全文获取类型
收费全文 | 1287篇 |
免费 | 52篇 |
国内免费 | 26篇 |
专业分类
化学 | 730篇 |
晶体学 | 20篇 |
力学 | 24篇 |
数学 | 359篇 |
物理学 | 232篇 |
出版年
2023年 | 5篇 |
2022年 | 16篇 |
2021年 | 20篇 |
2020年 | 24篇 |
2019年 | 25篇 |
2018年 | 11篇 |
2017年 | 17篇 |
2016年 | 33篇 |
2015年 | 32篇 |
2014年 | 32篇 |
2013年 | 72篇 |
2012年 | 84篇 |
2011年 | 69篇 |
2010年 | 49篇 |
2009年 | 45篇 |
2008年 | 73篇 |
2007年 | 81篇 |
2006年 | 89篇 |
2005年 | 83篇 |
2004年 | 72篇 |
2003年 | 50篇 |
2002年 | 64篇 |
2001年 | 12篇 |
2000年 | 28篇 |
1999年 | 19篇 |
1998年 | 22篇 |
1997年 | 15篇 |
1996年 | 19篇 |
1995年 | 12篇 |
1994年 | 23篇 |
1993年 | 20篇 |
1992年 | 18篇 |
1991年 | 12篇 |
1990年 | 14篇 |
1989年 | 12篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1978年 | 9篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1973年 | 7篇 |
1972年 | 3篇 |
排序方式: 共有1365条查询结果,搜索用时 359 毫秒
211.
Greg S. Harms Steve W. Pauls John F. Hedstrom Carey K. Johnson 《Journal of fluorescence》1997,7(4):283-292
We have examined the lifetimes and rotational correlation times of dityrosine emission by time-correlated single-photon counting. We first noticed dityrosine fluorescence in samples of tyrosine and tyrosine dipeptides by its characteristic red-shifted emission at 400 to 430 nm. The longer rotational correlation time relative to tyrosine proved that this fluorescence emanated from a distinct species. Comparison with the fluorescence properties of synthesized dityrosine established the identity of the emitting species. Fluorescence intensity decays of dityrosine are generally characterized by two decay components, one with a lifetime in the range of 150 to 800 ps and another between 2.5 and 4.5 ns. We found no evidence for an excited-state reaction, since a rising phase (negative-amplitude component) was not observed. In the pH range from 4 to 10, two ground-state species exist in equilibrium with pK
a 7. Both species exhibit two fluorescence decays. The average fluorescence lifetime increases gradually with pH over the pH range from 4 to 10 and decreases at pH 2. Anisotropy decays were measured for dityrosine and the alanine–dityrosine–alanine and leucine–dityrosine–leucine dipeptides. The rotational correlation times of dityrosine and dityrosine dipeptides increase linearly with van der Waals volumes. The slope indicates a stronger solute–solvent interaction than predicted with stick boundary conditions. It is suggested that these interactions result from the presence of two zwitterionic pairs. 相似文献
212.
Paul K. Baker Michael G.B. Drew Steve P. Gonsalves Archie W. Johans Margaret M. Meehan 《Journal of chemical crystallography》2002,32(5-6):113-118
[WI2(CO)3{Ph2P(CH2)2PPh2}] (1) crystallizes out in the monoclinic space group P21/n, with a = 13.852(7) Å, b = 14.789(19) Å, c = 14.915(19) Å, = 102.86(1)°, Z = 4. [WI2(CO)3{Ph2P(CH2)3PPh2}] (2) crystallizes out in the monoclinic space group P21/n, with a = 10.499(15) Å, b = 14.58(2) Å, c = 20.75(3) Å, = 103.59(1)°, Z = 4. Both structures show the metal in a seven-coordinate environment with a carbonyl in the unique capping position, two further carbonyls and a phosphorus in the capped face, and two iodides and the second phosphorus in the uncapped face. 相似文献
213.
Surface active molecules collect at interfaces and have the potential to be used for water evaporation reduction. The objective of this work is to design surface active soluble peptides that collect at the air/water interface using molecular simulations. Rotational isomeric state Monte Carlo (RISMC) sampling together with a solvation model that we recently invented, the AAD solvation model [Gu, C.; Lustig, S.; Trout, B. J. Phys. Chem. B 2006, 110 (3), 1476-1484] was applied to calculate the adsorption free energy of the peptide molecule at the air/water interface. The results were validated by both molecular dynamics simulations with an explicit solvent model and surface tension measurements on synthesized peptides. It was demonstrated that this approach is able to give a reasonable prediction of surface activity with an approximately 50% hit rate in terms of designed surface active molecules actually being surface active. The relationship between the chemical composition and the surface morphology is also discussed. 相似文献
214.
215.
