全文获取类型
收费全文 | 30191篇 |
免费 | 828篇 |
国内免费 | 228篇 |
专业分类
化学 | 20132篇 |
晶体学 | 126篇 |
力学 | 691篇 |
综合类 | 1篇 |
数学 | 5650篇 |
物理学 | 4647篇 |
出版年
2021年 | 278篇 |
2020年 | 355篇 |
2019年 | 322篇 |
2018年 | 300篇 |
2017年 | 325篇 |
2016年 | 638篇 |
2015年 | 659篇 |
2014年 | 699篇 |
2013年 | 1499篇 |
2012年 | 1464篇 |
2011年 | 1808篇 |
2010年 | 998篇 |
2009年 | 847篇 |
2008年 | 1583篇 |
2007年 | 1564篇 |
2006年 | 1656篇 |
2005年 | 1449篇 |
2004年 | 1391篇 |
2003年 | 1154篇 |
2002年 | 1096篇 |
2001年 | 489篇 |
2000年 | 453篇 |
1999年 | 423篇 |
1998年 | 403篇 |
1997年 | 447篇 |
1996年 | 411篇 |
1995年 | 388篇 |
1994年 | 413篇 |
1993年 | 367篇 |
1992年 | 340篇 |
1991年 | 314篇 |
1990年 | 280篇 |
1989年 | 300篇 |
1988年 | 269篇 |
1987年 | 230篇 |
1986年 | 270篇 |
1985年 | 392篇 |
1984年 | 399篇 |
1983年 | 335篇 |
1982年 | 372篇 |
1981年 | 331篇 |
1980年 | 361篇 |
1979年 | 292篇 |
1978年 | 332篇 |
1977年 | 299篇 |
1976年 | 252篇 |
1975年 | 217篇 |
1974年 | 213篇 |
1973年 | 179篇 |
1972年 | 134篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Colin Eaborn Peter B. Hitchcock Paul D. Lickiss 《Journal of organometallic chemistry》1981,221(1):13-17
The structure of the crowded molecule (Me3Si)3C(SiMe2Ph) has been determined by single crystal X-ray diffraction. The steric strain manifest itself mainly in lengthening of the Me3SiC and Me2PhSiC bonds (average length 1.920(6) ) and closing up of the CSiC angles within the Me3Si and Me2PhSi groups (average 105.2(10)°), with correspondingly large C(1)SiC angles (113.5(13)°; C(1) is the central carbon atom). 相似文献
992.
Wu X Ding S Ding Q Gray NS Schultz PG 《Journal of the American Chemical Society》2002,124(49):14520-14521
Purmorphamine, which is a 2,6,9-trisubstituted purine compound, was discovered through cell-based high-throughput screening from a heterocycle combinatorial library. It differentiates multipotent mesenchymal progenitor cells into an osteoblast lineage. It will serve as a unique chemical tool to study the molecular mechanisms of osteogenesis of stem cells and bone development. 相似文献
993.
M. Šícha J. Glosík J. Pavlík Z. Němeček J. Šafránková M. Tichý 《Czechoslovak Journal of Physics》1983,33(11):1226-1229
Conclusion In the present report an attempt has been made to use the second derivative method for measurements of the electron distribution function in flowing afterglow plasma. It has been shown that using the cross-correlation technique, this method seems to be a useful tool for flowing afterglow plasma investigation. 相似文献
994.
Microstructured cocultures of cardiac myocytes and fibroblasts: a two-dimensional in vitro model of cardiac tissue. 总被引:3,自引:0,他引:3
Cardiac myocytes and fibroblasts are essential elements of myocardial tissue structure and function. In vivo, myocytes constitute the majority of cardiac tissue volume, whereas fibroblasts dominate in numbers. In vitro, cardiac cell cultures are usually designed to exclude fibroblasts, which, because of their maintained proliferative potential, tend to overgrow the myocytes. Recent advances in microstructuring of cultures and cell growth on elastic membranes have greatly enhanced in vitro preservation of tissue properties and offer a novel platform technology for producing more in vivo-like models of myocardium. We used microfluidic techniques to grow two-dimensional structured cardiac tissue models, containing both myocytes and fibroblasts, and characterized cell morphology, distribution, and coupling using immunohistochemical techniques. In vitro findings were compared with in vivo ventricular cyto-architecture. Cardiac myocytes and fibroblasts, cultured on intersecting 30-microm-wide collagen tracks, acquire an in vivo-like phenotype. Their spatial arrangement closely resembles that observed in native tissue: Strands of highly aligned myocytes are surrounded by parallel threads of fibroblasts. In this in vitro system, fibroblasts form contacts with other fibroblasts and myocytes, which can support homogeneous and heterogeneous gap junctional coupling, as observed in vivo. We conclude that structured cocultures of cardiomyocytes and fibroblasts mimic in vivo ventricular tissue organization and provide a novel tool for in vitro research into cardiac electromechanical function. 相似文献
995.
