全文获取类型
收费全文 | 1999篇 |
免费 | 80篇 |
国内免费 | 7篇 |
专业分类
化学 | 1397篇 |
晶体学 | 16篇 |
力学 | 32篇 |
数学 | 128篇 |
物理学 | 513篇 |
出版年
2023年 | 18篇 |
2022年 | 28篇 |
2021年 | 24篇 |
2020年 | 29篇 |
2019年 | 35篇 |
2018年 | 31篇 |
2017年 | 19篇 |
2016年 | 53篇 |
2015年 | 44篇 |
2014年 | 56篇 |
2013年 | 84篇 |
2012年 | 101篇 |
2011年 | 125篇 |
2010年 | 78篇 |
2009年 | 79篇 |
2008年 | 121篇 |
2007年 | 115篇 |
2006年 | 108篇 |
2005年 | 99篇 |
2004年 | 78篇 |
2003年 | 62篇 |
2002年 | 45篇 |
2001年 | 40篇 |
2000年 | 44篇 |
1999年 | 27篇 |
1998年 | 20篇 |
1997年 | 17篇 |
1996年 | 33篇 |
1995年 | 10篇 |
1994年 | 22篇 |
1993年 | 20篇 |
1992年 | 25篇 |
1991年 | 18篇 |
1990年 | 23篇 |
1989年 | 32篇 |
1988年 | 29篇 |
1987年 | 25篇 |
1986年 | 28篇 |
1985年 | 27篇 |
1984年 | 29篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 24篇 |
1980年 | 13篇 |
1978年 | 20篇 |
1977年 | 10篇 |
1976年 | 15篇 |
1975年 | 16篇 |
1973年 | 15篇 |
1969年 | 8篇 |
排序方式: 共有2086条查询结果,搜索用时 15 毫秒
61.
62.
DL-2-(4-2-Thienylcarbonyl)phenyl)propionic acid (suprofen) was rapidly absorbed in both sexes of rats, guinea pigs, and rabbits after oral administration. Blood levels after a single dose of 2 mg/kg 3H-suprofen in all the animals reached maxima within 15 min, and elimination of the 3H from blood was rapid; the radioactivity was mostly excreted in the urine and feces within 24 h after dosing. 相似文献
63.
The influence of amino acids on the formation of hematite particles from a forced hydrolysis reaction of acidic FeCl3 solution was examined. The spherical particles were produced on the systems with L-phenylalanine (L-Phe), L-serine (L-Ser) and L-alanine (L-Ala), though L-glutamine (L-Gln) and L-glutamic acid (L-Glu) gave ellipsoidal hematite particles. This morphological change in hematite particles is consistent with the order of stability constant of amino acids against to Fe3+ ions (K). The hematite particles produced with L-Glu, L-Gln and L-Ser were highly porous because they are formed by aggregation of cluster particles. These particles exhibited microporous behavior by outgassing the particles below 200 degrees C while they changed to mesoporous after treating above 300 degrees C by elimination of amino acids molecules remained between the cluster particles within the hematite particles. The hematite particles strongly depended on the nature of amino acids such as alternation of solution pH and adsorption affinity to beta-FeOOH and/or polynuclear primary (PN) particles. The systems on L-Ala and L-Phe, showing very rapid phase transformation from beta-FeOOH to hematite, exhibited the Ostwald ripening. A rotational particle preparation procedure suggested that the morphology of hematite particle is governed by the mode and strength of amino acid adsorption onto beta-FeOOH and/or PN particles. 相似文献
64.
65.
Effects of magnetization on the complex modulus of kappa-carrageenan magnetic gels have been investigated. The magnetic gel was made of a natural polymer, kappa-carrageenan, and a ferrimagnetic particle, barium ferrite. The complex modulus was measured before and after magnetization of the gel by dynamic viscoelastic measurements with a compressional strain. The gels showed a giant reduction in the storage modulus of approximately 10(7) Pa and also in the loss modulus of approximately 10(6) Pa due to magnetization. The reduction increased with increasing volume fraction of ferrite, and it was nearly independent of the frequency. It was also found that the change in the modulus was nearly independent of the magnetization direction and irradiation time of the magnetic fields to the gel. The magnetic gels demonstrating the giant reduction in the dynamic modulus showed a large nonlinear viscoelastic response. It was observed that the magnetic gel was deformed slightly due to magnetization. The observed giant complex modulus reduction could be attributed to the nonlinear viscoelasticity and deformation caused by magnetization. Magnetism, nonlinear viscoelasticity, and effects of magnetization on the morphological and shape changes were discussed. 相似文献
66.
