全文获取类型
收费全文 | 1233篇 |
免费 | 19篇 |
国内免费 | 7篇 |
专业分类
化学 | 929篇 |
晶体学 | 17篇 |
力学 | 22篇 |
数学 | 54篇 |
物理学 | 237篇 |
出版年
2023年 | 8篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 9篇 |
2018年 | 9篇 |
2017年 | 5篇 |
2016年 | 10篇 |
2015年 | 12篇 |
2014年 | 22篇 |
2013年 | 40篇 |
2012年 | 48篇 |
2011年 | 53篇 |
2010年 | 26篇 |
2009年 | 30篇 |
2008年 | 66篇 |
2007年 | 61篇 |
2006年 | 65篇 |
2005年 | 52篇 |
2004年 | 51篇 |
2003年 | 51篇 |
2002年 | 29篇 |
2001年 | 35篇 |
2000年 | 30篇 |
1999年 | 13篇 |
1998年 | 8篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 16篇 |
1994年 | 27篇 |
1993年 | 24篇 |
1992年 | 38篇 |
1991年 | 24篇 |
1990年 | 26篇 |
1989年 | 15篇 |
1988年 | 19篇 |
1987年 | 28篇 |
1986年 | 37篇 |
1985年 | 29篇 |
1984年 | 22篇 |
1983年 | 13篇 |
1982年 | 21篇 |
1981年 | 21篇 |
1980年 | 14篇 |
1979年 | 25篇 |
1978年 | 20篇 |
1977年 | 20篇 |
1976年 | 10篇 |
1975年 | 8篇 |
1974年 | 9篇 |
1973年 | 6篇 |
排序方式: 共有1259条查询结果,搜索用时 31 毫秒
11.
12.
Warunee Klinklai Tomonobu Mizumo Jitladda Tangpakdee Sakdapipanich Hiroyuki Ohno 《European Polymer Journal》2003,39(8):1707-1712
Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (Tg) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH4)2S2O8 in the presence of propanal. The resulting liquid epoxidized rubber (Mn≈104) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li+ as an ionic conducting medium, that is, solid polymer electrolyte. 相似文献
13.
Y Nomoto H Takai T Hirata M Teranishi T Ohno K Kubo 《Chemical & pharmaceutical bulletin》1991,39(1):86-90
A series of 1-(6,7-dimethoxy-4-quinazolinyl)piperidines carrying various 5-membered heterocycles at the 4-position was synthesized and examined for cardiotonic activity in anesthesized dogs. The (4-oxo-2-thioxo-3-imidazolindinyl)amino derivatives showed the most potent inotropic activity. Marked loss of activity was observed in the 2,4-dihydro-3-thioxo-3H-1,2,4-triazolyl, the 2,4-dihydro-3-oxo-3H-pyrazolyl and the (2,3-dihydro-2-thioxo-3H-1,3,4-thiadiazol-5-yl)amino derivatives. The synthesis and structure-activity relationships are discussed. 相似文献
14.
Supranee Wiwatchaiwong Hirotoshi Matsumura Nobuhumi Nakamura Masafumi Yohda Hiroyuki Ohno 《Electroanalysis》2007,19(5):561-565
We have studied the characterization of thermophilic cytochrome P450 (P450st)‐didodecyldimethylammonium bromide (DDAB) films by using UV‐vis absorption, resonance Raman spectroscopy, and electrochemical methods. The observed Raman spectrum indicated near‐native conformation of the heme iron in DDAB film on the surface of a glass slide, while on the surface of a plastic‐formed carbon (PFC) electrode, the conformation of P450st‐DDAB was very similar to that of heme‐DDAB film, suggesting the release of heme from P450st in DDAB films on PFC electrodes. When NaBr was added as salt to the casting solution, the result of Raman spectrum indicated near‐native conformation of P450st in DDAB film even on the PFC electrode, but no redox potential of P450st which has near native structure was observed. This study suggests the essential experimental conditions when working with heme protein‐DDAB films as, in some cases, heme iron from proteins is released on the surface of the electrode. 相似文献
15.
We developed a rapid, microscale and reliable analytical method for binding of drugs to plasma proteins using capillary electrophoresis (CE) with ionic cyclodextrins (CD) combined with frontal analysis. These CDs were used as pseudostationary phases of electrokinetic chromatography (EKC). The CD-modified EKC (CDEKC) approach allowed us to separate anionic drugs from plasma proteins, whereas CZE could not separate these drugs from plasma proteins because they had a similar mobility like plasma proteins. CDs uniquely interact with these drugs but not with plasma proteins. Therefore, CDEKC could be coupled with frontal analysis to measure the binding of anionic drugs to plasma proteins. The binding values obtained by CDEKC were highly consistent with those determined by the ultrafiltration method. Our CDEKC approach should expand the applicability of CE to protein binding analysis. 相似文献
16.
