全文获取类型
收费全文 | 354篇 |
免费 | 12篇 |
国内免费 | 1篇 |
专业分类
化学 | 221篇 |
晶体学 | 6篇 |
力学 | 7篇 |
数学 | 8篇 |
物理学 | 125篇 |
出版年
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 8篇 |
2012年 | 25篇 |
2011年 | 21篇 |
2010年 | 10篇 |
2009年 | 16篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 20篇 |
2005年 | 26篇 |
2004年 | 14篇 |
2003年 | 18篇 |
2002年 | 16篇 |
2001年 | 10篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 3篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 7篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1942年 | 1篇 |
1932年 | 1篇 |
1930年 | 2篇 |
1928年 | 1篇 |
排序方式: 共有367条查询结果,搜索用时 31 毫秒
51.
Hironori Okamura Takanobu Fujioka Naoki Mori Tohru Taniguchi Kenji Monde Hidenori Watanabe Hirosato Takikawa 《Tetrahedron letters》2019,60(32):150917
Salinipostins are cyclic enol-phosphotriesters isolated from a marine-derived Salinispora sp. as antimalarial compounds. Herein, the first enantioselective synthesis of salinipostin A was achieved. Organocatalyst-mediated asymmetric cyclopropanation and regioselective cyclopropane ring opening were the key steps. 相似文献
52.
Hiryu S Hagino T Fujioka E Riquimaroux H Watanabe Y 《The Journal of the Acoustical Society of America》2008,124(2):EL51-EL56
Echolocation pulses emitted by wild Pipistrellus abramus were investigated while foraging for insects in the field. Similar to other European pipistrelles, the frequency structure during foraging varied. During the search phase, the bats emitted long shallow frequency-modulated pulses 9-11 ms in duration, whereas the maximum pulse duration of the bats approaching a large target wall in the laboratory was 3 ms. No significant difference was observed between decreases in the interpulse interval during these two approach flights. It is concluded that the bats use a long quasi-constant frequency pulse to find a weak echo from a small prey target. 相似文献
53.
Murai K Morishita M Nakatani R Kubo O Fujioka H Kita Y 《The Journal of organic chemistry》2007,72(23):8947-8949
The first asymmetric total synthesis of spongotine A is described. The oxidative synthesis of the imidazoline/ketone unit from keto aldehyde and diamine is a key step in this synthesis. The absolute stereochemistry of the asymmetric center of natural spongotine A is revealed as the (S)-configuration. 相似文献
54.
Enders D Nagao T Nakayama T Aono M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(11):6119-6125
The adsorption and desorption of Au nanoparticles (AuNP) in colloidal D2O suspension on the (3-aminopropyl)triethoxysilane treated SiO2/Si surface was investigated by in situ attenuated total reflection surface enhanced infrared absorption (ATR-SEIRA) spectroscopy with a liquid flow cell. With increasing surface density of AuNP, the absorption of the vibrational modes of D2O and of the citrate molecules covering the AuNP increases due to SEIRA. Repulsive electrostatic Coulomb forces between the AuNP lead to the saturation of the AuNP surface density at submonolayer coverage. We show that the adsorption kinetics can be investigated by monitoring in situ the molecular vibrational modes of D2O and the citrate molecules. Furthermore, we clarify that the adsorption process can be described very well by a diffusion-limited first-order Langmuir kinetics model. When exposing a saturated AuNP submonolayer to 2-aminoethanethiol (AET)/D2O solution, the AuNP are removed from the surface and the IR absorption of the D2O vibrational modes become weaker again. Taking into account the time dependencies of the OD and the CH peaks, we propose a microscopic model where the AET molecules quickly adsorb on the AuNP by replacing most of the precovering citrate molecules exposed to the AET solution. As this takes place, the AuNP agglomerate-as we could detect with scanning electron microscopy-and are finally removed from the surface. 相似文献
55.
A new regime of chemical oxygen-iodine laser (COIL), high-pressure subsonic mode operation, was demonstrated using a jet-type
singlet oxygen generator (SOG). The laser output power of 342 W with chemical efficiency of 20.9% was obtained at the Cl2 flow rate of 18 mmol/s and the operating pressure of 6.4 Torr in the laser cavity. The specific energy was 3.1 J/l which
was four times higher than our supersonic device, and was comparable to the highest value for the supersonic regime. The experimental
results were in good agreement with the numerical simulation results.
Received: 26 February 1999 / Revised version: 13 July 1999 / Published online: 30 November 1999 相似文献
56.