Gehrhus B Hitchcock PB Parruci M 《Dalton transactions (Cambridge, England : 2003)》2005,(16):2720-2725
The thermally stable silylene Si[(NCH2But)2C6H4-1,2] 1 undergoes oxidative addition reactions with the lithium amides LiNRR'(R = SiMe3, R' = But; R = SiMe3, R' = C6H3Me2-2,6; R = R' = Me or R = R' = Pri) to afford the new lithium amides Li(THF)2[N(R)Si(SiMe3){(NCH2But)2C6H4-1,2}][R = But2 or R = C6H3Me2-2,6 (3a)] or the new tris(amino)functionalised silyllithiums Li(THF)x[Si{(NCH2But)2C6H4-1,2}NRR'][R = SiMe3, R' = C6H3Me2-2,6, x = 2 (3); R = R'= Me, x = 3 (4) or R = R' = Pri, x = 3 (5)]. Compounds 4 and 5 are stable at ambient temperature but compound 3 is thermally labile and converts into 3a upon heating. The pathway for the formation of 2 and 3 is discussed and the X-ray structures of 2-5 are presented. 相似文献
996.
Michels JJ O'Connell MJ Taylor PN Wilson JS Cacialli F Anderson HL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6167-6176
A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers. 相似文献
997.
H. Wetzel und S. Peter 《Fresenius' Journal of Analytical Chemistry》1962,190(1):208-212
Zusammenfassung Die Methode der Ringpapierchromatographie unter Anwendung von UV-Licht als einfachem Hilfsmittel zur Unterscheidung organischen Materials wurde hinsichtlich der Möglichkeit überprüft, zahlenmäßig greifbare Ergebnisse zu erhalten, die eine sichere Klassifizierung und Unterscheidung bituminöser Stoffe ermöglichen. Es wurde gefunden, daß für eine gute Reproduzierbarkeit der Ergebnisse die gleichmäßige Aufgabe der Lösung auf das Papier wesentlich ist. Ein äußerst gleichmäßiger Zufluß, der mit der Sauggeschwindigkeit des Papieres korrespondiert, konnte mit Hilfe eines Mikrodosiergerätes, das von einem Motor gleichmäßig angetrieben wurde, erzielt werden. Die erhaltenen Flächen für die verschiedenen Substanzgruppen stellen ein relatives, gut reproduzierbares Maß für die Zusammensetzung der untersuchten Proben dar.Herrn Prof. Dr. W. Fischer zum 60. Geburtstag gewidmet. 相似文献
998.
Some aspects of the transition probability P(, ) between states , on unital *-algebras are discussed. It is shown that P increases under the action of any stochastic linear map T, i.e., P(T, T)P(, ). Some properties of P are derived in starting from a recently-proved characterization of the quantity in question. 相似文献
999.
Milan Melník Peter Mikuš 《Phosphorus, sulfur, and silicon and the related elements》2020,195(5):367-370
AbstractIn this review, the structural data of monomeric platinum(II) complexes with inner coordination spheres of Pt(η2-P2L)(SiL)2, Pt(η2-P2L)(η2-Si2L) and Pt(η2-P,SiL)2 are classified and analyzed. These complexes crystallize in three crystal systems: monoclinic (8 examples), triclinic (4 examples) and orthorhombic (4 examples). Distorted square-planar environments about the Pt(II) atoms are built up by combination of homobi-P,P with two monodentate Si donor ligands; homobi-PP with homo-Si,Si donor ligands, or heterobi-P,Si donor ligands. The chelating ligands create metallacycles with the following angles: 65.0° (SiOSi) < 83.1° (SiC2Si) < 85.2° (PC2P) < 88.8° (SiSi2Si)). The mean Pt-P and Pt-Si bond distances in Pt(η2-P2L)·(SiL)2 complexes are 2.319 and 2.365?Å; in Pt(η2-P2L)(η2-Si2L) the values are 2.316 and 2.360?Å. The complex [Pt{η2-Me2P(C2B10H10)SiMe2}2] exists in two isomeric forms, a monoclinic cis- and a triclinic trans-isomer. The structural data are compared and discussed with the complexes of inner coordination spheres: Pt(η2-P2L)(XL)2 (X?=?O, N, CN, BL, Cl, SL, SeL, Br, or I) and Pt(η2-P2L)(η2-X2L) (X?=?OL, NL, SL or SeL). 相似文献
1000.
In the Claus process hydrogen sulfide reacts to elemental sulfur. Because the Claus reaction is thermodynamically limited, sulfur compounds are still present in Claus tailgas. To avoid air pollution, the tailgas has to be treated.Alfa- and gamma-alumina are being used either as a catalyst or as a support for an active component in the Claus process and some tailgas treatment processes. In order to elucidate the mechanism of the Claus reaction, the adsorption of sulfur dioxide on both of the above aluminas was investigated using Fourier transform infrared spectroscopy.Different adsorbed species displaying a different heat of adsorption were detected. A broad band near 3500 cm–1 is associated with the basic hydroxyl groups. This band is assigned to a hydrogen bond between the surface of alumina and a bisulfite species. As bisulfite species are reactive towards hydrogen sulfide, we assume that bisulfite species are active intermediates on alumina in the Claus reaction. 相似文献