全文获取类型
收费全文 | 400篇 |
免费 | 12篇 |
国内免费 | 3篇 |
专业分类
化学 | 325篇 |
晶体学 | 3篇 |
数学 | 9篇 |
物理学 | 78篇 |
出版年
2022年 | 4篇 |
2021年 | 1篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2017年 | 1篇 |
2016年 | 9篇 |
2015年 | 14篇 |
2014年 | 3篇 |
2013年 | 18篇 |
2012年 | 26篇 |
2011年 | 29篇 |
2010年 | 10篇 |
2009年 | 8篇 |
2008年 | 33篇 |
2007年 | 18篇 |
2006年 | 25篇 |
2005年 | 35篇 |
2004年 | 24篇 |
2003年 | 22篇 |
2002年 | 17篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 5篇 |
1993年 | 1篇 |
1992年 | 9篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1975年 | 2篇 |
1973年 | 3篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1965年 | 1篇 |
排序方式: 共有415条查询结果,搜索用时 31 毫秒
61.
The aggregation and assembly of crescent oligoamides with two to six benzene residues are investigated. In chloroform, the pentamer and hexamer are found to associate into large aggregates. In the solid state, all oligomers examined associate into columnar assemblies via stacking interactions, as shown by X-ray diffraction data from single crystals and powder samples. The columnar assemblies of the pentamer and hexamer should contain hydrophilic channels defined by the constituent oligomers. 相似文献
62.
Tsutomu Ohzuku Ryoji Yamato Toru Kawai Kingo Ariyoshi 《Journal of Solid State Electrochemistry》2008,12(7-8):979-985
Steady-state polarization measurements of lithium titanium oxide (LTO; Li[Li1/3Ti5/3]O4) were carried out using the 0-V lithium-ion cells consisting of two identical LTO-electrodes with a parallel-plate symmetrical electrode configuration. The sinusoidal voltage with the peak amplitude of 1.0 V was imposed at 0.1 Hz upon the 0-V cells and the current response was measured as a function of time. The steady-state polarization, obtained by plotting the current versus applied voltage, was linear in current up to approximately 60 mA cm?2 or 4 A g?1 based on the LTO weight and suggested the resistance polarization only for the lithium insertion electrode of the LTO. The method was also applied to lithium aluminum manganese oxide (LAMO; Li[Li0.1Al0.1Mn1.8]O4) and the resistance polarization of the LAMO-electrode was determined for currents up to approximately 25 mA cm?2 or 2 A g?1 based on the LAMO weight. The validity of the results was examined for the polarization measurements of the 2.5-V lithium-ion battery consisting of LTO and LAMO, and the significance of the polarization measurements of lithium insertion electrodes for high-power applications was discussed. 相似文献
63.
Chong Wu Jiang-Lin Zhao Xue-Kai Jiang Xin-Long Ni Xi Zeng Carl Redshaw Takehiko Yamato 《Analytica chimica acta》2016
A new type of chemosensor-based approach to the detection of 2,4,6-trinitrophenol (TNP) is described in this paper. Two hexahomotrioxacalix[3]arene-based chemosensors 1 and 2 were synthesized through click chemistry, which exhibited high binding affinity and selectivity toward TNP as evidenced by UV–vis and fluorescence spectroscopy studies. 1H NMR titration analysis verified that CH?O hydrogen bonding is demonstrated as the mode of interaction, which possibly facilitates effective charge-transfer. 相似文献
64.
Kajita Y Arii H Saito T Saito Y Nagatomo S Kitagawa T Funahashi Y Ozawa T Masuda H 《Inorganic chemistry》2007,46(8):3322-3335
Six Cu(I) complexes with cis,cis-1,3,5-triaminocyclohexane derivatives (R3CY, R = Et, iBu, and Bn), [Cu(MeCN)(Et3CY)]SbF6 (1), [Cu(MeCN)(iBu3CY)]SbF6 (2), [Cu(MeCN)(Bn3CY)]SbF6 (3), [Cu(CO)(Et3CY)]SbF6 (4), [Cu(CO)(iBu3CY)]SbF6 (5), and [Cu(CO)(Bn3CY)]SbF6 (6), were prepared to probe the ability of copper complexes to effectively catalyze oxygenation reactions. The complexes were characterized by elemental analysis, electrochemical and X-ray structure analyses, electronic absorption spectroscopy, IR spectroscopy, 1H NMR spectroscopy, and ESI mass spectrometry. The crystal structures of 1-3 and 6 and the CO stretching vibrations (nuCO) of 4-6 demonstrate that the ability of R3CY to donate electron density to the Cu(I) atom is stronger than that of the previously reported ligands, 1,4,7-triazacyclononane (R3TACN) and 1,4,7-triazacyclodecane (R3TACD). Reactions of complexes 1-3 with dioxygen in THF or CH2Cl2 at -105 to -80 degrees C yield bis(mu-oxo)dicopper(III) complexes 7-9 as intermediates as confirmed by electronic absorption spectroscopy and resonance Raman spectroscopy. The Cu-O stretching vibrations, nu(Cu-O) for 7 (16O2: 553, 581 cm-1and 18O2: 547 cm-1) and 8 (16O2: 571 cm-1 and 18O2: 544 cm-1), are observed in a lower energy region than previously reported for bis(micro-oxo) complexes. The decomposition rates of complexes 7-9 in THF at -90 degrees C are 2.78 x 10-4 for 7, 8.04 x 10-4 for 8, and 3.80 x 10-4 s-1 for 9. The decomposition rates of 7 and 8 in CH2Cl2 were 5.62 x 10-4 and 1.62 x 10-3 s-1, respectively, and the thermal stabilities of 7-9 in CH2Cl2 are lower than the values measured for the complexes in THF. The decomposition reactions obeyed first-order kinetics, and the H/D isotope experiments for 8 and 9 indicate that the N-dealkylation reaction is the rate-determining step in the decomposition processes. On the other hand, the decomposition reaction of 7 in THF results in the oxidation of THF (acting as an exogenous substrate) to give 2-hydroxy tetrahydrofuran and gamma-butyrolactone as oxidation products. Detailed investigation of the N-dealkylation reaction for 8 by kinetic experiments using N-H/D at -90 degrees C showed a kinetic isotope effect of 1.25, indicating that a weak electrostatic interaction between the N-H hydrogen and mu-oxo oxygen contributes to the major effect on the rate-determining step of N-dealkylation. X-ray crystal structures of the bis(micro-hydroxo)dicopper(II) complexes, [Cu2(OH)2(Et3CY)2](CF3SO3)2 (10), [Cu2(OH)2(iBu3CY)2](CF3SO3)2 (11), and [Cu2(OH)2(Bn3CY)2](ClO4)2 (12), which have independently been prepared as the final products of bis(micro-oxo)dicopper(III) intermediates, suggest that an effective interaction between N-H and mu-oxo in the Cu(III)2(micro-O)2 core may enhance the oxidation ability of the metal-oxo species. 相似文献
65.
