全文获取类型
收费全文 | 2994篇 |
免费 | 54篇 |
国内免费 | 5篇 |
专业分类
化学 | 2094篇 |
晶体学 | 20篇 |
力学 | 37篇 |
数学 | 612篇 |
物理学 | 290篇 |
出版年
2020年 | 22篇 |
2019年 | 25篇 |
2017年 | 22篇 |
2016年 | 63篇 |
2015年 | 40篇 |
2014年 | 53篇 |
2013年 | 123篇 |
2012年 | 98篇 |
2011年 | 102篇 |
2010年 | 73篇 |
2009年 | 73篇 |
2008年 | 118篇 |
2007年 | 91篇 |
2006年 | 105篇 |
2005年 | 82篇 |
2004年 | 95篇 |
2003年 | 68篇 |
2002年 | 68篇 |
2001年 | 44篇 |
2000年 | 37篇 |
1999年 | 65篇 |
1998年 | 45篇 |
1997年 | 42篇 |
1996年 | 51篇 |
1995年 | 41篇 |
1994年 | 43篇 |
1993年 | 43篇 |
1992年 | 39篇 |
1991年 | 46篇 |
1990年 | 49篇 |
1989年 | 50篇 |
1988年 | 57篇 |
1987年 | 53篇 |
1986年 | 43篇 |
1985年 | 60篇 |
1984年 | 68篇 |
1983年 | 59篇 |
1982年 | 72篇 |
1981年 | 58篇 |
1980年 | 53篇 |
1979年 | 49篇 |
1978年 | 60篇 |
1977年 | 51篇 |
1976年 | 42篇 |
1975年 | 53篇 |
1974年 | 40篇 |
1973年 | 25篇 |
1972年 | 34篇 |
1971年 | 28篇 |
1970年 | 30篇 |
排序方式: 共有3053条查询结果,搜索用时 15 毫秒
91.
Rolf C. Schulz 《Colloid and polymer science》1962,182(1-2):99-104
Zusammenfassung Durch Radikalketten-Polymerisation von Acrolein erhält man Polymere mit Aldehydgruppen. Diese sind zu vielfältigen Umsetzungen befähigt. In dieser Mitteilung werden nur zwei Arten von Reaktionen behandelt; nämlich die Reaktion der Aldehydgruppen untereinander, wobei unter Disproportionierung Polyhydroxypolycarbonsäuren entstehen. DieseCannizzaro-Reaktion tritt auch an der Oberfläche fester Polyacroleine ein. Eingehend behandelt wird die Umsetzung wäßriger Polyacrolein-Lösungen mit anderen Polymeren, welche Amino-, Hydroxyl-oder Mercaptangruppen enthalten. Die Kennzeichen der entstehenden Verbundpolymeren werden beschrieben und mit denWillstätterschen Symplexen verglichen. Auf Beziehungen dieser Reaktionen zu biochemischen Prozessen wird hingewiesen. Ferner wird die Diffusion von Polymeren durch Membranen mit reaktiven Gruppen (Agar-Agar und Gelatine) untersucht. In einigen Fällen tritt eine Oberflächen-Pfropfung ein.19. Mitt, üiber Polymere Acroleine, vorgetragen auf der 20. wissenschaftlichen Arbeitstagung der Kolloid-Gesellschaft vom 19. bis 20. 10. 1961 in Bad Oeynhausen; 18. Mitt, siehe Angew. Chem.72, 771 (1960).Fräulein Dr.Irmela Löflund und Herrn Dr.Mathias Marx, die an diesen Untersuchungen maßgebend beteiligt waren, möchte ich für ihre Mitarbeit herzlich danken. Herrn Prof. Dr.W. Kern, Direktor des Organisch-Chemischen Instituts, danke ich für mannigfache Förderung und anregende Diskussionen. Die Untersuchungen wurden durch Mittel des Fonds der Chemischen Industrie sowie der Firma Degussa, Frankfurt/Main, unterstützt, wofür ebenfalls herzlichst gedankt sei. 相似文献
92.
