全文获取类型
收费全文 | 3820篇 |
免费 | 137篇 |
国内免费 | 18篇 |
专业分类
化学 | 2875篇 |
晶体学 | 15篇 |
力学 | 58篇 |
数学 | 620篇 |
物理学 | 407篇 |
出版年
2023年 | 21篇 |
2022年 | 21篇 |
2021年 | 44篇 |
2020年 | 61篇 |
2019年 | 53篇 |
2018年 | 33篇 |
2017年 | 27篇 |
2016年 | 109篇 |
2015年 | 97篇 |
2014年 | 93篇 |
2013年 | 175篇 |
2012年 | 156篇 |
2011年 | 185篇 |
2010年 | 130篇 |
2009年 | 117篇 |
2008年 | 183篇 |
2007年 | 196篇 |
2006年 | 173篇 |
2005年 | 167篇 |
2004年 | 177篇 |
2003年 | 129篇 |
2002年 | 132篇 |
2001年 | 75篇 |
2000年 | 58篇 |
1999年 | 64篇 |
1998年 | 68篇 |
1997年 | 63篇 |
1996年 | 69篇 |
1995年 | 60篇 |
1994年 | 64篇 |
1993年 | 54篇 |
1992年 | 49篇 |
1991年 | 38篇 |
1990年 | 27篇 |
1989年 | 66篇 |
1988年 | 57篇 |
1987年 | 64篇 |
1986年 | 43篇 |
1985年 | 42篇 |
1984年 | 54篇 |
1983年 | 43篇 |
1982年 | 57篇 |
1981年 | 49篇 |
1980年 | 50篇 |
1979年 | 40篇 |
1978年 | 27篇 |
1977年 | 38篇 |
1976年 | 22篇 |
1975年 | 30篇 |
1973年 | 25篇 |
排序方式: 共有3975条查询结果,搜索用时 15 毫秒
101.
Rudolf Schmid Marco Cereghetti Bernd Heiser Peter Schnholzer Hans-Jürgen Hansen 《Helvetica chimica acta》1988,71(4):897-929
The axially dissymmetric diphosphines (?)-(R)- and (+)-(S)-(6-6′-dimethylbiphenyl-2,2′-diyl)bis(diphenyl-phosphine) ((?)-(R)- 10 and (+)-(S)- 10 ; ‘BIPHEMP’) have been synthesized, starting from (R)- and (S)-6,6′-dimethylbiphenyl-2,2′-diamine ((R)- and(S)- 16 ), respectively, via Sandmeyer reaction, liathiation, and phosphinylation. Moreover, racemic 4,4′- dimethyl- and 4,4′-bis(dimethylamino)-substituted analogues 11 and 12 respectively, and the 6,6′-bridged analogues 1,11-bis(diphenylphosphino)-5,7-dihydrodibenz[c,e]oxepin (13) were synthesized and resolved into optically pure (R)- and(S)-enantiomers via complexation with di-μ-chlorob is {(R)-2-[1-(dimethylamino)ethyl]pheny-C? N}dipalladium(II) ((R)- 18 ). The molecular structures of the diphosphines (S)- 10 and (R)- 13 and of two derived cationic Rh(I) complexes,[Rh((S)- 10 )(nbd)]BF4 and [Rh((R)- 13 )(nbd)]BF 4 were determined by x-ray analyses. Absolute configurations were established for (+)-(S)- 10 by X-ray analyses of both the free diphosphine and of the derived Rh(I) complex, and for (?)-(R)- 13 by X-ray analysis of the derived Rh(I) complex. Configurational assignments for the substituted BIPHEMP analogues 11 12 were achieved by means of 1H-NMR comparisons. The BIPHEMP ligand 10 and analogues 11 , 12 and 13 are the first examples of optically active bis(triaylphosphines) containing the axially dissymmetric biphenyl moiety. All these new diphosphines proved to be excellent asymmetry-inducing ligands in Rh(I)-catalyzed isomerizations of N,N-diethylnerylamine affording citronellat enamine of 98-99% ee. 相似文献
102.
We show, for any operatorT from aC(K)-space into a Banach space with rank (T)≤n, the inequality
, whereC≤4.671 is a numerical constant. The factor (1+logn)1−1/p
is asymptotically correct. This inequality extends a result of Jameson top ≠ 2. Several applications are given — one is a positive solution of a conjecture of Rosenthal and Szarek: For 1≤p<q<2,
相似文献
103.
