全文获取类型
收费全文 | 363篇 |
免费 | 11篇 |
国内免费 | 4篇 |
专业分类
化学 | 155篇 |
晶体学 | 1篇 |
力学 | 11篇 |
数学 | 159篇 |
物理学 | 52篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 17篇 |
2021年 | 8篇 |
2020年 | 10篇 |
2019年 | 21篇 |
2018年 | 16篇 |
2017年 | 16篇 |
2016年 | 14篇 |
2015年 | 9篇 |
2014年 | 18篇 |
2013年 | 23篇 |
2012年 | 29篇 |
2011年 | 38篇 |
2010年 | 24篇 |
2009年 | 18篇 |
2008年 | 15篇 |
2007年 | 12篇 |
2006年 | 9篇 |
2005年 | 8篇 |
2004年 | 10篇 |
2003年 | 4篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1972年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有378条查询结果,搜索用时 0 毫秒
1.
Beyer RL Hoang HN Appleton TG Fairlie DP 《Journal of the American Chemical Society》2004,126(46):15096-15105
Short peptides corresponding to two to four alpha-helical turns of proteins are not thermodynamically stable helices in water. Unstructured octapeptide Ac-His1-Ala2-Ala3-His4-His5-Glu6-Leu7-His8-NH(2) (1) reacts with two [Pd((15)NH(2)(CH(2))(2)(15)NH(2))(NO(3))(2)] in water to form a kinetically stable intermediate, [[Pden](2)[(1,4)(5,8)-peptide]](2), in which two 19-membered metallocyclic rings stabilize two peptide turns. Slow subsequent folding to a thermodynamically more stable two-turn alpha-helix drives the equilibrium to [[Pden](2)[(1,5)(4,8)-peptide]] (3), featuring two 22-membered rings. This transformation from unstructured peptide via turns to an alpha-helix suggests that metal clips might be useful probes for investigating peptide folding. 相似文献
2.
Thermal oxidation of sulfur vulcanized polyisoprene samples was studied by gravimetry and IR mapping of carbonyl groups (to determine the oxidized layer thickness (TOL)) at temperatures ranging from 60 to 150 °C in air. Oxidation appears noticeably lower than that for the starting non-vulcanized polyisoprene, revealing a stabilizing effect of sulfur-containing species. After a short period where mass loss presumably due to water evaporation predominates, the sample mass increases until a plateau corresponding to 6.3% (at 60 °C) to 0.5% (at 140 °C) mass gain. Practically no weight gain (∼0.1%) was observed at 150 °C. The mass uptake is due to oxygen grafting to the chains. TOL varies from about 4.6 mm (70 °C) to about 1 mm (150 °C).A kinetic model, derived from a mechanistic scheme of radical chain oxidation including stabilizing events due to hydroperoxide reduction by sulfur-containing groups and taking into account the diffusion-reaction coupling, was established and numerically resolved. The model predictions for mass changes and TOL values are in good agreement with experimental data. 相似文献
3.
The dependence of electron density, superdelocalizability and localization energy on the value of the parameter for the inductive effect of the methyl group in 1,4-dimethyl naphthalene is exactly the same when calculated by the Omega or by the Pople-Pariser-Parr techniques.
This work was done with financial assistance from the National Research Council of Canada. L.-K. H. wishes to acknowledge the award of a Colombo Plan scholarship. 相似文献
Zusammenfassung Die Abhängigkeit der Elektronendichte, der Superdelokalisierbarkeit und der Lokalisierungsenergie vom Wert des Parameters für den induktiven Effekt der Methylgruppe in 1,4-Dimethylnaphthalin ist genau dieselbe, wenn man diese Größen mit der Omegatechnik oder der PPP-Methode berechnet.
Résumé La densité électronique, la super délocalisabilité et l'énergie de localisation du 1,4 diméthyl naphtalène dépendent de la même manière de la valeur du paramètre de l'effet inductif du groupe méthyle selon que les calculs sont effectués par la méthode oméga ou par la méthode de Pople-Pariser-Parr.
This work was done with financial assistance from the National Research Council of Canada. L.-K. H. wishes to acknowledge the award of a Colombo Plan scholarship. 相似文献
4.