On the Mechanism of Sequential Radical Cyclization of (Bromomethyl)silyl Ethers of Terpernoid Alcohols The cyclic products of the Bu3SnH-promoted radical reaction of (E)-1-[(bromomethyl)dimethylsilyloxy]-2-methylhept-2-ene ( 6 ) consists to 98% of a 1:2 mixture of (±)-(4RS,5RS)- and (±)-(4-RS,5SR)-4-butyl-2,2,5-trimethyl-1-oxa-2-silacyclohexane ( 8a and 8b , respectively). It is, therefore, concluded that the 6-‘endo’→5-‘exo’ tandem cyclization of the 5-mehtyl-3-oxa-2-siladeca-5,9-dien-l-yl radical (reaction 1 → 2 ) is not necessarily a concerted process, but may be explained as a sequence of individual steps via free-radical intermediates. 相似文献
93.
Photoelectron Spectra and Molecular Properties. 133. Trifluoromethyldisulfane and Derivates F3CSSX (X?CF3, F, Cl, Br) The He(I) photoelectron spectra of trifluoromethyldisulfane F3CSSH and its derivatives F3CSSX (X?CF3, F, Cl, Br) are assigned by Koopmans correlations, IE = ?ε, with MNDO eigenvalues and by radical cation state comparison. Of special interest are the n/n splittings, which amount to 1.15 eV F3C? SS? F or 0.87 eV in F3? SS? Cl, and the dependance of which on the dihedral angle ω(XS? SX), on the SS bond length and on the acceptor effect of the F3C substituents is discussed. 相似文献
94.
The systematic integration of the small 2π- and 4π-electron systems cyclopropenylium ion, cyclopropenone, oxo-cyclobutenylium ion, and cyclobutadiene into phane chemistry was initiated only a few years ago. [n2]Cyclopropenylophanes, [n2]cyclopropenonophanes, metal-capped [n4]cyclobutadienosuperphanes, and other new families of double-decker phane species became available from cycloalkydiynes through special methods of double [2+1]cycloaddition with carbenes and metal complex induced dimerization by double [2+2]cycloaddition. Phane-specific structural features were elucidated by X-ray structural analyses. Cyclic voltammetry and PE spectroscopy as well as MO calculations reealed considerable interactions between closely spaced π-electron systems. Decapping cyclobutadienosuperphanes formally extended the synthetic principle to threefold [2+2]cycloadditions resulting in [n4]-bridged tricyclo-[4.2.0.03, 5]octa-3,7-dienes, which represent a new type of cage compounds. Moreover, completion to fourfold [2+2]addition was achieved with the photoinduced transformation of [34]bridged tricyclo[4.2.0.03, 5]octa-3,7-diene into propella[34]cubane. 相似文献
95.
Douglas A. Livingston Andreas Pfaltz Jakob Schreiber Albert Eschnmoser Dorothe Ankel-Fuchs Johanna Moll Rolf Jaenchen Rudolf K. Thauer 《Helvetica chimica acta》1984,67(1):334-351
Factor F430 from Methanogenic Bacteria: Structure of the Protein-free Factor Factor F430, the porphinoid nickel-containing coenzyme of the methylcoenzyme-M reductase of metanogenic bacteria is shown to be the 33,83,122,133,182-pentaacid derivative of the pentamethylester F430M, the structure of which had been determined previously (see structural formulae 1 and 2 ). The structure assignment rests on chromatographic, UV/VIS-, CD-, IR-, and 13C-NMR-spectroscopic as well as FAB-mass spectral comparision of F430 with F430M and the pentaacid prepared by acid-catalyzed hydrolysis of F430M. In the cells of Methanobacterium thermoautotrophicum, factor F430 is present in a ‘bound’ and also, depending on the growth conditions, in ‘free’ form, the latter being defined as the part of total F430 that can be extracted from the cells under extremely mild conditions (80% EtOH at 0–4°). From the (protein)-‘bound’ form, F430 is extracted by subsequently treating the cells at 0–4° with 80% EtOH containing (e.g.), 2m LiCi. From both sources, the extracted factor is the same pentaacid, and there is no indication for the existence of a protein-free F430 species that would contain additional (covalently bound) structural elements. 相似文献
96.
