全文获取类型
收费全文 | 2544篇 |
免费 | 87篇 |
国内免费 | 5篇 |
专业分类
化学 | 1929篇 |
晶体学 | 44篇 |
力学 | 22篇 |
数学 | 120篇 |
物理学 | 521篇 |
出版年
2023年 | 12篇 |
2022年 | 16篇 |
2021年 | 32篇 |
2020年 | 24篇 |
2019年 | 34篇 |
2018年 | 28篇 |
2017年 | 22篇 |
2016年 | 47篇 |
2015年 | 42篇 |
2014年 | 57篇 |
2013年 | 130篇 |
2012年 | 121篇 |
2011年 | 136篇 |
2010年 | 75篇 |
2009年 | 75篇 |
2008年 | 165篇 |
2007年 | 179篇 |
2006年 | 147篇 |
2005年 | 193篇 |
2004年 | 165篇 |
2003年 | 108篇 |
2002年 | 109篇 |
2001年 | 56篇 |
2000年 | 58篇 |
1999年 | 32篇 |
1998年 | 36篇 |
1997年 | 27篇 |
1996年 | 41篇 |
1995年 | 29篇 |
1994年 | 29篇 |
1993年 | 20篇 |
1992年 | 21篇 |
1991年 | 18篇 |
1990年 | 15篇 |
1989年 | 16篇 |
1988年 | 20篇 |
1987年 | 12篇 |
1986年 | 19篇 |
1985年 | 32篇 |
1984年 | 34篇 |
1983年 | 12篇 |
1982年 | 27篇 |
1981年 | 17篇 |
1980年 | 26篇 |
1979年 | 19篇 |
1978年 | 16篇 |
1977年 | 18篇 |
1975年 | 15篇 |
1974年 | 13篇 |
1972年 | 9篇 |
排序方式: 共有2636条查询结果,搜索用时 78 毫秒
21.
Adachi I Aihara H Dijkstra HB Enomoto R Fujii H Fujii K Fujii T Fujimoto J Fujiwara N Hayashii H Higashi S Iida N Imanishi A Ikeda H Ishii T Itoh R Iwasaki H Iwata S Kajikawa R Kamae T Kato S Kawabata S Kichimi H Kishida T Kobayashi M Kuroda S Kusuki N Maruyama A Maruyama K Masuda H Matsuda T Miyamoto A Morimoto T Nakamura K Nitoh O Noguchi S Ochiai F Okuno H Okusawa T Ohshima T Ozaki H Sato T Sai F Shimonaka J Shimozawa K Shirahashi A Sugahara R Sugiyama A Suzuki S Suwada T Takahashi K 《Physical review letters》1988,60(2):97-100
22.
Takanori Suzuki Tomohiro Iwai Eisuke Ohta Hidetoshi Kawai Kenshu Fujiwara 《Tetrahedron letters》2007,48(20):3599-3603
Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity. 相似文献
23.
Keitaro Yoshihara Yutaka Nagasawa Arkadiy Yartsev Shigeichi Kumazaki Hideki Kandori Alan E. Johnson Keisuke Tominaga 《Journal of photochemistry and photobiology. A, Chemistry》1994,80(1-3):169-175
We have investigated the ultrafast intermolecular electron transfer (ET) from an electron-donating solvent (aniline (AN) or N, N-dimethylaniline (DMA)) to an excited dye molecule (oxazines (Nile blue and oxazine 1) or coumarins). A non-exponential time dependence was observed in AN and can be explained by solvent reorientation and nuclear motion of the reactants. However, in DMA, a single exponential process was observed for Nile blue (160 fs) and oxazine 1 (280 fs), which can be explained by assuming that the rate of ET is limited mainly by ultrafast nuclear motion. A clear substituent effect on intermolecular ET was observed for the 7-aminocoumarins. When the alkyl chain on the 7-amino group is extended and a hexagonal ring with the benzene moiety is formed, the rate of ET is reduced by three orders of magnitude. This effect can be explained by a change in the free energy difference of the reaction and by the vibrational motion of the amino group. 相似文献
24.
Hideki Nishimori Masahiro Tatsumisago Tsutomu Minami 《Journal of Sol-Gel Science and Technology》1997,9(1):25-31
Monodispersed silica particles up to ca. 1.2 μm in diameter were prepared by hydrolysis of tetraethoxysilane in the presence
of sodium dodecyl sulfate (SDS). The particle size was increased with an increase of SDS added. The geometrical standard deviation
of the particles was decreased with an increase of SDS. In the earlier reaction stage, double spherical particles by the coalescence
of the particles were frequently observed when large amounts of SDS were added. Particle size was gradually increased after
the coalescence occurred and spherical particles were finally obtained. The results of Nielsen’s chronomal analysis suggest
that the polynuclear layer growth took place after the coalescence of the particles in the presence of larger amount of SDS. 相似文献
25.
The first total synthesis of (+)?3-deoxyaphidicolin, a selective inhibitor of eukaryotic DNA polymerase α, has been completed efficiently and stereoselectively starting from 1-abietic acid. 相似文献
26.
1-Alkoxy-3-trimethylsilylmethyl- and 1-alkoxy-3-trimethylsilyl-l,3-butadienes () were newly prepared. The cycloaddition reactions of with various dienophiles including heterodienophiles were found to proceed very smoothly in a perfectly regiospecific mode. 相似文献
27.
Nagaoka Y Inoue H el-Koussi N Tomioka K 《Chemical communications (Cambridge, England)》2002,(2):122-123
Upon treatment with lithium diisopropylamide achiral and chiral alpha,beta,psi,omega-unsaturated bisphosphine oxides underwent lithiation-conjugate addition tandem cyclization to afford the corresponding endo-alpha,beta-unsaturated cyclic bisphosphine oxides; sequential stereoselective reduction of the cyclized bisphosphine oxide gave the corresponding trans- and cis-bisphosphines that were successfully applicable in a catalytic asymmetric hydrogenation as chiral bisphosphine ligands. 相似文献
28.
Takanori Suzuki Prof. Shoko Tanaka Hidetoshi Kawai Dr. Kenshu Fujiwara Prof. 《化学:亚洲杂志》2007,2(1):171-177
The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H+, Δ) and two‐way‐output (UV/Vis, CD) response systems. 相似文献
29.
30.
S Yokohama T Miwa S Aibara H Fujiwara H Matsumoto K Nakayama T Iwamoto M Mori R Moroi W Tsukada 《Chemical & pharmaceutical bulletin》1992,40(9):2391-2398
A series of 6-alkyl- or 6-(cycloalkylalkyl)-[1,3,4]thiadiazolo[3,2- a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-ones 1b--o was synthesized from the corresponding 1,3,4-thiadiazol-5-amines 3b--o and the antiallergic activities of the products were evaluated. Among the compounds 6-(2-cyclohexylethyl)- [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one 1h, whose X-ray crystallographic stereostructure is shown, was found to be a promising new antiallergic agent, which has low toxicity and dual activity as a leukotriene D4 receptor antagonist and as an orally active mast cell stabilizer. 相似文献