Jiang C Lesbani A Kawamoto R Uchida S Mizuno N 《Journal of the American Chemical Society》2006,128(44):14240-14241
An ionic crystal of Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40].4H2O 1a with hydrophilic and hydrophobic channels has been designed and successfully synthesized. The guest-free phase 1b sorbs dichloromethane and water in the hydrophobic and hydrophilic channels, respectively. The rate and equilibrium amount of the dichloromethane sorption into the hydrophobic channel and those of water into the hydrophilic channel were independent of each other. The sorption properties can be applied to the channel-selective sorption and collection of hydrophobic (dichloromethane) and hydrophilic (water) molecules from the mixture. 相似文献
67.
Jinnouchi R Kodama K Hatanaka T Morimoto Y 《Physical chemistry chemical physics : PCCP》2011,13(47):21070-21083
A first principles-based mean field model was developed for the oxygen reduction reaction (ORR) taking account of the coverage- and material-dependent reversible potentials of the elementary steps. This model was applied to the simulation of single crystal surfaces of Pt, Pt alloy and Pt core-shell catalysts under Ar and O(2) atmospheres. The results are consistent with those shown by past experimental and theoretical studies on surface coverages under Ar atmosphere, the shape of the current-voltage curve for the ORR on Pt(111) and the material-dependence of the ORR activity. This model suggests that the oxygen associative pathway including HO(2)(ads) formation is the main pathway on Pt(111), and that the rate determining step (RDS) is the removal step of O(ads) on Pt(111). This RDS is accelerated on several highly active Pt alloys and core-shell surfaces, and this acceleration decreases the reaction intermediate O(ads). The increase in the partial pressure of O(2)(g) increases the surface coverage with O(ads) and OH(ads), and this coverage increase reduces the apparent reaction order with respect to the partial pressure to less than unity. This model shows details on how the reaction pathway, RDS, surface coverages, Tafel slope, reaction order and material-dependent activity are interrelated. 相似文献
68.
Photoinduced Charge‐Transfer State of 4‐Carbazolyl‐3‐(trifluoromethyl)benzoic Acid: Photophysical Property and Application to Reduction of Carbon−Halogen Bonds as a Sensitizer 下载免费PDF全文
Prof. Dr. Ryosuke Matsubara Toshiyuki Shimada Prof. Dr. Yasuhiro Kobori Tatsushi Yabuta Prof. Dr. Toshiyuki Osakai Prof. Dr. Masahiko Hayashi 《化学:亚洲杂志》2016,11(14):2006-2010
The photoinduced persistent intramolecular charge‐transfer state of 4‐carbazolyl‐3‐(trifluoromethyl)benzoic acid was confirmed. It showed a higher catalytic activity in terms of yield and selectivity in the photochemical reduction of alkyl halides compared to the parent carbazole. Even unactivated primary alkyl bromides could be reduced by this photocatalyst. The high catalytic activity is rationalized by considering the slower backward single‐electron transfer owing to the spatial separation of the donor and acceptor subunits. 相似文献
69.
Akira Hirota Masahira Nakagawa Heiichi Sakai Akira Isogai Kazuo Furihata Haruo Seto 《Tetrahedron letters》1985,26(32):3845-3848
Feeding experiments with [2-3H3]acetate and [2-13C2H3]acetate in Thom No. 14 indicated that the hydrogen at C-2 in terrecyclic acid A is incorporated without migration from the precursor acetic acid; the results favour our group's earlier speculation for the cyclization to the tricyclic skeleton in the biosynthetic scheme. 相似文献
70.
Fragmentation of the pyridine ring followed by K-shell excitation/ionization has been studied with 2-fluoropyridine (2FPy) by electron impact. Ab initio molecular orbital (MO) calculations were also carried out to investigate the electronic states correlating with specific fragment ions. The fragment ions are produced characteristically at the N 1s edge, while the spectra observed at the F 1s and C 1s edges exhibit a small difference from that at the valence ionization. The production of the C(4)H(2)(+), C(4)H(3)(+) and C(4)H(2)F(+) ions indicates that the cleavage of the N-C6 and C2-C3 bonds or the N-C2 and C5-C6 bonds is likely to occur after the N 1s excitation/ionization. Ab initio MO calculations indicate that the former fission is likely to proceed through the n(N)(1)π(2)(1)π(3)(2) and n(N)(0)π(2)(2)π(3)(2) excited states of the parent molecular dication. On the other hand, the breakage of the N-C2 and C4-C5 bonds, which specifically proceeds at the N 1s edge for 2-methylpyridine, does not occur for 2FPy. The present calculation reveals that the products of this channel are unstable by the electronegativity of fluorine and that the relative energy of the Auger-final states of 2FPy is lowered by the reorganization and electron correlation effects. 相似文献