrates. The technique for generating such structures comprises (i) formation of a molecular gradient of polymerization initiator on the solid substrate and (ii) polymerization from the substrate-bound initiator centers ("grafting from"). We measure the mushroom-to-brush transition in grafted polyacrylamides and show that the mushroom and brush behavior can be described using existing scaling theories. 相似文献
503.
In a short sequence, 5-vinyloxazolidin-2-ones were converted into the 3,6-disubstituted 3,6-dihydropyridin-2-ones via Pd-catalysed carbonylation and enolate alkylation with high diastereoselectivity. Alkylation of 6-substituted N-methylpyridin-2-ones gives stereoselectively the 3,6-anti diastereoisomer with MeI, BuI and i-PrI. Alkylation of the corresponding N-BOC pyridinones gives the 3,6-syn diastereoisomer with high selectivity. 相似文献
504.
Tatiana A. Stromnova Oleg N. Shishilov Kirill Yu. Monakhov Ludmila G. Kuz’mina 《Journal of organometallic chemistry》2006,691(18):3730-3736
The interaction of palladium(+1) cluster Pd4(μ-CO)4(μ-OAc)4 with saturated and unsaturated carboxylic acids was studied. It was found, that the substitution of acetates groups on others carboxylates leads to the clusters with different nuclearity. Palladium(+1) carbonyl carboxylate complexes of composition [Pd(μ-CO)(μ-OCOR)]n, where R = CF3, CCl3, CH2Cl, MeCH = CMe, Me, Pri, Bu, Bui, Butert, n-C5H11 and n = 4 or 6 were synthesized. According to X-ray data all clusters possess cyclic planar metal cores with alternate pairs of μ-carbonyl and μ-carboxylate ligands. The presence of bulky alkyl fragments in the carboxylate ligand increases the nuclearity of the cluster compared to that of the starting palladium(+1) carbonyl acetate of composition Pd4(μ-CO)4(μ-OAc)4 due, apparently, to steric hindrance. 相似文献
505.
Nuzhdin KB Nesterov SV Tyurin DA Feldman VI Wei L Lund A 《The journal of physical chemistry. A》2005,109(28):6166-6173
The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular sigma-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well. 相似文献
506.
Blinov KA Larin NI Kvasha MP Moser A Williams AJ Martin GE 《Magnetic resonance in chemistry : MRC》2005,43(12):999-1007
Indirect covariance NMR offers an alternative method of extracting spin-spin connectivity information via the conversion of an indirect-detection heteronuclear shift-correlation data matrix to a homonuclear data matrix. Using an IDR (inverted direct response)-HSQC-TOCSY spectrum as a starting point for the indirect covariance processing, a spectrum that can be described as a carbon-carbon COSY experiment is obtained. These data are analogous to the autocorrelated 13C-13C double quantum INADEQUATE experiment except that the indirect covariance NMR spectrum establishes carbon-carbon connectivities only between contiguous protonated carbons. Cyclopentafuranone and the complex polynuclear heteroaromatic naphtho[2',1':5,6]-naphtho[2',1':4,5]thieno[2,3-c]quinoline are used as model compounds. The former is a straightforward example because of its well-resolved proton spectrum, while the latter, which has considerable resonance overlap in its congested proton spectrum, gives rise to two types of artifact responses that must be considered when using the indirect covariance NMR method. 相似文献
507.
Olga A. Maloshitskaya Valery V. Alekseyev Kirill N. Zelenin Kalevi Pihlaja 《Tetrahedron》2006,62(40):9456-9466
The reaction products of 1,3-butanediamine and 2-methyl-2,4-pentanediamine with β-keto aldehydes were shown by 1H and 13C NMR spectroscopy to exist as tautomeric mixtures in solutions, comprising one cyclic and two open-chain forms due to the non-equivalence of the amino groups. The chain products exist as Z- and E-isomers. After equilibration, the products from 1,3-butanediamine contain relatively less of the cyclic form than those from 2-methyl-2,4-pentanediamine. The products of 2-methyl-2,4-pentanediamine with p-substituted aroylacetaldehydes, exhibit a linear correlation between log K of the ring-chain equilibria and Hammett's σ values of the aromatic ring substituents. α-Substitution of β-keto aldehydes notably increased the relative amounts of the chain E-isomers in their condensation products and also resulted in the formation of two diastereomers for each of the cyclic products. No ring-chain equilibria were observed in the products of 1,3-butanediamine and 2-methyl-2,4-pentanediamine with β-diketones, β-keto esters, or β-keto amides. 相似文献
508.
On treatment with trifluoroacetic acid butenolide 14 undergoes N-Boc deprotection and condensation followed by an iminium ion activated intramolecular Diels-Alder cycloaddition to give the (+)-himbacine precursor 11 on reductive work up. Compound 11 was converted into (+)-himbacine in four synthetic steps. [reaction: see text] 相似文献
509.
510.
Double asymmetric induction in Michael reactions has been studied. Enantioselective alkylation of a cyclic ketone (1-indanone) with α-phenyl-nor-gramine was carried out. The relative configuration of (2S∗)-2-[(R∗)-1H-indol-3-yl(phenyl)methyl]-2,3-dihydro-1H-inden-1-one was established by X-ray diffraction. The relative configuration of (R∗,R∗,S∗)- and (S∗,R∗,S∗)-2-1H-indol-3-yl(phenyl)methyl]-2,3-dihydro-1H-inden-1-ols was established by 1H NMR studies. 相似文献