5.
Ngoc Hoa Tran Huy Francois Mathey 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):477-481
Abstract The reaction of electron-rich alkynes such as ethoxyacetylene or propynyldiethylamine with a transient terminal phosphinidene complex such as [PhP?W(CO)5] directly yields the corresponding phosphole complexes via a formal [2 + 2 + I] cycloaddition involving two molecules of alkyne and one phosphorus center. 相似文献
6.
As part of our study of the mesomorphic properties of glucopyranosides containing fluorinated chains, this paper focuses on an investigation of the liquid crystalline behaviour of nonaromatic compounds. The synthesis of eight single-tailed materials which contain a semiperfluoroalkyl chain linked to the polar glucose head group is described. Using polarized optical microscopy, DSC and X-ray diffraction all the materials were found to show only monomesomorphism, a smectic A phase with bimolecular layers. The thermal behaviour is discussed in comparison with the previously reported data on the series of parent compounds. 相似文献
7.
Nguyen Huy Thuan Ramesh Prasad Pandey Ta Thi Thu Thuy Je Won Park Jae Kyung Sohng 《Applied biochemistry and biotechnology》2013,171(8):1956-1967
Myricetin is an important flavonol whose medically important properties include activities as an antioxidant, anticarcinogen, and antimutagen. The solubility, stability, and other biological properties of the compounds can be enhanced by conjugating aglycon with sugar moieties. The type of sugar moiety also plays a significant role in the biological and physical properties of the natural product glycosides. Reconstructed Escherichia coli containing thymidine diphosphate-α-l-rhamnose sugar gene cassette and Arabidopsis-derived glycosyltransferase were used for rhamnosylation of myricetin. Myricetin (100 μM) was exogenously supplemented to induced cultures of engineered E. coli. The formation of target product—myricetin-3-O-α-l-rhamnoside—was confirmed by chromatographic and NMR analyses. The yield of product was improved by using various mutants and methylated cyclodextrin as a molecular carrier for myricetin in combination with E. coli M3G3. The maximal yield of product is 55.6 μM (3.31-fold higher than the control E. coli MG3) and shows 55.6 % bioconversion of substrate under optimized conditions. 相似文献
8.
Atomic Force Microscopy (AFM) probes the surface features of specimens using an extremely sharp tip scanning the sample surface while the force is applied. AFM is also widely used for investigating the electrically non-conductive materials by applying an electric potential on the tip. Piezoresponse Force Microscopy (PFM) and Electrochemical Strain Microscopy (ESM) are variants of AFM for different materials. Both PFM and ESM signals are obtained by observing the displacement of the tip when applying electric fields during the scanning process. The PFM technique is based on converse piezoelectric effect of ferroelectrics and the ESM technique is based on electrochemical coupling in solid ionic conductors. In this work, two continuum-mechanical formulations for simulation of PFM and ESM are discussed. In the first model, for PFM simulation, a phase field approach based on the Allen-Cahn equation for non-conserved order parameters is employed for ferroelectrics. Here, the polarization vector is chosen as order parameter. Since ferroelectrics have highly anisotropic properties, this model accounts for transversely isotropic symmetry using an invariant formulation. The polarization switching behavior under the electric field will be discussed with some numerical examples. In the simulation of ESM, we employ a constitutive model based on the work of Bohn et al. [8] for the modeling of lithium manganese dioxide LiMn2O4 (LMO). It simulates the deformation of the LMO particle according to an applied voltage and the evolution of lithium concentration after removing a DC pulse. The modeling results are compared to experimental data. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
9.
Nguyen Huy Tuan Nguyen Hoang Tuan Dumitru Baleanu Tran Ngoc Thach 《Mathematical Methods in the Applied Sciences》2020,43(3):1292-1312
In the present paper, we study the initial inverse problem (backward problem) for a two-dimensional fractional differential equation with Riemann-Liouville derivative. Our model is considered in the random noise of the given data. We show that our problem is not well-posed in the sense of Hadamard. A truncated method is used to construct an approximate function for the solution (called the regularized solution). Furthermore, the error estimate of the regularized solution in L2 and Hτ norms is considered and illustrated by numerical example. 相似文献
10.