全文获取类型
收费全文 | 530篇 |
免费 | 15篇 |
专业分类
化学 | 314篇 |
晶体学 | 16篇 |
力学 | 17篇 |
数学 | 48篇 |
物理学 | 150篇 |
出版年
2020年 | 6篇 |
2017年 | 7篇 |
2016年 | 11篇 |
2015年 | 10篇 |
2014年 | 7篇 |
2013年 | 20篇 |
2012年 | 19篇 |
2011年 | 17篇 |
2010年 | 8篇 |
2009年 | 12篇 |
2008年 | 16篇 |
2007年 | 16篇 |
2006年 | 14篇 |
2005年 | 14篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 7篇 |
1997年 | 11篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1990年 | 6篇 |
1989年 | 12篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 9篇 |
1985年 | 5篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1981年 | 12篇 |
1979年 | 9篇 |
1978年 | 10篇 |
1977年 | 6篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1972年 | 8篇 |
1971年 | 5篇 |
1967年 | 7篇 |
1939年 | 5篇 |
1938年 | 4篇 |
1933年 | 8篇 |
1932年 | 6篇 |
1930年 | 6篇 |
排序方式: 共有545条查询结果,搜索用时 343 毫秒
11.
12.
13.
A new version of the oxidoketone-alkynone fragmentation is described. Two steroidal α,β-oxido-oximes are shown to fragment to the corresponding alkynones when treated with hydroxylamine-O-sulfonic acid in alcaline solution at room temperature. 相似文献
14.
Lee KJ Mao S Sun C Gao C Blixt O Arrues S Hom LG Kaufmann GF Hoffman TZ Coyle AR Paulson J Felding-Habermann B Janda KD 《Journal of the American Chemical Society》2002,124(42):12439-12446
Overexpression of the cell-surface glycosphingolipid G(M3) is associated with a number of different cancers, including those of the skin, colon, breast, and lung. Antibodies against the G(M3) epitope have potential application as therapeutic agents in the treatment of these cancers. We describe the chemoenzymatic synthesis of two G(M3)-derived reagents and their use in the panning of a phage-displayed human single-chain Fv (scFv) antibody library derived from the blood of cancer patients. Three scFv-phage clones, GM3A6, GM3A8, and GM3A15, were selected for recombinant expression and were characterized using BIAcore and flow cytometry. BIAcore measurements using the purified, soluble scFvs yielded dissociation constants (K(d)) ranging from 4.2 x 10(-7) to 2.1 x 10(-5) M. Flow cytometry was used to evaluate the ability of each scFv to discriminate between normal human cells (human dermal fibroblast, HDFa), melanoma cells (HMV-1, M21, and C-8161), and breast cancer cells (BCM-1, BCM-2, and BMS). GM3A6 displayed cross-reactivity with normal cells, as well as tumor cells, and GM3A15 possessed little or no binding activity toward any of the cell lines tested. However, GM3A8 bound to five of the six tumor cell lines and showed no measurable reactivity against the HDFa cells. Hence, we have demonstrated that a synthetic G(M3) panning reagent can be used to isolate a fully human scFv that is highly specific for native G(M3) on the surface of tumor cells. The result is a significant step toward effective immunotherapies for the treatment of cancer. 相似文献
15.
D. S. Baranov N. Y. Chabrov V. A. Filipov A. A. Ivanilov P. V. Ivanov V. I. Konyushko V. M. Korablev V. A. Korotkov V. A. Krupnov V. V. Makeev A. G. Myagkov A. Yu. Polyarush A. A. Sokolov E. P. Kuznetsov H. -J. Grabosch H. H. Kaufmann U. Krecker R. Nahnhauer S. Nowak H. Vogt 《Zeitschrift fur Physik C Particles and Fields》1984,21(3):189-196
We present data on the multiplicity structure of inclusive charged hadron production in charged current neutrino and antineutrino freon interactions in the energy range 3–30 GeV resulting from an experiment with the bubble chamber SKAT. Average multiplicities, dispersions and correlation coefficients are investigated. Furthermore, KNO-scaling is studied and average net charges are calculated in different kinematical regions. Our data are compared with results from \(\begin{array}{*{20}c} {( - )} \\ v \\ \end{array} \) -interactions on an isoscalar target of “free” nucleons to study the influence of nuclear effects. 相似文献
16.
Bernd A Simon S Ramirez Bosca A Kippenberger S Diaz Alperi J Miquel J Villalba Garcia JF Pamies Mira D Kaufmann R 《Photochemistry and photobiology》1999,69(2):218-221
Extracts of Hypericum perforatum (St. John's wort) are used in the treatment of depression. They contain the plant pigment hypericin and hypericin derivates. These compounds have light-dependent activities. In order to estimate the potential risk of phototoxic skin damage during antidepressive therapy, we investigated the phototoxic activity of hypericin extract using cultures of human keratinocytes and compared it with the effect of the well-known phototoxic agent psoralen. The absorbance spectrum of our Hypericum extract revealed maxima in the whole UV range and in parts of the visible range. We cultivated human keratinocytes in the presence of different Hypericum concentrations and irradiated the cells with 150 mJ/cm2 UVB, 1 J/cm2 UVA or 3 h with a white light of photon flux density 2.6 mumol m-2 s-1. The determination of the bromodeoxyuridine incorporation rate showed a concentration- and light-dependent decrease in DNA synthesis with high hypericin concentrations (> or = 50 micrograms/mL) combined with UVA or visible light radiation. In the case of UVB irradiation a clear phototoxic cell reaction was not detected. We found phototoxic effects even with 10 ng/mL psoralen using UVA with the same study design as in the case of the Hypericum extract. These results confirm the phototoxic activity of Hypericum extract on human keratinocytes. However, the blood levels that are to be expected during antidepressive therapy are presumably too low to induce phototoxic skin reactions. 相似文献
17.
