全文获取类型
收费全文 | 3008篇 |
免费 | 111篇 |
国内免费 | 11篇 |
专业分类
化学 | 2334篇 |
晶体学 | 46篇 |
力学 | 22篇 |
综合类 | 1篇 |
数学 | 165篇 |
物理学 | 562篇 |
出版年
2023年 | 19篇 |
2022年 | 29篇 |
2021年 | 35篇 |
2020年 | 41篇 |
2019年 | 42篇 |
2018年 | 31篇 |
2017年 | 23篇 |
2016年 | 70篇 |
2015年 | 53篇 |
2014年 | 84篇 |
2013年 | 164篇 |
2012年 | 197篇 |
2011年 | 168篇 |
2010年 | 96篇 |
2009年 | 106篇 |
2008年 | 161篇 |
2007年 | 188篇 |
2006年 | 194篇 |
2005年 | 162篇 |
2004年 | 128篇 |
2003年 | 108篇 |
2002年 | 88篇 |
2001年 | 70篇 |
2000年 | 74篇 |
1999年 | 42篇 |
1998年 | 29篇 |
1997年 | 23篇 |
1996年 | 45篇 |
1995年 | 36篇 |
1994年 | 22篇 |
1993年 | 24篇 |
1992年 | 39篇 |
1991年 | 33篇 |
1990年 | 31篇 |
1989年 | 22篇 |
1988年 | 44篇 |
1987年 | 19篇 |
1986年 | 23篇 |
1985年 | 40篇 |
1984年 | 28篇 |
1983年 | 29篇 |
1982年 | 29篇 |
1981年 | 30篇 |
1980年 | 19篇 |
1979年 | 37篇 |
1978年 | 23篇 |
1976年 | 13篇 |
1975年 | 14篇 |
1974年 | 15篇 |
1973年 | 20篇 |
排序方式: 共有3130条查询结果,搜索用时 15 毫秒
51.
Yoshio Ueno Yutaka Takeuchi Jinya Koshitani Takatoshi Yoshida 《Journal of heterocyclic chemistry》1981,18(3):645-647
4-Acyl-1,2-dimethyl-3H-phenothiazin-3-ones were prepared by the photochemical reaction of 1,2-dimethyl-3H-phenothiazin-3-one with aldehydes. The structures of the newly prepared compounds were determined by elemental analysis, spectroscopic methods (ir, nmr and ms) and comparison with a sample prepared by an alternate route. 相似文献
52.
Fumiyo Saito Ryo Takeuchi Tomoyuki Kamino Kouji Kuramochi Kengo Sakaguchi Susumu Kobayashi Masashi Tsuda 《Tetrahedron letters》2004,45(43):8069-8071
A total synthesis of the proposed structure of plakevulin A was accomplished. However, the NMR spectral data of the synthetic plakevulin A were not identical of those of the reported compound. We next converted the synthetic plakevulin A into 1-dihydrountenone A. The 1H and 13C NMR spectral data of 1-dihydrountenone A were identical with those of reported plakevulin A except for the peaks derived from levulinic acid. Thus, we repurified sample of the natural product and confirmed that the natural sample contained 1-dihydrountenone A and levulinic acid in the ratio of one to one. We also found that not plakevulin A but 1-dihydountenone A possessed the inhibitory activity against mammalian DNA polymerases α and β. 相似文献
53.
T. Takeuchi S. Uehara T. Hayashi 《Journal of Radioanalytical and Nuclear Chemistry》1980,56(1-2):25-35
Several dead time correction methods were compared experimentally with the exact correction method and their limits were discussed.
These correction methods were applied to neutron activation analysis of a biological sample. A special electronic circuit
and an additional counting equipment were used to obtain the fractional dead time with a suficiently high frequency. 相似文献
54.
Application of dibutyltin oxide method to regioselective acylation and alkylation of tylosin at C-4' 总被引:1,自引:0,他引:1
K Kiyoshima M Sakamoto T Ishikura Y Fukagawa T Yoshioka H Naganawa T Sawa T Takeuchi 《Chemical & pharmaceutical bulletin》1989,37(4):861-865
4'-O-Acyl-, 4'-O-alkyl- and 4'-deoxy-tylosin derivatives were synthesized using 2'-O-acetyl-3',4'-O-(dibutyl-stannio)tylosin as a synthetic intermediate. The in vitro biological evaluation showed that the new derivatives were active against macrolide-resistant clinical isolates of bacteria and mycoplasmas, and that they were resistant to hepatic esterase. 相似文献
55.
Kenjiro Hattori Tomoko Takeuchi Mika Ogata Ayumi Takanohashi Katsuhiko Mikuni Katsuyoshi Nakanishi Hideo Imata 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):339-342
We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G2βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G2βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on
the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The
SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful
for the repeated measurement. 相似文献
56.
