全文获取类型
收费全文 | 808篇 |
免费 | 28篇 |
国内免费 | 9篇 |
专业分类
化学 | 670篇 |
晶体学 | 9篇 |
力学 | 7篇 |
数学 | 66篇 |
物理学 | 93篇 |
出版年
2023年 | 5篇 |
2021年 | 13篇 |
2020年 | 17篇 |
2019年 | 17篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 22篇 |
2015年 | 10篇 |
2014年 | 14篇 |
2013年 | 38篇 |
2012年 | 47篇 |
2011年 | 56篇 |
2010年 | 37篇 |
2009年 | 27篇 |
2008年 | 52篇 |
2007年 | 47篇 |
2006年 | 41篇 |
2005年 | 57篇 |
2004年 | 44篇 |
2003年 | 43篇 |
2002年 | 23篇 |
2001年 | 6篇 |
2000年 | 15篇 |
1999年 | 9篇 |
1998年 | 10篇 |
1997年 | 11篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 8篇 |
1993年 | 10篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 11篇 |
1983年 | 4篇 |
1982年 | 13篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1975年 | 4篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1962年 | 3篇 |
排序方式: 共有845条查询结果,搜索用时 0 毫秒
771.
Nohta H Sonoda J Yoshida H Satozono H Ishida J Yamaguchi M 《Journal of chromatography. A》2003,1010(1):37-44
A highly sensitive and selective fluorimetric determination method for dicarboxylic acids (C5-C12) has been developed. This method is based on an intramolecular excimer-forming fluorescence derivatization with a pyrene reagent, 4-(1-pyrene)butyric acid hydrazide (PBH), followed by reversed-phase liquid chromatography (LC). The carboxylic acids were converted to the corresponding dipyrene-labeled derivatives by reaction with PBH in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The derivatives afforded intramolecular excimer fluorescence (450-550 nm) which can clearly be discriminated from the normal fluorescence (370-420 nm) emitted from PBH and monopyrene-labeled derivatives of monocarboxylic acids. The structures of the derivatives and the emission of excimer fluorescence were studied by LC with mass spectrometry and with spectrofluorimetry, respectively. The PBH derivatives of the carboxylic acids could be separated by reversed-phase LC on an ODS column with isocratic elution. The detection limits (signal-to-noise ratio = 3) were 1.3 fmol to undetectable for a 20-microl injection. 相似文献
772.
773.
Yoshihiro Mimaki Hiroshi Harada Chiseko Sakuma Mitsue Haraguchi Satoru Yui Tomoya Kudo Masatoshi Yamazaki Yutaka Sashida 《Helvetica chimica acta》2004,87(4):851-865
Seven new bisdesmosidic triterpene saponins, with up to eight monosaccharides, which were given the trivial names contortisiliosides A–G ( 1 – 7 ), were isolated from Enterolobium contortisiliquum. The structures of the new saponins were determined on the basis of extensive spectroscopic and chromatographic analyses of both intact and acid‐hydrolyzed compounds. The isolated saponins were evaluated for their cytotoxic activities against BAC1.2F5 mouse macrophages, EL‐4 mouse lymphoma cells, and L‐929 mouse fibroblasts. Whereas contortisiliosides A ( 1 ) and C ( 3 ) were moderately cytotoxic to both BAC1.2F5 macrophages and EL‐4 cells, and contortisiliosides D–G ( 4 – 7 ) did not show any apparent cytotoxic activities against the three cell lines, contortisilioside B ( 2 ) exhibited selective cytotoxic activity against BAC1.2F5 mouse macrophages, with an IC50 value of 3.4 μM . The macrophage death caused by 2 was shown to be neither necrotic nor apoptosis‐inducing based on the unique morphological change of the killed cells, whose cytosols were transformed into large vacuoles, and according to the TUNEL assay. 相似文献
774.
We investigated electron transport kinetics in terms of electron diffusion coefficient (D) and electron lifetime (tau) in coumarin-dye-sensitized nanocrystalline TiO2 electrodes by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). We found that the values of tau for coumarin-dye-sensitized TiO2 electrodes were much shorter than that for an electrode coated with a Ru complex (N719 dye), suggesting that the back-electron-transfer process corresponding to recombination between conduction-band electrons in the TiO2 and I3- ions in the electrolyte occurs more easily in coumarin-dye-sensitized solar cells. In addition, the values of tau depended on the kind of coumarin dye, each of which has a different number of thiophene moieties, suggesting that the molecular structure of the adsorbed dyes also affects the kinetics of electron transport in the TiO2 electrodes. 相似文献
775.
Terada E Okamoto T Kozaki M Masaki ME Shiomi D Sato K Takui T Okada K 《The Journal of organic chemistry》2005,70(24):10073-10081
[structures: see text] 5,5'-(m-Phenylene)bis[(10-aryl-5,10-dihydrophenazine) dications, 3a2+ and 3b2+, and their p-analogues 4a2+ and 4b2+, were prepared, and their exchange interaction was investigated. The EPR spectra of these dications at 123 K in a butyronitrile matrix showed the population of a triplet state. The temperature dependence of the EPR signal intensity (absolute value(delta m(s)) = 2) showed that these dications had singlet ground states with deltaE(ST)/k(B) = -27 to -21 K for the m-isomer 3(2+) and with deltaE(ST)/k(B) = -10 to -8 K for the p-isomer 4(2+). Theoretical calculation of the exchange interaction J for these dications at the orthogonal torsion angle geometries was carried out for 3a2+ and 4a2+ and for (m- and p-phenylene)bisphenothiazine dications 1(2+) and 2(2+) using the broken-symmetry approach for the singlet states. A good correlation was observed between the calculated J and a MO-energy term in the triplet state, deltaE(TMO) = absolute value(HOMO(alpha) - (HOMO - 1)(alpha)). The calculated J values were negative in the order of 10 K for the m-dications (J/k(B) = -14.7 K for 1(2+), -11.5 K for 3a(2+)), but much smaller negative values were found for the p-isomers (J/k(B) = -0.9 K for 2(2+), -0.8 K for 4a2+). The smaller absolute value(J) values for the p-dications are qualitatively consistent with the experimental deltaE(ST) (2J) values. 相似文献
776.
