全文获取类型
收费全文 | 1276篇 |
免费 | 33篇 |
国内免费 | 15篇 |
专业分类
化学 | 989篇 |
晶体学 | 15篇 |
力学 | 7篇 |
数学 | 45篇 |
物理学 | 268篇 |
出版年
2022年 | 11篇 |
2020年 | 14篇 |
2019年 | 13篇 |
2018年 | 10篇 |
2017年 | 12篇 |
2016年 | 22篇 |
2015年 | 16篇 |
2014年 | 14篇 |
2013年 | 46篇 |
2012年 | 42篇 |
2011年 | 56篇 |
2010年 | 35篇 |
2009年 | 27篇 |
2008年 | 57篇 |
2007年 | 72篇 |
2006年 | 41篇 |
2005年 | 62篇 |
2004年 | 73篇 |
2003年 | 67篇 |
2002年 | 65篇 |
2001年 | 43篇 |
2000年 | 35篇 |
1999年 | 25篇 |
1998年 | 11篇 |
1997年 | 14篇 |
1996年 | 15篇 |
1995年 | 16篇 |
1994年 | 12篇 |
1993年 | 13篇 |
1992年 | 28篇 |
1991年 | 23篇 |
1990年 | 21篇 |
1989年 | 21篇 |
1988年 | 15篇 |
1987年 | 14篇 |
1986年 | 22篇 |
1985年 | 17篇 |
1984年 | 18篇 |
1983年 | 14篇 |
1982年 | 13篇 |
1981年 | 20篇 |
1980年 | 21篇 |
1979年 | 19篇 |
1978年 | 16篇 |
1977年 | 16篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1974年 | 12篇 |
1973年 | 11篇 |
1972年 | 9篇 |
排序方式: 共有1324条查询结果,搜索用时 31 毫秒
21.
The pinacol reaction of beta-halogenated alpha,beta-unsaturated aldehydes was promoted by titanium tetraiodide to give coupling products in good yields with high dl-selectivity. Subsequent reduction with H(2)/Pd-C gave saturated vic-diols in good yields. Heck coupling reaction enabled the displacement of halogens with vinyl groups without the loss of stereochemical integrities. [reaction: see text] 相似文献
22.
A catalytic photometric method with a flow-injection system is described for the determination of 9,10-phenanthrenequinone. It is based on the catalytic effect of 9,10-phenanthrenequinone on the redox reaction of 1,2-dinitrobenzene with formaldehyde under alkaline conditions. 9,10-Phenanthrenequinone at the 5.0 x 10(-8)-5.0 x 10(-6)M level can be determined at a rate of 20 samples/hr. The detection limit is 1.0 x 10(-8)M (40 pg in a 10-microl injection). 相似文献
23.
Liposomes prepared from synthetic amphiphiles. I. Their technetium labeling and stability 总被引:1,自引:0,他引:1
In order to apply liposomes prepared from synthetic amphiphiles containing amino acid residues to radiopharmaceuticals, their labeling with 99Tc or 99mTc and stability in saline or in serum were investigated. These liposomes were highly labeled by embedding stearylamine-diethylenetriamine pentaacetic acid as a ligand of technetium. The labeling was more efficient at pH 7.0 than at pH 4.0 or 8.5. Among these technetium-labeled liposomes tested, liposomes containing the alanine residue were stable in saline or in 50% serum at 37 degrees C for at least 24 h, in contrast to liposomes (phosphatidylcholine: cholesterol = 1:1 molar ratio) whose stability had been enhanced by adding cholesterol. 相似文献
24.
S. Tamai J. Kamada T. Ono T. Kuroki K. Goto A. Yamaguchi 《Journal of polymer science. Part A, Polymer chemistry》2002,40(3):423-428
Polyimide containing an indan unit and alkyl moiety with a high molecular weight was prepared from 5,7‐diamino‐1,1,4,6‐tetramethylindan and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride. This polyimide was amorphous and soluble in common organic solvents, such as tetrahydrofuran, chloroform, and cyclopentanone. Thermogravimetry of the polyimide showed good thermal stability, indicating that a 10% weight loss of the polyimide was observed at 500 °C in nitrogen. The glass‐transition temperature of the polyimide was not observed by DSC measurement between room temperature and 400 °C at a heating rate of 10 °C/min (Apparatus: DSC3100 MAC Science Co., Ltd.). Transparency of the polyimide at 365 nm was 80%. The polyimide acted as a photosensitive resist of negative type by UV radiation. The resist had a sensitivity of 31 mJ/cm2 and a contrast of 2.3 when it was developed with cyclopentanone at room temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 423–428, 2002 相似文献
25.