Bernd A. Kniehl 《Zeitschrift fur Physik C Particles and Fields》1992,55(4):605-618
The \(ZHf\bar f\) four-point function is calculated in the one-loop approximation of the Standard Model and full analytic results are presented. The loop contributions due to both light and new heavy fermions are inspected in detail. The dominant mechanisms of Higgs-boson production from fermions are compared. The effect of radiative corrections on the cross section of \(f\bar f \to ZH\) including bremsstrahlung is studied. The spectrum of hard bremsstrahlung is integrated analytically. The implications for Higgs-boson searches at futuree + e ? colliders in the energy range 200 \(200GeV \le \sqrt s \le 1.5TeV\) , which includes both LEP 2 and the Next Linear Collider, are analyzed. ForM H <2m t weak corrections in the modified on-mass-shell scheme are generally negative and feebly vary withM H , while forM H >2m t , they strongly increase withM H and may take large positive values. Electromagnetic corrections dramatically reduce the cross section close to theZH-production threshold, while they may considerably enhance it far above this threshold. 相似文献
104.
Bernd S. W. Schröder 《Order》1992,9(4):311-319
The following theorem is proved: If Q=L{P
t
tT} is a finite lexicographic sum of posets such that T and all P
t
have the strong fixed point property then Q has the strong fixed point property. Moreover we show the strong fixed point property for two more classes of posets. 相似文献
105.
106.
Kocher N Henn J Gostevskii B Kost D Kalikhman I Engels B Stalke D 《Journal of the American Chemical Society》2004,126(17):5563-5568
The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment. 相似文献
107.
Oliver Mechnich Gerhard Messier Horst Kessler Michael Bernd Bernhard Kutscher 《Helvetica chimica acta》1997,80(5):1338-1354
The conformational analysis of naturally occurring cytostatic cyclic heptapeptides axinastatin 2, 3, and 4 was carried out by two-dimensional NMR spectroscopy in combination with distance-geometry (DG) and molecular-dynamics (MD) calculations in explicit solvents. The synthesized secondary metabolites were examined in (D6)DMSO. Axinastatin 2 was also investigated in CD3OH. In all structures, Pro2 is in the i + 1 position of a βI turn and Pro6 occupies the i + 2 position of a βVIa turn about the cis amide bond between residue 5 and Pro6. In all peptides, a bifurcated H-bond occurs between residue 4 CO and the amide protons of residue 1 and 7. For axinastatin 2 and 3, an Asn Ig turn was found about Asn1 and Pro2. We compared these structures with conformations of cyclic heptapeptides obtained by X-ray and NMR studies. A β-bulge motif with two β turns and one bifurcated H-bond is found as the dominating backbone conformation of cyclic all-L-heptapeptides. Axinastatin 2, 3, and 4 can be characterized by six trans and one cis amide bond resulting in a β/βVI(a)-turn motif, a conformation found for many cyclic heptapeptides. Detailed biological tests of the synthetic compounds in different human cancer cell lines indicates these axinastatins to be inactive or of low activity. 相似文献
108.
Stíbr B Holub J Bakardjiev M Pavlík I Tok OL Císarová I Wrackmeyer B Herberhold M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2239-2244
The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed. 相似文献
109.
N‐Silylaminotitanium trichlorides, Me3S(R)N‐TiCl3 ( 18 ) [R = tBu ( a ), SiMe3 ( b ), 9‐borabicyclo[3.3.1]nonyl (9‐BBN)( c )], and (CH2SiMe2)2N‐TiCl3 ( 18d ) were obtained in high yield and high purity from the reaction of the respective bis(silylamino)plumbylene with an excess of titanium tetrachloride. The crystal structure of 18a was determined by X‐ray analysis. The reactions of the analogous stannylenes with an excess of TiCl4 did not lead to 18 . N‐Lithio‐trimethylsilyl[9‐(9‐borabicyclo[3.3.1]nonyl)]amine ( 8 ) was prepared, structurally characterized and used for the synthesis of a new bis(amino)stannylene 10 and a plumbylene 11 . The compounds 18a—d served as ideal starting materials for the synthesis of bis(silylamino)titanium dichlorides, where the silylamino groups can be identical ( 19 ) or different ( 20 ). This was achieved either by the reaction of 18 again with bis(amino)plumbylenes or with lithium N‐silylamides. In contrast to the direct synthesis starting from titanium tetrachloride and two equivalents of the respective lithium amide, which in general affords 19 with identical amino groups only in low yield, the procedure starting from 18 is much more versatile and gave the pure compounds 19 or 20 in almost quantitative yield. Further treatment of the dichlorides 19 or 20 with lithium amides led to tris(amino)titanium chlorides 21 . The dichlorides 19 or 20 reacted with two equivalents of alkynyllithium reagents to give the first well characterized examples of di(alkyn‐1‐yl)bis(N‐silylamino)titanium compounds 22 — 27 . These compounds reacted with trialkylboranes (triethyl or tripropylborane) by 1, 1‐organoboration. In some cases, the extremely reactive reaction products could be identified as novel 1, 1‐bis(silylamino)titana‐2, 4‐cyclopentadienes 28 — 31 bearing a dialkylboryl group in 3‐position. In solution, the proposed structures of all products were deduced from a consistent set of data derived from multinuclear magnetic resonance spectroscopy (1H, 11B, 13C, 14N, 15N, 29Si, 35Cl NMR). 相似文献
110.
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