Shunsaku Shiotani Hiroyuki Morita Masatoshi Inoue Toshimasa Ishida Mitsunobu Doi Yasuko In 《Journal of heterocyclic chemistry》1986,23(1):233-240
Reaction of 5-methyl-4,5,6,7-tetrahydrofuro[3,2-c]- ( 1 ) and 6-methyl-4,5,6,7-tetrahydrofuro[2,3-c]pyridine ( 2 ) with hydrochloric acid gave novel dimerized compounds 3a-d and 4a-d , respectively. The structures of 3a, 3b, 4a and 4b were determined by spectroscopic method, and 3c, 3d, 4c and 4d by single crystal X-ray analysis. The reaction courses for the formation of these compounds are proposed. 相似文献
777.
Luminol-type chemiluminescence derivatization reagents for liquid chromatography and capillary electrophoresis 总被引:3,自引:0,他引:3
The present paper provides the principles for chemiluminescence of luminol-type compounds and their wide and powerful application to the detection system in liquid chromatography and capillary electrophoresis as derivatization reagents. The reagents can be classified into two types, chemiluminescence labeling and chemiluminogenic reagents. The former reagents are highly chemiluminescent themselves and used for tagging their intense chemiluminophores to analytes, whereas the latter are weakly chemiluminescent but generate intense chemiluminescence by reaction with analytes. The liquid chromatographic methods utilizing chemiluminescence derivatizing reactions with luminol-type reagents allow the analytes to be detected at pmol–sub-fmol levels. Furthermore, the chemiluminogenic reactions show high selectivity owing to their selective reaction against the analytes permitting facile and reproducible detection. 相似文献
778.
Analysis of mitochondrial membrane potential in the cells by microchip flow cytometry 总被引:3,自引:0,他引:3
The mitochondrial membrane potential (DeltaPsi(m)) is an important indicator of the energetic state of both the mitochondria and the cells. To develop a sensitive, convenient, and rapid method for the measurement of DeltaPsi(m), we carried out cell fluorescence assays using the Agilent 2100 bioanalyzer system which, unlike the conventional flow cytometry, is based on microfluidic technology employing fluorescence detection with a 3,3'-dihexyloxacarbocyanine iodide (DiOC(6)(3)) fluorescent probe. The use of DiOC(6)(3) in the fluorometer was shown to be feasible for monitoring variations in DeltaPsi(m) in the mitochondria isolated from rat liver and treated with rotenone, succinate, ADP, and carbonylcyanide-p-trifluoromethoxyphenylhydrazone (FCCP). Flow cytometry analysis showed severe reduction of fluorescence intensity in Jurkat cells after treatment with 1.0 and 10 microM FCCP. However, fluorescence microscopy demonstrated obvious accumulation of fluorescence in the mitochondria and induction of diffuse cytoplasmic fluorescence not localized to the mitochondria in these cells. The dose response range of DiOC(6)(3) in the Agilent 2100 bioanalyzer system for yielding sufficient fluorescence intensity in the mitochondria of the cells was 20 nm-2.0 microM. Furthermore, significant reduction of fluorescence intensity in the cells stained with 2.0 microM DiOC(6)(3) was observed after treatment with 10 microM FCCP for 30 min. These results indicate that the Agilent 2100 bioanalyzer is potentially useful for monitoring DeltaPsi(m) in cell assays. 相似文献
779.
Kawano S Takahashi M Hine T Yamamoto E Asakawa N 《Rapid communications in mass spectrometry : RCM》2005,19(19):2827-2832
A novel methylcellulose-immobilized restricted access media column with strong cation-exchange groups on an internal surface (MC-SCX) was evaluated for the direct injection analysis of basic polar drugs in plasma by column-switching liquid chromatography/mass spectrometry (LC/MS). Analytical conditions, including an automated pretreatment step and MS detection, were optimized for a series of basic drugs (doxepin, desipramine, imipramine, nortriptyline, amitriptyline, clomipramine). On-line pretreatment with the MC-SCX column followed by fast gradient analysis using a C18 column resulted in a total analysis cycle time of 7 min for each spiked plasma sample. More than 150 plasma samples spiked with target compounds were measured without compromising MS detection (relative standard deviations less than 11% for all compounds, and regression coefficients greater than 0.99). 相似文献
780.
Masatoshi Fujii Eizaburo Kamei 《Proceedings of the American Mathematical Society》1996,124(9):2751-2756
Very recently, Furuta obtained the grand Furuta inequality which is a parameteric formula interpolating the Furuta inequality and the Ando-Hiai inequality as follows : If and is invertible, then for each ,
is a decreasing function of both and for all and . In this note, we employ a mean theoretic approach to the grand Furuta inequality. Consequently we propose a basic inequality, by which we present a simple proof of the grand Furuta inequality.