全文获取类型
收费全文 | 1146篇 |
免费 | 60篇 |
国内免费 | 22篇 |
专业分类
化学 | 840篇 |
晶体学 | 8篇 |
力学 | 40篇 |
数学 | 86篇 |
物理学 | 254篇 |
出版年
2023年 | 8篇 |
2022年 | 17篇 |
2021年 | 24篇 |
2020年 | 17篇 |
2019年 | 24篇 |
2018年 | 5篇 |
2017年 | 9篇 |
2016年 | 23篇 |
2015年 | 27篇 |
2014年 | 53篇 |
2013年 | 48篇 |
2012年 | 75篇 |
2011年 | 96篇 |
2010年 | 58篇 |
2009年 | 74篇 |
2008年 | 91篇 |
2007年 | 82篇 |
2006年 | 74篇 |
2005年 | 55篇 |
2004年 | 35篇 |
2003年 | 30篇 |
2002年 | 33篇 |
2001年 | 19篇 |
2000年 | 15篇 |
1999年 | 14篇 |
1998年 | 12篇 |
1997年 | 20篇 |
1996年 | 13篇 |
1995年 | 11篇 |
1994年 | 16篇 |
1993年 | 12篇 |
1992年 | 14篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 8篇 |
1975年 | 5篇 |
1974年 | 12篇 |
1973年 | 12篇 |
1964年 | 2篇 |
排序方式: 共有1228条查询结果,搜索用时 31 毫秒
31.
Separations of small ions were carried out under nonequilibrated conditions using capillaries treated with NaOH, HCl, or tris(hydroxymethyl)aminomethane (Tris) prior to analysis. For separations of benzoic acid isomers or acids and amines under weakly acidic conditions, capillaries flushed with 0.1 M NaOH and subsequently with running buffers prior to analysis were used. Separations of six benzoic acid isomers were accomplished in 4 min in 1 mM phosphate buffers, pH 4.01, containing 2.5 mM hydroxypropyl-beta-cyclodextrin. Without additives, the separation of biological amines and acids were also achieved in 10 min at pH 4.01. Capillaries treated with 0.1 M HCl prior to analysis were tested in separations of six phenols in 5 mM Tris solutions at pH 7.0. As a result of small electrophoretic mobilities of phenols against a small electroosmotic flow, resolution was optimized. We also found that reproducibility was improved using capillaries treated with HCl. The relative standard deviations of migration mobility of phenols were less than 1%, which were smaller than those obtained using capillaries treated with 0.1 M NaOH or Tris. 相似文献
32.
Lee CM Hsieh CH Dutta A Lee GH Liaw WF 《Journal of the American Chemical Society》2003,125(38):11492-11493
Iron-nitrosyl complex containing S-bonded monosulfinate [PPN][(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (3) has been isolated from sulfur oxygenation of complex [PPN][(NO)Fe(S,S-C6H4)2] (2) which is obtained from addition of NO molecule to [PPN][(C4H8O)Fe(S,S-C6H4)2] (1) in organic solvents. This result reveals that binding of NO to the iron center promotes sulfur oxygenation of iron dithiolates by dioxygen and stabilizes the S-bonded sulfinate iron species. Analysis of the bond angles for complexes 2 and 3 reveals that iron is best described as existing in a distorted trigonal bipyramidal coordination environment surrounded by one NO, three thiolates, and one sulfinate in complex 3, whereas the distorted square pyramidal geometry is adopted in complex 2. Complex 3 further reacts in organic solvents with molecular oxygen in the presence of [PPN][NO2] to produce the dinuclear bis(sulfinate) complex [PPN]2[(NO)Fe(SO2,SO2-C6H4)(S,S-C6H4)]2 (4). Complex 3 showed reaction with PPh3 in THF/CH2Cl2 to yield complex 2 and Ph3PO. Upon photolysis of CH2Cl2 solution of complex 3 under N2 purge at ambient temperature, the UV-vis and IR spectra consistent with the formation of complex 2 demonstrate that complex 2 and 3 are photochemically interconvertible. Obviously, complex 3 is thermally quite stable but is photochemically active toward [O] release. Also described are the X-ray crystal structures of 3 and 4. 相似文献
33.
Yi-Chun Lai 《Tetrahedron》2005,61(40):9484-9489
Palladium-catalyzed Suzuki cross-coupling reactions employing Schiff-bases as ligands toward a series of substituted arylbromides and boronic acids were pursued. In the presence of a N,O-bidentate ligand, 2-[1-(2,4,6-trimethyl-phenylimino)-ethyl]-phenol 5, the catalytic reactions could be carried out efficiently at room temperature with a wide array of arylbromides, even with electronically deactivated arenes. A deprotonated 5, 5′, chelated palladium acetate complex, [5′Pd(II)(OAc)(solv)] 8, was proposed as a precursor of a genuine catalytically active species. 相似文献
34.
We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS. 相似文献
35.
Bingham RJ Findlay JB Hsieh SY Kalverda AP Kjellberg A Perazzolo C Phillips SE Seshadri K Trinh CH Turnbull WB Bodenhausen G Homans SW 《Journal of the American Chemical Society》2004,126(6):1675-1681
In the present study we examine the thermodynamics of binding of two related pyrazine-derived ligands to the major urinary protein, MUP-I, using a combination of isothermal titration calorimetry (ITC), X-ray crystallography, and NMR backbone (15)N and methyl side-chain (2)H relaxation measurements. Global thermodynamics data derived from ITC indicate that binding is driven by favorable enthalpic contributions, rather than the classical entropy-driven hydrophobic effect. Unfavorable entropic contributions from the protein backbone and side-chain residues in the vicinity of the binding pocket are partially offset by favorable entropic contributions at adjacent positions, suggesting a "conformational relay" mechanism whereby increased rigidity of residues on ligand binding are accompanied by increased conformational freedom of side chains in adjacent positions. The principal driving force governing ligand affinity and specificity can be attributed to solvent-driven enthalpic effects from desolvation of the protein binding pocket. 相似文献
36.
37.
38.
39.
Reaction of chiral allylic cyclic carbonates with Grignards reagent in the presence of NiCl2(dppe) as a catalyst afforded the alkylated (E)-allylic alcohols with high regio- and diastereoselectivity. 相似文献
40.
Ya‐Chu Hsieh Hau‐Yu Fang Yi‐Ting Chen Rong Yang Chen‐I Yang Pi‐Tai Chou Ming‐Yu Kuo Yao‐Ting Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(10):3112-3116
The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature 1H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σmax=4323 GM at 530 nm]. 相似文献