全文获取类型
收费全文 | 4079篇 |
免费 | 82篇 |
国内免费 | 16篇 |
专业分类
化学 | 2584篇 |
晶体学 | 38篇 |
力学 | 116篇 |
数学 | 885篇 |
物理学 | 554篇 |
出版年
2022年 | 44篇 |
2021年 | 71篇 |
2020年 | 57篇 |
2019年 | 60篇 |
2018年 | 33篇 |
2017年 | 25篇 |
2016年 | 99篇 |
2015年 | 93篇 |
2014年 | 79篇 |
2013年 | 174篇 |
2012年 | 172篇 |
2011年 | 180篇 |
2010年 | 120篇 |
2009年 | 106篇 |
2008年 | 190篇 |
2007年 | 152篇 |
2006年 | 142篇 |
2005年 | 137篇 |
2004年 | 118篇 |
2003年 | 77篇 |
2002年 | 106篇 |
2001年 | 43篇 |
2000年 | 60篇 |
1999年 | 65篇 |
1998年 | 49篇 |
1997年 | 47篇 |
1996年 | 49篇 |
1995年 | 46篇 |
1994年 | 34篇 |
1993年 | 38篇 |
1992年 | 51篇 |
1991年 | 29篇 |
1990年 | 34篇 |
1989年 | 33篇 |
1988年 | 46篇 |
1987年 | 53篇 |
1986年 | 40篇 |
1985年 | 64篇 |
1984年 | 48篇 |
1983年 | 39篇 |
1982年 | 44篇 |
1981年 | 46篇 |
1980年 | 46篇 |
1979年 | 41篇 |
1978年 | 28篇 |
1977年 | 50篇 |
1976年 | 34篇 |
1975年 | 26篇 |
1974年 | 21篇 |
1930年 | 21篇 |
排序方式: 共有4177条查询结果,搜索用时 0 毫秒
41.
Claudio Tavagnacco Gabriele Balducci Giacomo Costa Karl Tschler Wolfgang von Philipsborn 《Helvetica chimica acta》1990,73(5):1469-1480
In four series of strictly related organocobalt complexes, derived from cobaloximes by replacement of the O…H…O with O…-BF2…O and/or (CH2)3 groups, the trends of 59Co-NMR shielding and electrochemical data are discussed. A largely parallel behaviour of the plots of E1/2(I) values for the first Co(III)/Co(II) electron transfer vs. the 59Co chemical shifts reflects the similar sensitivity of the two parameters to a change in electron affinity of the central metal ion due to a variation of the organic group R. E1/2(II) values for the second Co(II)/CO(I) electron transfer are less sensitive to the change of R, but the trend of the plot vs. δ(59Co) is still parallel in the four series. Consistent deviations from a roughly linear dependence of E1/2(I) on pKa of the hydrocarbon acid corresponding to R, on Taft constant s?* and on 59Co shielding are noticed for the isopropyl derivatives and attributed to a steric effect. This was confirmed in a series of R? Co(DMG)pyridine complexes in which 59Co shielding decreases steadily with increasing steric parameter Es (Taft) of the alkyl group. There is experimental evidence from X-ray data that δ(59Co) decreases with an increase of the Co? C bond length, illustrating steric hindrance in alkyl coordination to be responsible for the decreased shielding of the 59Co nucleus. The relative displacements of the graphic displays for the different series reflect the effect of changes in electron affinity of the redox center, due to the equatorial ligand, which, in turn, is caused by variations in the electron-withdrawing power due to the introduction of the BF2 group and by the change from ?2 to ?1 valence of the (CH2)3-capped ligands. 相似文献
42.