To avoid changes in the original As species distribution in natural water after sampling, a method of immediate separation
of As(V) by anion exchange at the sampling site was developed. The procedure consists of two steps. The total concentration
of arsenic is determined in one part of the water sample acidified on site. Another part of the water samples is pressed through
a column filled with an anion exchanger. The As(III) species that is not redox-stable remains in the effluent of the sorbents
column and can be analyzed with conventional methods after stabilization by addition of conc. HNO3. As(V) is sorbed by the exchanger material. The As(V) concentration can be calculated as the difference between Assol and As(III), neglecting very low contents of methylated species.
Oxidation of Fe(II) by air followed by co-precipitation of arsenic with iron hydroxide was applied in field experiments to
minimize the As concentration in seepage and mining water. 相似文献
97.
The universal voltammetric instrument, described in part I of this series, is used for comparative studies on the most important polarographic methods, direct current, derivative pulse, simple and phase-sensitive alternating current, double-tone, and harmonic-wave polarography. In general the peak-heights of these methods are influenced in the same measure by the composition of base electrolyte. In single cases characteristic differences are observed. 相似文献
98.
The reaction of tribromophosphine oxide in the superacidic systems XF/MF(5) (X = H, D; M = As, Sb) leads to tribromohydroxyphosphonium hexafluorometalates. The structure was successfully elucidated in the case of tribromohydroxyphosphonium hexafluoroarsenate. Br(3)POH(+)AsF(6)(-) crystallizes in the orthorhombic space group Pnma (No. 53 with a = 1292.5(1) pm, b = 871.6(1) pm, and c = 845.0(1) pm) with four formula units per cell. The Raman, IR, (1)H NMR, and (31)P NMR spectra of Br(3)POX(+)MF(6)(-) (X = H, D; M = As, Sb) are reported. 相似文献
99.
Rolf Huisgen 《Angewandte Chemie (International ed. in English)》1980,19(12):947-973
The principle of orbital control of pericyclic reactions has deepened our understanding of reaction phenomena and provided an excellent classification of these one-step processes. The electrocyclic reaction of the pentadienyl anion ? cyclopentenyl anion type is relatively unimportant in all-carbon systems and has not even been verified in the case of the parent compound. In the heterocyclic series, however, where up to five C-atoms of the pentadienyl anion are replaced by heteroatoms, a multitude of ring closures and ring openings find their ordering principle in the mentioned electrocyclic reaction. The replacement of the carbon atoms by heteroatoms can take place isoinically, i. e., with retention of the anionic character, or isoelectronically. An isoelectronic replacement of CR2 in position 1 by NR2 OR, and or CR in position 3 by NR or O leads to a charge-free resonance structure for the open-chain species; the migration of the charge during the electrocyclization results in a correlation with a cyclic zwitterion. Conversely, isoelectronic exchange of CR in position 2 by NR or O produces a conjugated 1,3-dipole, which cyclizes to a charge-free unsaturated five-membered ring. Twofold isoelectronic exchange allows the whole process to take place in a cation. Selected examples are to shed light on the classification and the thermodynamics of this electrocyclic reaction. 相似文献
100.
Rolf Holderegger Luigi M. Venanzi Fiorella Bachechi Pasquale Mura Luigi Zambonelli 《Helvetica chimica acta》1979,62(7):2159-2167
The preparation of the nucleophile trans-[RuCl(NO)( 1 )], where 1 is the bidentate ligand Ph2PCH2C18CH2PPh2, and of the five-coordinate species [RuCl(CO)(NO)( 1 )], [RuCl(CO)(NO)(Ph2PCH2Ph)2] and [RuCl(NO)( 2 )( 1 )] are reported. The crystal structure of [RuCl(CO)(NO)( 1 )] shows that the coordination around the metal atom is distorted trigonal bipyramidal with the phosphorus atoms in axial positions. The Ru? N? O bond angle is 142.8°. 1H- and 31P-NMR. and \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \nu $\end{document}NO IR.-data for the above complexes are reported and related to the coordination geometry. 相似文献