Rogach AL Gaponik N Lupton JM Bertoni C Gallardo DE Dunn S Li Pira N Paderi M Repetto P Romanov SG O'Dwyer C Sotomayor Torres CM Eychmüller A 《Angewandte Chemie (International ed. in English)》2008,47(35):6538-6549
Colloidal semiconductor nanocrystals are promising luminophores for creating a new generation of electroluminescence devices. Research on semiconductor nanocrystal based light-emitting diodes (LEDs) has made remarkable advances in just one decade: the external quantum efficiency has improved by over two orders of magnitude and highly saturated color emission is now the norm. Although the device efficiencies are still more than an order of magnitude lower than those of the purely organic LEDs there are potential advantages associated with nanocrystal-based devices, such as a spectrally pure emission color, which will certainly merit future research. Further developments of nanocrystal-based LEDs will be improving material stability, understanding and controlling chemical and physical phenomena at the interfaces, and optimizing charge injection and charge transport. 相似文献
216.
The Suzuki-Miyaura (SM) cross-coupling reaction has recently become one of the most efficient methods for C-C bond construction opening a wide range of opportunities in organic synthesis. This study focused on the evaluation of the use of the SM reaction to modify peptides using a solid-phase synthesis approach, an avenue that was still not investigated intensively. We used as a peptide model [Ala (1,2,3), Leu (8)]Enk linked to a polystyrene support on which it was previously assembled. The aromatic residues Tyr (4) and Phe (7) of [Ala (1,2,3), Leu (8)]Enk were respectively substituted with p-iodo-Phe, and an SM-related strategy was developed. Results indicated that the reaction conditions involving K 3PO 4 or Na 2CO 3 (base), DMF (solvent), Pd(PPh 3) 4 (catalyst), and temperatures ranging from 50 to 80 degrees C during 20 h were found as optimal. Finally applying those optimal conditions, a series of [Ala (1,2,3), Leu (8)]Enk analogs modified at Tyr (4) or Phe (7) positions was synthesized using diverse boronic acid derivatives. 相似文献
217.
Methodology has been sought towards obtaining a 2-chloro-1,4-naphthoquinone bearing hydroxyl groups in the adjoining ring for obtaining either kermesic or carminic acids. In the first of these objectives, kermesic acid has been synthesised from 6-chloro-2,5,8-trihydroxynaphtho-1,4-quinone by the regioselective cycloaddition of the 1,2-diacetate formed by its acetylation-aided tautomerism and cycloaddition with (E)- and (Z)-3-alkoxycarbonyl-2,4-bis(trimethylsilyloxy)penta-1,3-dienes. The parent unacetylated quinone resists cycloaddition. 相似文献
218.
Molecules containing a C-C triple bond, such as HC[triple bond]CH, FC[triple bond]CF, and the C[triple bond]CH radical, are allowed to interact with a partner molecule of H2O, NH3, or HF. Quantum chemical calculations show that these C[triple bond]CH...X H-bonded complexes are bound by up to 4 kcal x mol(-1). More importantly, they can rearrange in such a way that the partner molecule adds to the triple bond so as to form a double C=C bond. Whereas this process is strongly exoergic, there is a high-energy barrier to this rearrangement process. On the other hand, when a second water molecule is added to the complex, it can shuttle protons from the donor part of the complex to the acceptor, and thereby greatly reduce the rearrangement energy barrier. In the case of CCH + 2H2O, this barrier is computed to be less than 4 kcal x mol(-1). 相似文献
219.
Scott Matteucci Victor A. Kusuma David Sanders Steve Swinnea Benny D. Freeman 《Journal of membrane science》2008
Titanium dioxide (TiO2) nanoparticles were dispersed via solution processing in poly(1-trimethylsilyl-1-propyne) (PTMSP) to form nanocomposite films. Nanoparticle dispersion was investigated using atomic force microscopy and transmission electron microscopy. At low-particle loadings, nanoparticles were dispersed individually and in nanoscale aggregates. At high-particle loadings, some nanoparticles formed micron-sized aggregates. The gas transport and density exhibited a strong dependence on nanoparticle loading. At low-TiO2 loadings, the composite density was similar to or slightly higher than that predicted by a two-phase additive model. However, at particle loadings exceeding approximately 7 nominal vol.%, the density was markedly lower than predicted, suggesting that the particles induced the creation of void space within the nanocomposite. For example, when the TiO2 nominal volume fraction was 0.35, the polymer/particle composite density was 40% lower than expected based on a two-phase additive model for density. At low-nanoparticle loading, light gas permeability was lower than that of the unfilled polymer. At higher nanoparticle loadings, light gas permeability (i.e., CO2, N2, and CH4) increased to more than four times higher than in unfilled PTMSP. At most, selectivity changed only slightly with particle loading. 相似文献
220.
Anthony SM Kim M Granick S 《Langmuir : the ACS journal of surfaces and colloids》2008,24(13):6557-6561
We describe algorithms and an experimental method based on differential interference contrast microscopy to discriminate optically anisotropic colloidal spheres under situations where diffraction owing to their close proximity causes overlapping images. The data analysis is applied to modulated optical nanoprobes (MOONs) that are coated with metal on one hemisphere. These methods enable single-particle tracking of rotation in addition to translation not only in concentrated suspensions but also in dilute suspensions when particles come into transient hydrodynamic contact. An illustrative example is given. 相似文献