Säurekatalysierte Umlagerungen von 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.02,7]oct-3-en-8endo-olen
Gabriele Mukherjee-Müller Paul Gilgen Janos Zsindely Hans Schmid 《Helvetica chimica acta》1977,60(5):1758-1780
Acid Catalysed Rearrangement of 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.02,7]oct-3-en-8endo-ols The tricyclic alcohols 2,3,4 and 6 (Scheme 1) are synthesized by the reaction of the tricyclic ketone 1 with sodiumborohydrid or metalloorganic reagents. Their configuration at C(8) is determined by NMR. in the presence of Eu(fod)3. The exo-attack of 1 by the nucleophil forming the endo-alcohol is favored, the π-electrons of C(3) = C(4) hindering the endo-attack. On treatment with sulfuric acid in dioxane/water at 25° the tertiary alcohols yield aryl-substituted ketones. 3 gives in 78.5% yield a mixture of the 3-(dimethylphenyl)-2-butanones 12 and 13 , in addition to 16.5% of (2,3,4-trimethylphenyl)-2-propanon ( 14 ) (Scheme 2). The alcohols 4 and 6 yield mixtures of the 2-(dimethylphenyl)-3-pentanones 19 and 20 (72%), and 2-(dimethylphenyl)-propiophenones 21 and 22 (68%), respectively (Scheme 2). In the case of the secondary alcohol 2 mainly products derived from hydration at the C(6), C(9) double bond are formed, namely the mixture of diols 23 and 24 (21%), and the mixture of the isomeric 2-(dimethylphenyl)propanals 25, 26 and 27 (3%) (Scheme 3). - The structures of 12–14, 19/20, 21/22, 23/24 and 25/26/27 were established by spectroscopic data. In the case of 12 and 13 the degradation of their mixture to the known 1-(dimethylphenyl)ethanols 17/18 confirmed the assignment. - The most probable mechanism for the rearrangement of 3 is shown in Schemes 4 and 5. The reaction proceeds from 3 through a, b and g to 12 and 13; 14 is formed via e, f and i . In the case of 4 and 6 only the reaction analogue to 3 → a → b → g ?12/13 takes place. The isomeric aldehyds 25–27 formed from 2 could have the structures s, t , and v . The former two could be generated in a similar way as 12/13 from 3 , the latter one as shown in Scheme 8. 相似文献
43.
Friedrich Bossert Horst Meyer Egbert Wehinger 《Angewandte Chemie (International ed. in English)》1981,20(9):762-769
The aryldihydropyridines first prepared by Hantzsch almost 100 years ago have recently been found to be highly effective calcium antagonists with suitable pharmacological profiles. An illustrative example is dimethyl-l,4-dihydro-2,6-dimethyl-4-(o-nitrophenyl)pyridine-3,5-dicarboxylate (Nifedipine) which is already employed therapeutically. This substance lowers the frequency of attack of angina pectoris and reduces blood pressure. The discovery of the therapeutic activity of this class of substances initiated renewed investigation of the Hantzsch condensation and the synthesis of numerous 4-aryldihydropyridines and related compounds. Qualitative and quantitative structure/activity relationships of these substances can be deduced from their biological data. 相似文献
44.
Hofmann C Boll R Heitmann B Hauser G Dürr C Frerich A Weitnauer G Glaser SJ Bechthold A 《Chemistry & biology》2005,12(10):1137-1143
The oligosaccharide antibiotic avilamycin A is composed of a polyketide-derived dichloroisoeverninic acid moiety attached to a heptasaccharide chain consisting of six hexoses and one unusual pentose moiety. We describe the generation of mutant strains of the avilamycin producer defective in different sugar biosynthetic genes. Inactivation of two genes (aviD and aviE2) resulted in the breakdown of the avilamycin biosynthesis. In contrast, avilamycin production was not influenced in an aviP mutant. Inactivation of aviGT4 resulted in a mutant that accumulated a novel avilamycin derivative lacking the terminal eurekanate residue. Finally, AviE2 was expressed in Escherichia coli and the gene product was characterized biochemically. AviE2 was shown to convert UDP-D-glucuronic acid to UDP-D-xylose, indicating that the pentose residue of avilamycin A is derived from D-glucose and not from D-ribose. Here we report a UDP-D-glucuronic acid decarboxylase in actinomycetes. 相似文献
45.