A recombinant mycobacterial heat shock protein of relative molecular mass 60,000 was purified by hydrophobic interaction chromatography. Chromatographic media with ligands of medium hydrophobicity, such as phenyl-Sepharose, bound too strongly to be used for the purification of this heat shock protein. Butyl-Sepharose, with weak hydrophobicity, allowed binding and elution with decreasing concentrations of ammonium sulphate, but only alkyl-Superose allowed the separation of two similar proteins from the Escherichia coli clone expressing the recombinant heat shock protein (relative molecular mass 60,000) of Mycobacterium bovis BCG. The binding parameters of recombinant human heat shock proteins of relative molecular mass 60,000 and 70,000 indicate that phenyl-Sepharose also binds too strongly for the separation of these two heat shock proteins. 相似文献
18.
The seeds of Stapelia gigantea are very rich in ester glycosides (ca. 5,9%). Mild acid hydrolysis gave a mixture of sugars which, after paper chromatography and electrophoresis, was found to be probably composed of cymarose, oleandrose, digitoxose, arabino-2,6-dideoxyhexose (= canarose) and pachybiose. The mixture of the raw genins gave after alkaline hydrolysis a mixture of about nine deacyl genins (C, D, E, F1, F2, F3, G, H, J); the acids split off during hydrolysis were not identified. The nine deacyl genins are probably closely related pregnane derivatives. The main component (E), C21H30O4, was obtained in crystalline state, and was named stapelogenin. Its probable structure is reported in the following publication. 相似文献
19.
B. Kaufmann S. Souverain S. Cherkaoui P. Christen J. -L. Veuthey 《Chromatographia》2002,56(3-4):137-141
Summary A rapid analytical method has been developed for the mutual resolution of three steroidal compounds, withaferin A, iochromolide,
and withacnistin. Liquid chromatography was performed on a Chromolith analytical column (4.6 mm i.d.×50 mm), made from a cylindrical
silica rod, operated at a flow rate of 4 mL min−1 with a simple linear gradient prepared from 0.1% aqueous formic acid and 0.1% formic acid in acetonitrile. Under optimum
conditions simultaneous separation of the compounds was achieved in less than 7 min, one eighth the time required for conventional
LC separation. The overall analysis time was reduced without sacrificing chromatographic performance—essential for the resolution
of positional isomers such as iochromolide and withacnistin. The column was coupled to a single-quadrupole mass spectrometer
and the method was characterized by good performance in terms of repeatability, selectivity, linearity, and sensitivity. Detection
limits in the single-ion-monitoring mode were 0.15 μg mL−1 or below. Finally, the developed method was successfully applied to the determination of withanolides in extracts fromlochroma gesnerioides obtained by three different processes—traditional Soxhlet extraction and two faster methods, microwave-assisted extraction
and pressurized solvent extraction. 相似文献
20.
Herbert Schumann Sebastian Dechert Frank Girgsdies Bernd Heymer Markus Hummert Ji‐Young Hyeon Jens Kaufmann Stefan Schutte Sonja Wernik Birgit C. Wassermann 《无机化学与普通化学杂志》2006,632(2):251-263
Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me2Al{μ‐O(CH2)3NMe2}]2 ( 1a ), Me2AlOC6H2(CH2NMe2)3‐2,4,6 ( 2a ), [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]2 ( 3a ) and [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NHCH2Ph}]2 ( 4 ) are formed by reacting equimolar amounts of AlMe3 and Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH2OH, or (S)‐PhCH2NHCH(i‐Pr)CH2OH, respectively. An excess of AlMe3 reacts with Me2N(CH2)2OH, Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH2OH producing the “pick‐a‐back” complexes [Me2AlO(CH2)2NMe2](AlMe3) ( 5 ), [Me2AlO(CH2)3NMe2](AlMe3) ( 1b ), [Me2AlOC6H2(CH2NMe2)3‐2,4,6](AlMe3)2 ( 2b ), and [(S)‐Me2AlOCH2CH(i‐Pr)NH‐i‐Pr](AlMe3) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 6 ) and [{CH2=C(CH3)}(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 8 ) are to obtain from Me2AlCl and Me2N(CH2)2OH and from [Cl2Al{μ‐O(CH2)2NMe2}]2 ( 7 ) and CH2=C(CH3)MgBr, respectively. The analogous dimethylgallium alkoxides [Me2Ga{μ‐O(CH2)3NMe2}]2 ( 9 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]n ( 10 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NHCH2Ph}]n ( 11 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)N(Me)CH2Ph}]n ( 12 ) and [(S)‐Me2Ga{μ‐OCH2(C4H7NHCH2Ph)}]n ( 13 ) result from the equimolar reactions of GaMe3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, 1H‐, 13C‐ and 27Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction. 相似文献