T. Saiki S. Motokoshi K. Fujioka H. Fujita C. Yamanaka 《Optics Communications》2009,282(13):2556-2984
Laser pulses with high repetitive rate generated from a Q-switch microchip Nd:YAG oscillator were amplified by Active mirror composed of Nd/Cr:YAG ceramic pumped by CW arc-lamp. The laser pulses were amplified, and saturation of averaged output laser power was observed. Repetitive ratio of injected laser pulses was changed from 20 to 100 kHz. Averaged output laser power and gain were measured, and gain coefficient and power-extraction efficiency were evaluated. Output laser power was calculated and compared to experimentally measured one, and the calculated results are consistent with the experimental ones. For amplification of laser pulses with high repetitive ratio, this laser material can realize very high laser gain with low pumping power density and high optical-optical conversion efficiency under CW-lamp-light pumping. 相似文献
57.
Tomohito Kameda Katsuaki Imai Guido Grause Tadaaki Mizoguchi Toshiaki Yoshioka 《Polymer Degradation and Stability》2009,94(9):1595-1597
The dehydrochlorination of PVC in the presence of NaOH was investigated in different diols. Diethylene glycol (DEG), triethylene glycol (TEG), and propylene glycol (PG) were found to be effective in accelerating the dechlorination of PVC. The dehydrochlorination was promoted in the order TEG > DEG > PG, which was in agreement with the compatibility between PET and the diol. Compatibility resulted in an improved penetration of the PVC particle by the solvent, leading to the acceleration of the dehydrochlorination. The dehydrochlorination of PVC in NaOH/diol followed first-order kinetics, confirming the progress of the reaction under chemical reaction control. The apparent activation energies were 82 kJ mol−1, 109 kJ mol−1, and 151 kJ mol−1 for TEG, DEG, and PG, respectively. The lower the activation energy became the faster the dehydrochlorination of PVC proceeded. 相似文献
58.
Fujioka H Okitsu T Sawama Y Murata N Li R Kita Y 《Journal of the American Chemical Society》2006,128(17):5930-5938
We report here unexpected highly chemoselective deprotection of the acetals from aldehydes. Treatment of acetal compounds from aldehydes with TESOTf-2,6-lutidine or TESOTf-2,4,6-collidine in CH2Cl2 at 0 degrees C followed by H2O workup at the same temperature caused the conversion of the acetal functions to aldehyde functions. The reaction had generality and was applied to many acetal compounds. Study using various bases revealed the reaction and reached the best combination of TESOTf-base. It was very mild and highly chemoselective and proceeded under weakly basic conditions. Then, many functional groups such as allyl alcohol, silyl ether, acetate, methyl ether, triphenylmethyl (Tr) ether, 1,3-dithiolane, methyl ester, and tert-butyl ester could survive under these conditions. Furthermore, this methodology could selectively deprotect the acetals in the presence of ketals as the most characteristic feature, although this chemoselectivity is difficult to achieve by other previously reported methods. A detailed study of the reaction including MS and NMR studies revealed the reaction mechanism for determining the structures of the intermediates, pyridinium-type salts. These intermediates had a weak electrophilicity and were successfully applied to the efficient formation of the mixed acetals in high yields. 相似文献
59.
Ma G Li W Dou D Chang X Bai H Satou T Li J Sun D Kang T Nikaido T Koike K 《Chemical & pharmaceutical bulletin》2006,54(8):1229-1233
Five new monoterpene glycosides, rhodiolosides A-E (1-5), were isolated from the roots of Rhodiola rosea (Crassulaceae). Their structures were elucidated as (2E,6E,4R)-4,8-dihydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranoside (1), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl alpha-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside (2), (2E,4R)-4-hydroxy-3,7-dimethyl-2,6-octadienyl beta-D-glucopyranosyl(1-->3)-beta-D-glucopyranoside (3), (2E,4R)-4,7-dihydroxy-3,7-dimethyl-2-octenyl beta-D-glucopyranoside (4), and (2E)-7-hydroxy-3,7-dimethyl-2-octenyl alpha-L-arabinopyranosyl(1-->6)-beta-D-glucopyranoside (5), on the basis of various spectroscopic analyses and chemical degradation. 相似文献
60.
Murai K Nakamura A Matsushita T Shimura M Fujioka H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8448-8453
A method for conducting enantioselective bromolactonization reactions of trisubstituted alkenoic acids, using the C(3)-symmetric trisimidazoline 1 and 1,3-dibromo-5,5-dimethyl hydantoin as a bromine source, has been developed. The process generates chiral δ-lactones that contain a quaternary carbon. The results of studies probing geometrically different olefins show that (Z)-olefins rather than (E)-olefins are favorable substrates for the process. The method is not only applicable to acyclic olefin reactants but can also be employed to transform cyclic trisubstituted olefins into chiral spirocyclic lactones. Finally, the synthetic utility of the newly developed process is demonstrated by its application to a concise synthesis of tanikolide, an antifungal marine natural product. 相似文献