Practical asymmetric synthesis of (S)-MA20565, a wide-spectrum agricultural fungicide 总被引:1,自引:0,他引:1
Tanaka K Katsurada M Ohno F Shiga Y Oda M Miyagi M Takehara J Okano K 《The Journal of organic chemistry》2000,65(2):432-437
A practical asymmetric synthesis of a wide-spectrum agricultural fungicide, (S)-MA20565 (1), is described. The convergent synthesis was achieved starting from commercially available 3-(trifluoromethyl)aniline (7) in 44% overall yield through five steps and 2-bromobenzaldehyde (9) in 48% overall yield through four steps, respectively. (S)-O-[1-(3-Trifluoromethylphenyl)ethyl]hydroxylamine (2), a key intermediate of 1, was prepared via ruthenium(II)-catalyzed asymmetric transfer hydrogenation of 1-(3-trifluoromethylphenyl)ethanone (6) followed by chlorination using methanesulfonyl chloride and oxyamination using potassium acetohydroxamate with high level of stereocontrol. 相似文献
17.
Taxifolin 3-O-glucoside isomers, [(2R, 3R)-, (2R, 3S)-, (2S, 3R)- and (2S, 3S)-] were isolated from leaves of Chamaecyparis obtuse (Cupressaceae). Their structures were elucidated on the basis of UV, MS, CD, 1H- and 13C-NMR spectral data, including 2D shift correlation. It was found that the compounds could be distinguished by the use of 1H- and 13C-NMR spectral data. 相似文献
18.
SSG is an antitumor branched (1----3)-beta-D-glucan obtained from the culture filtrate of Sclerotinia sclerotiorum IFO 9395. Hydroxyethylation of SSG higher than MS 0.45 (MS value represents molar ratio of hydroxyethyl group vs. glucosyl group) by ethyleneoxide in aqueous sodium hydroxide lose the antitumor activity. Degradation of branching point of hydroxyethylated SSG (HE-SSG) by the sequential treatments of periodate oxidation, borohydride reduction, and mild acid hydrolysis of these derivatives regenerated the antitumor activity. These results directly demonstrated that the branching point covered, at least a part of, the dormant active site of SSG. 相似文献
19.
Toshinobu Higashimura Yoshitsugu Hirokawa Kei Matsuzaki Toshiyuki Uryu 《Journal of polymer science. Part A, Polymer chemistry》1980,18(5):1489-1498
Acetal additions to β-substituted vinyl ethers having a variety of substituents (alkenyl ethers) were stereochemically investigated as model reactions for their cationic polymerization. The reactions catalyzed by BF3O(C2H5)2 in CH2Cl2 at O°C gave 1:1 adducts, the steric structure of which was determined by means of 13C-NMR spectroscopy. trans-Alkenyl ethers always gave adducts with a single structure stereospecifically, indicating that the intermediate carbocation attacks a trans-alkenyl ether from a definite direction independent of the bulkiness of substituents. On the other hand, cis-alkenyl ethers formed adducts with two steric structures, and the direction of cation addition was found to depend on the bulkiness of the alkoxy group involved. The above trends were in agreement with the results for poly(alkenyl ether)s and allowed detailed discussion of the stereochemistry of the propagation processes in alkenyl ether polymerizations. 相似文献
20.
New results on the high resolution spectrum of ArI in the 3s-subshell excitation region are reported. The spectra are recorded in the second order of a 3-meter vacuum spectrograph and synchrotron radiation as the background source of continuum. The transitions: $$\begin{array}{*{20}c} {3s^2 3p^6 {}^1S_0 \to 3s({}^2S_{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} )3p^6 np} & {{}^1P_1 (4 \leqq n \leqq 25)} \\ \end{array} $$ have been extended to highern-values and more accurate level positions and binding energy of the 3s-subshell is achieved from the series limit. The spectrum has been analysed within the framework of non-relativistic Hartree-Fock and relativistic Hartree-Fock calculations. Intensity anomalies aroundn=9 have been atributed to an additional level arising from doubly excited state 3s 23p 44s4p. 相似文献