全文获取类型
收费全文 | 19658篇 |
免费 | 629篇 |
国内免费 | 113篇 |
专业分类
化学 | 14103篇 |
晶体学 | 189篇 |
力学 | 378篇 |
综合类 | 1篇 |
数学 | 2956篇 |
物理学 | 2773篇 |
出版年
2022年 | 164篇 |
2021年 | 199篇 |
2020年 | 294篇 |
2019年 | 290篇 |
2018年 | 186篇 |
2017年 | 181篇 |
2016年 | 406篇 |
2015年 | 357篇 |
2014年 | 451篇 |
2013年 | 929篇 |
2012年 | 977篇 |
2011年 | 1268篇 |
2010年 | 619篇 |
2009年 | 524篇 |
2008年 | 1014篇 |
2007年 | 1092篇 |
2006年 | 1073篇 |
2005年 | 1038篇 |
2004年 | 881篇 |
2003年 | 745篇 |
2002年 | 732篇 |
2001年 | 250篇 |
2000年 | 254篇 |
1999年 | 230篇 |
1998年 | 223篇 |
1997年 | 259篇 |
1996年 | 284篇 |
1995年 | 227篇 |
1994年 | 212篇 |
1993年 | 244篇 |
1992年 | 203篇 |
1991年 | 185篇 |
1990年 | 163篇 |
1989年 | 141篇 |
1988年 | 140篇 |
1987年 | 158篇 |
1986年 | 135篇 |
1985年 | 202篇 |
1984年 | 249篇 |
1983年 | 178篇 |
1982年 | 220篇 |
1981年 | 241篇 |
1980年 | 180篇 |
1979年 | 181篇 |
1978年 | 214篇 |
1977年 | 159篇 |
1976年 | 157篇 |
1975年 | 150篇 |
1974年 | 165篇 |
1973年 | 140篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
151.
Bartlett PA Yusuff N Rico AC Lindvall MK 《Journal of the American Chemical Society》2002,124(15):3853-3857
The hydrophobic component to the binding affinities of one acyclic phosphinate (4) and three macrocyclic phosphonamidate inhibitors (1-3) to the zinc peptidase thermolysin was probed by varying the solvent composition. Increasing the percentage of ethanol in the buffer solution over the range 0-9% increases the inhibition constants, K(i), by up to an order of magnitude. This approach represents an experimental method for distinguishing solvation from conformational or other effects on protein-ligand binding. The size of the "antihydrophobic effect" is correlated with the amount of hydrophobic surface area sequestered from solvent on association of the inhibitor and enzyme, although it is attenuated from that calculated from the surface tension of ethanol-water mixtures. The results are consistent with the Lum-Chandler-Weeks explanation for the size dependence of the hydrophobic effect. 相似文献
152.
This review addresses the special problems associated with the micro-structural characterization of thin and ultrathin organic films, primarily by optical spectroscopies. Films which are deposited by Langmuir-Blodgett techniques, self-assembly chemistry, and bulk film deposition techniques are considered. The use of enhanced optical excitation using surface phasma resonances and integrated optical structures is discussed extensively, as is the use of ellipsometry. Discussion of the spectroscopies used is broken into a section on electronic spectroscopies and an extensive discussion of vibrational spectroscopies. Vibrational information may be obtained with photons (absorption or scattering) or electrons (loss spectra), and the types of experimental systems amenable to each, along with the advantages and disadvantages of each are explored. 相似文献
153.
Ab initio molecular orbital structures and energies of B2F4, B2Cl4, N2O4, and C2O have been calculated for both perpendicular D2d and planar D2h rotamers. The experimental trend toward greater preference for the D2d forms in going from B2F4 to B2Cl4 is reproduced. N2O4 favors the planar conformation, although the rotation barrier is overestimated at the theoretical levels used. The oxalate dianion is calculated to be more stable in the D2d conformation; the experimental planar arrangement in the solid may be due to crystal packing forces. The preferences for one conformation over another are small; analysis indicates that different effects may predominate in each case: π stabilization for B2F4, hyperconjugation for B2Cl4, lone-pair interactions for N2O4, and electrostatic repulsions for C2O. 相似文献
154.
The results of allowing tetrahydro-as-triazine-3(2H)-thiones to react with various α,β-diiunctional compounds, such as, α-bromoethyl p-toluenesulfonate, chloroacetaldehyde, α-bromophenylacet-uldehyde, phenaeyl bromide, chloroacetonitrile, α-bromophenylaeelonitrile, and α-cyanobenzyl p-toluenesulfonate are discussed. These condensations give either a 5H-thiazolo[3,2-b]-as-triazine or a 2H-thiazolo[2,3-c]-as-triazine. 相似文献
155.