Yanagi T Kikuchi K Takeuchi H Ishikawa T Nishimura T Yamamoto I 《Chemical & pharmaceutical bulletin》2001,49(8):1018-1023
The synthetic route for a uterine relaxant, bis(2-[[(2S)-2-([(2R)-2-hydroxy-2-[4-hydroxy-3-(2-hydroxyethyl)-phenyl]ethyl]amino)-1,2,3,4-tetrahydronaphthalen-7-yl]oxy]-N,N-dimethylacetamide) sulfate (KUR-1246), was established by the coupling of optically active components, the bromohydrin 14 and the amine 24. We now describe the practical synthesis of these two optically active components. Bromohydrin 14 was obtained by the asymmetric borane reduction of the prochiral phenacyl bromide 13 using a catalyst prepared from aluminum triethoxide and a chiral amino alcohol. The other optically active component 24 was prepared from (S)-AMT. 相似文献
57.
Ogawa T Araki M Miyamae T Okayama T Hagiwara M Sakurada S Morikawa T 《Chemical & pharmaceutical bulletin》2003,51(7):759-771
To improve the oral bioavailability of a dermorphin tetrapeptide analog, N(alpha)-1-iminoethyl-Tyr-D-MetO-Phe-MebetaAla-OH (III), which has a potent analgesic activity after oral administration, various derivatives were synthesized to increase lipophilicity by esterification of the C-terminal carboxyl group and/or acylation of the phenolic hydroxyl group on Tyr1. Antinociceptive activity was evaluated after subcutaneous or oral administration using the mouse tail pressure test. As a result, increased antinociceptive activity after oral administration as well as an improved ED50(p.o.)/ED50(s.c.) ratio, which is an indicator of oral bioavailability, were found for some compounds. With regard to the improvement of bioavailability, derivatives with acylation of the phenolic hydroxyl group on Tyr1 showed better results than derivatives with esterification of the C-terminal carboxyl group. In particular, an ED50(p.o.)/ED50(s.c.) ratio equivalent to that of morphine was found for an acetylated derivative, N(alpha)-1-iminoethyl-Tyr(COMe)-D-MetO-Phe-MebetaAla-OH (7a), as well as for a methoxycarbonylated derivative, N(alpha)-1-iminoethyl-Tyr(CO2Me)-D-MetO-Phe-MebetaAla-OH (7l). 相似文献
58.
Toshiaki Sunazuka Masaki Handa Tatsuya Shirahata Kazuhiko Otoguro Satoshi ōmura 《Tetrahedron》2004,60(36):7845-7859
In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins. 相似文献
59.
Y Takeuchi H Yasukawa Y Yamaoka Y Morimoto S Nakao Y Fukumori T Fukuda 《Chemical & pharmaceutical bulletin》1992,40(2):484-487
Whole skin lipid bio-liposomes (skin bio-liposomes), in size ranging from 2 to 8 microns, were prepared by a reverse phase evaporation technique using rat full thickness skin. Leakage of an encapsulated fluorescence probe, ANTS (delta-amino-1,3,6-naphthalene-trisulfonate), was measured by adding transdermal penetration enhancers (penetrants) into the medium where the skin bio-liposomes were present. Oleylamine induced a fast release of ANTS from the liposomes compared to lauryl-amine which showed a weak action. With these penetrants, the degree of ANTS release from the prepared bio-liposomes was found to correlate well with the results of frequency changes in the CH-asymmetric stretching band near 2920 cm-1 in the rat stratum corneum. The penetrant which caused relatively strong leakage of ANTS induced the significantly large shift of the peak toward the higher wave-numbers due to the perturbation in the structure of lipids of the stratum corneum. The skin bio-liposomes prepared from the rat full thickness skin could be useful in evaluating the penetrants. 相似文献
60.
Fluorine has come to be recognized as a key element in materials science: in heat‐transfer agents, liquid crystals, dyes, surfactants, plastics, elastomers, membranes, and other materials. Furthermore, many fluorine‐containing biologically active agents are finding applications as pharmaceuticals and agrochemicals. Progress in synthetic fluorine chemistry has been critical to the development of these fields and has led to the invention of many novel fluorinated molecules as future drugs and materials. As a result of the electronic effects of fluorine substituents, fluorinated substrates and reagents often exhibit unusual and unique chemical properties, which often make them incompatible with established synthetic methods. Thus, the problem of how to control the unusual properties of compounds with fluorine substituents deserves much attention, so as to promote the design of facile, efficient, and environmentally benign methods for the synthesis of valuable organofluorine targets. 相似文献