SYNTHESIS OF POSITIVELY CHARGED PHTHALOCYANINES and THEIR ACTIVITY IN THE PHOTODYNAMIC THERAPY OF CANCER CELLS 总被引:1,自引:0,他引:1
D. Wöhrle N. Iskander G. Graschew H. Sinn E. A. Friedrich W. Maier-Borst J. Stern P. Schlag 《Photochemistry and photobiology》1990,51(3):351-356
Positively charged zinc containing or metal free phthalocyanines 6a-c and 7a-c were prepared via a three step procedure starting from 4-nitrophthalonitrile. The phthalocyanines contain alkyl chains of different length in order to influence the hydrophilic vs lipophilic character of the compounds. The partition between a hydrophilic (water) and lipophilic (octanol-1) phase was determined, and the photoredox activities were investigated. Initial results on the photodynamic activity of these compounds were compared with those of Dougherty's Photofrin II on different malignant and non-malignant cell lines (XP 29MAmal, CX1, HeLa, S180 and NO17). Positively charged phthalocyanines in vitro showed a higher photodynamic activity than Photofrin II. 相似文献
46.
Theoretical and experimental study of the adsorption on radioactive gases on continuous flow columns
A bimolecular reaction model was used to describe the adsorption process in continuous flow columns filled with solid adsorbents. The analytical solution of the model for low gas concentrations and a cascade-type numerical method for higher gas concentrations were developed. An air flow apparatus using activated carbon as adsorbent and methyl-iodide labelled with125I as adsorbate was constructed for measuring breakthrough- and accumulation curves. 相似文献
47.
Zusammenfassung Das Nicotellin enthält wahrscheinlich nicht, wie die meisten anderen Tabakalkaloide, 2 N-Atome in der Molekel, sondern hat die Formel C15H11N3. Es werden gewichtige Gründe dafür beigebracht, es als 3,2;6,3-Terpyridyl (I) aufzufassen. Diese Hypothese wird durch Synthese des damit isomeren 3,2;4,3-Terpyridyls (V) und Vergleich der Infrarotspektren der beiden Terpyridyle mit denen von 4 bekannten Bipyridylen gestützt. Betrachtungen über eine mögliche Synthese des Nicotellins in der Pflanze führen zu Versuchen, diese Synthese in vitro nachzuahmen; diese Versuche geben aber eine andere Verbindung, wahrscheinlich das 1,5-Di--pyridyl-pentadien-(1,4)-on-(3).Herrn Prof. Dr.L. Ebert zum 60. Geburtstage in aufrichtiger Verehrung gewidment. 相似文献
48.
Azomethine ylide 3 , generated by thermolysis of 3,4-diphenyl-Δ1-1,2,3-triazoline-5,5-dimethyldicarboxylate 1 , can be trapped by isonitriles to give 3-imino-1,4-diphenylazetidine-2,2-dimethyldicarboxylates 5 . The IR, 1H-NMR, 13C-NMR and mass spectral data of the new compounds are discussed. 相似文献
49.
Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes 总被引:4,自引:0,他引:4
Bavykin DV Lapkin AA Plucinski PK Friedrich JM Walsh FC 《The journal of physical chemistry. B》2005,109(41):19422-19427
The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered. 相似文献
50.
Dimethyl 1′,1′-ureylenedi(1-ferrocenecarboxylate) (1) formed during the synthesis of 1-amino, 1′-ferrocenecarboxylic acid shows virtual molecular centrosymmetry. Electronic coupling between the two Fc groups through the ureylene bridge results in both Fc groups being individually oxidizable (ΔE1/2?0.14 V). The possible existence of intermolecular electronic communication has discussed. The oxidation was followed by spectroelectrochemistry. The separation between the two halfwave potentials ΔE1/2=137±5 mV and the comproportionation constant Kc=207. 相似文献