Ichinose H Michizoe J Maruyama T Kamiya N Goto M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(13):5564-5568
Enzyme-based electron-transfer reactions involved in the cytochrome P450 monooxygenase system were investigated in nanostructural reverse micelles. A bacterial flavoprotein, putidaredoxin reductase (PdR), was activated and shown to be capable of catalyzing the electron transport from NADH to electron-carrier proteins such as cytochrome b5 (tCyt-b5) and putidaredoxin (Pdx) in reverse micelles. Ferric tCyt-b5 in reverse micelles was effectively converted to its ferrous form by the exogenous addition of separately prepared reverse micellar solution harboring PdR and NADH. The fact that direct interactions of macromolecular proteins should be possible in the reverse micellar system encouraged us to functionalize a multicomponent monooxygenase system composed of the bacterial cytochrome P450cam (P450cam), putidaredoxin (Pdx), and PdR in reverse micelles. The successful camphor hydroxylation reaction catalyzed by P450cam was significantly dependent on the coexistence of Pdx, PdR, and NADH but not H2O2, suggesting that the oxygen-transfer reactions proceeded via a "monooxygenation" mechanism. This is the first report of a multicomponent cytochrome P450 system exhibiting enzymatic activity in organic media. 相似文献
26.
Y Kusumoto M Goto H Tajima K Nakata R Furukawa A Satoh K Kawahara N Ishii T Munehisa T Koji 《Radioisotopes》1984,33(10):686-690
To determine the diagnostic value of anti-HBc IgM in acute viral hepatitis or chronic liver disease B, Anti-HBc IgM was measured by a RIA and an ELISA in 32 patients with acute hepatitis (4 with type A, 15 with type B and 13 with type non A non B), 18 patients with chronic hepatitis and 19 patients with liver cirrhosis. In acute hepatitis B, anti-HBc IgM (both RIA and ELISA) was positive in 14(93%) of 15 patients and its cut-off index value was very high. However, anti-HBc IgM was always negative in one patient with typical course of type B. In 1 of 4 patients with acute hepatitis A and 2 of 13 with non A non B, anti-HBc IgM (RIA and/or ELISA) was positive. These 3 patients were positive for anti-HBs at the onset of disease, so we could not made the diagnosis of acute hepatitis B. Anti-HBc IgM was positive in 21(51%) of 37 patients with HBsAg-positive chronic liver disease by RIA and in 11 (30%) by ELISA, and its cut-off index value was relatively low. These results suggest that when adequate cut-off index value is established, anti-HBc analysis is useful for differentiating recent and current infections from remote infections. 相似文献
27.
Carmenza Duque Masuo Morisaki Nobuo Ikekawa Mikio Shikita 《Tetrahedron letters》1979,20(46):4479-4482
Cholesterol and 20-hydroxycholesterol labelled at C-22 stereospecifically by deuterium were incubated with the enzyme of bovine adrenocortical mitochondria. The results indicated that hydroxylation occurs with retention of the configuration of C-22 to give exclusively the 22R stereoisomers of 22-hydroxy- and/or 20,22-dihydroxycholesterol. 相似文献
28.
Ochiai M Suefuji T Miyamoto K Tada N Goto S Shiro M Sakamoto S Yamaguchi K 《Journal of the American Chemical Society》2003,125(3):769-773
Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10. 相似文献
29.
Goto S Masuda K Miura M Kanazawa K Sasaki M Masui M Shiramizu M Terada H Chuman H 《Chemical & pharmaceutical bulletin》2002,50(4):445-449
We measured the affinity of more than 20 sugars with concanavalin A (ConA) by an optical biosensor (surface plasmon resonance sensor) using asialofetuin (ASF) as an immobilized binding partner of ConA. We determined kinetic parameters of the effects of sugars on the dissociation of ConA from ASF quantitatively, and the structural requirements of the functional groups of sugars for binding with ConA. We found that the affinity of ConA for sugars is dependent on its conformation induced by interaction with the binding partner. In addition, the results showed that optical biosensor system is well mimics the interaction of ConA with sugars in biomembrane. 相似文献
30.
Solid sampling technique for direct detection of condensed tannins in bark by matrix-assisted laser desorption/ionization mass spectrometry 总被引:2,自引:0,他引:2
Ishida Y Kitagawa K Goto K Ohtani H 《Rapid communications in mass spectrometry : RCM》2005,19(5):706-710
A novel method for the direct analysis of condensed tannin components in bark was developed on the basis of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) combined with a simple solid sampling technique. The MALDI mass spectra obtained from the wood (bark) powder sample clearly showed a series of peaks corresponding to the sodium ion adducts of condensed tannin oligomers up to around m/z 3000. The results indicate that the condensed tannins in the bark sample used in this work mostly consist of combinations of flavan-3-ol units such as profisetinidin (PF), prorobinetinidin (PR) and prodelphinidin (PD), at least up to 10-mers (m/z approximately 3000). 相似文献