Katsuhiro Saito Yoichi Omura Etsuro Maekawa Paul G. Gassman 《Tetrahedron letters》1984,25(24):2573-2576
Addition reactions of cyclooctatetraene with 1,3-diphenylisobenzofuran resulted in the formation of three 1:1 cycloadducts, 1, 2, and 3, and a 1:2 cycloadduct, 4. Single crystal x-ray analysis established 3 to be a cage compound formed by an unprecedented [4+2] cycloaddition reaction of 1 in which the double bond of the benzene moiety acted as the dienophile. 相似文献
156.
Reinhard Schubert Achim Ansmann Paul Bleckmann Bernhard Schrader 《Journal of Molecular Structure》1975,26(2):429-438
By using the values of the vibrational frequencies of normal and deuterated cyclopropenone (II-d0 , II-d2 ) and 16 O-and 18 O-substituted dimethylcyclopropenone (III) as -well as the infrared and Raman intensities of II a consistent set of force constants has been derived for the cyclopropenone skeleton. The derived values show that the zwitterionic form makes a substantial contribution to the electronic ground state of the molecule. The combined frequency and intensity calculation - simulation of the infrared and the Raman spectrum - is shown to be a good method for making a proper assignment of calculated and observed vibrations and deriving realistic sets of force constants. 相似文献
157.
Yannick Ortin Paul O'Donohue Helge Müller-Bunz Anthony R. Manning 《Journal of organometallic chemistry》2004,689(9):1657-1664
Treatment of the aldehyde (η4-C4Ph4)Co(η5-C5H4-CHO) (4b) with tert-butyllithium or phenyllithium yields the secondary alcohols (η4-C4Ph4)Co(η5-C5H4-CH(R)OH), where R=tert-butyl (5) or phenyl (6). Protonation of 5 and 6 at −80 °C furnishes the deep purple, cobalt-stabilized cations, 7 and 8, respectively, both of which exhibit restricted rotation about the external C5H4-CHR+ linkage on the NMR time-scale. These data indicate a minimum value for the barrier to rotation of 15 kcal mol−1, but it is certainly much higher, indicating a considerable degree of C-C double bond character. X-ray crystal structures of 4b, 5 and also of the ketone (η4-C4Ph4)Co(η5-C5H4-C(O)CH3 (4a) are reported. The secondary alcohol 5 exhibits disorder in the solid state because of the presence of diastereomers as a consequence of the stereogenic center at the α-carbon and the clockwise or anticlockwise propeller orientations of the tetraphenylcyclobutadiene ligand. 相似文献
158.
159.
Christoph Luef Aloke Paul Jiri Vizdal Ales Kroupa Alexander Kodentsov Herbert Ipser 《Monatshefte für Chemie / Chemical Monthly》2006,137(4):381-395
Summary. The partial and integral enthalpies of mixing of liquid Bi–Sn–Zn alloys were determined at 500°C by a drop calorimetric technique
using a Calvet-type microcalorimeter. The ternary interaction parameters in the Bi–Sn–Zn system were fitted using the Redlich-Kister-Muggianu model for substitutional solutions, and isoenthalpy curves of the integral molar enthalpy of mixing at 500°C were constructed.
Furthermore, a DSC technique was used to determine the liquidus temperatures in three sections (3, 5, and 7 at.% Zn) as well
as the invariant reaction temperature of the ternary eutectic L ⇄ (Bi) + (Sn) + (Zn). The ternary eutectic reaction was found
at 135°C. 相似文献
160.
Synthesis of a BQQ-neomycin conjugate is reported. The conjugate combines two ligands, one known to intercalate triplexes (BQQ) and another known to bind in the triplex groove (neomycin). The conjugate stabilizes T.A.T, as well as mixed base DNA triplex, better than neomycin, BQQ, or a combination of both. The conjugate selectively stabilizes the triplex (in the presence of physiological salt concentrations), with as little as 4 muM of the ligand leading to a DeltaTm of >60 degrees C. Competition dialysis studies show a clear preference for the drug binding to triplex DNA/RNA over the duplex/single strand structures. Modeling studies suggest a structure of neomycin bound to the larger W-H (Watson-Hoogsteen) groove with BQQ intercalated between the triplex bases. 相似文献