Vision begins when light is absorbed by visual pigments. It is commonly believed that the absorption spectra of visual pigments are modulated by interactions between the retinal and amino acids within or near 4.5 angstroms of the retinal in the transmembrane (TM) segments. However, this dogma has not been rigorously tested. In this study, we show that the retinal-opsin interactions extend well beyond the retinal binding pocket. We found that, although it is positioned outside of TM segments, the C-terminus of the rhodopsin in the rockfish longspine thornyhead (Sebastolobus altivelis) modulates its lambda(max) by interacting mainly with the last TM segment. Our results illustrate how amino acids in the C-terminus are likely to interact with the retinal. We anticipate our analyses to be a starting point for viewing the spectral tuning of visual pigments as interactions between the retinal and key amino acids that are distributed throughout the entire pigment. 相似文献
66.
Yamato T Ishikura T Kakitani T Kawaguchi K Watanabe H 《Photochemistry and photobiology》2007,83(2):323-327
We report a theoretical study on the optical properties of a small, water-soluble photosensory receptor, photoactive yellow protein (PYP). A hierarchical ab initio molecular orbital calculation accurately evaluated the optical absorption maximum of the wild-type, as well as the lambda(max) values of 12 mutants. Electronic excitation of the chromophore directly affects the electronic state of nearby atoms in the protein environment. This effect is explicitly considered in the present study. Furthermore, the spectral tuning mechanism of PYP was investigated at the atomic level. The static disorder of a protein molecule is intimately related to the complex nature of its energy landscape. By using molecular dynamics simulation and quantum mechanical structure optimization, we obtained multiple minimum energy conformations of PYP. The statistical distribution of electronic excitation energies of these minima was compared with the hole-burning experiment (Masciangioli, T. [2000] Photochem. Photobiol. 72, 639), a direct observation of the distribution of excitation energies. 相似文献
67.
Matsuura H Nomura S Subeki Yamada K Yamasaki M Yamato O Maede Y Katakura K Trimurningsih Chairul Yoshihara T Nabeta K 《Natural product research》2007,21(4):328-333
Anti-babesial ingredients, (12R)- and (12S)-12,13-dihydro-12,13-dihydroxyxanthorrhizols, were isolated from Curcuma xanthorrhiza. The structures were established by the extensive NMR techniques. The assignments of (1)H NMR data of (12R)-12,13-dihydro-12,13-dihydroxyxanthorrhizol was revised, and (12S)-12,13-dihydro-12,13-dihydroxyxanthorrhizol was isolated as a pure form for the first time. The IC(50) of the active compounds were compared with that of commercial drug, diminazene aceturate (Ganaseg). IC(50) values of Ganaseg, (12R)-, and (12S)-12,13-dihydro-12,13-dihydroxyxanthorrhizols were 0.6 microg mL(-1), 8.3 microg mL(-1) and 11.6 microg mL(-1), respectively. 相似文献
68.
69.
70.
Hideaki Tanaka Takahisa Akatsuka Toru Ohe Yoshiro Ogoma Koji Abe Yoshiyuki Kondo 《先进技术聚合物》1998,9(2):150-154
A fluorescence probe, fluorescein isothiocyanate (FITC), was introduced to proteins, and the morphology of protein-adsorbed stearic acid monolayer was observed by fluorescence microscopy and Brewster angle microscopy (BAM) in order to analyze images. At a low protein concentration, the surface pressure increased as shown by a sigmoidal curve. A number of stripe patterns in the BAM images increased and the shapes became clear with increasing concentration of proteins. Simultaneously, the size of circular islands also became small, and finally disappeared. These results suggest that the very large stripe patterns in the BAM image show the assembly of both proteins and stearic acid molecules, and small circular islands show only the stearic acid molecules. © 1998 John Wiley & Sons, Ltd. 相似文献