全文获取类型
收费全文 | 627篇 |
免费 | 23篇 |
国内免费 | 3篇 |
专业分类
化学 | 305篇 |
晶体学 | 2篇 |
力学 | 14篇 |
数学 | 162篇 |
物理学 | 170篇 |
出版年
2021年 | 5篇 |
2020年 | 9篇 |
2019年 | 6篇 |
2018年 | 7篇 |
2016年 | 10篇 |
2015年 | 11篇 |
2014年 | 14篇 |
2013年 | 32篇 |
2012年 | 18篇 |
2011年 | 24篇 |
2010年 | 16篇 |
2009年 | 16篇 |
2008年 | 14篇 |
2007年 | 23篇 |
2006年 | 25篇 |
2005年 | 9篇 |
2004年 | 17篇 |
2003年 | 12篇 |
2002年 | 14篇 |
2001年 | 8篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1989年 | 6篇 |
1988年 | 11篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1982年 | 5篇 |
1979年 | 7篇 |
1978年 | 6篇 |
1977年 | 9篇 |
1973年 | 5篇 |
1959年 | 5篇 |
1932年 | 12篇 |
1931年 | 6篇 |
1930年 | 5篇 |
1928年 | 9篇 |
1927年 | 6篇 |
1926年 | 5篇 |
1901年 | 6篇 |
1900年 | 5篇 |
1895年 | 4篇 |
1893年 | 14篇 |
1892年 | 4篇 |
排序方式: 共有653条查询结果,搜索用时 15 毫秒
21.
22.
Leopold Horner Gerhard Doms 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):259-265
Abstract Thioäther, Sulfoxide, Sulfone, organische Selenide und Telluride (R – Y – R': R, R', = Alkyl, Aryl, Y=S, SO, SO2, Se, Te) werden an der Grenzfläche von Raney-Nickel hydrogenolysiert. Als Spaltprodukte entstehen die Verbindungen RH und R'H sowie eine Grenzflächenverbindung (Raney-Nickel-Y) (Y=S, Se, Te; S auch aus Sulfoxiden und Sulfonen. Letztere entbinden ebenfalls mit Mineralsäuren YH2). Die Größe und ‘Struktur’ der Oberfläche des Raney-Nickels entscheidet über die Hydrogenolysekapazität. Bei einer technischen Raney-Nickel-Probe liegt bei Diphenylsulfid die Sättigungsausbeute an Benzol bei 1,1 mmol/g Raney-Nickel. Die Sättigungskapazität hängt ab von der Struktur von R bzw. R' und dem Heteroatom Y. (Auch Benzylether können–wenn auch langsamer als Thioether–zu Toluol aufgespalten werden). Auf Grund bekannter Daten werden Vorstellungen entwickelt, die ein Bild über den topochemischen Verlauf der Hydrogenolyse von R–Y–R' vermitteln sollen. Vergiftetes Raney-Nickel ist im Gegensatz zum aktivierten Raney-Nickel nicht mehr oder nur stark vermindert zur Isomerisierung, Disproportionierung und zum H-D-Austausch befähigt. Bei diesen Prozessen spielt offenbar der im Nickel strukturgebundene Wasserstoff eine wichtige Rolle. Some thioethers, sulphoxides, sulphones, organoselenium and tellurium compounds (R–Y–R' R, R'= Alkyl, Aryl, Y?S, SO, SO2, Se, Te) have been reductively cleaved on the surface of Raney-nickel. The products comprise RH and R'H, and a surface bound material (Raney-nickel-Y) (Y?S, also from sulphoxides and sulphones, Se, Te. The latter may be released as YH2 on treatment with mineral acids). The area and ‘structure’ of the surface determines the hydrogenolysis capacity of the catalyst. For technical quality Raney-nickel, the limiting yield of benzene from diphenylsulphide is 1.1 mmol/g. The limiting yield is dependent on the structure of R and R' and also the nature of Y. (Benzyl ethers may also be reduced to toluene, if somewhat slower than the corresponding thioether). Proposal for the processes possibly involved at the surface during hydrogenolysis of R–Y–R' are put forward in the basis of consideration of the available experimental data. Poisoned Raney-nickel (in contrast to the activated catalyst) is practically inactive as agent for isomerization, disproportionation, or H–D exchange, and hence surface bound hydrogen clearly plays an important role in these processes. 相似文献
23.
24.
Nicoleta E. Mircescu Haibo Zhou Nicolae Leopold Vasile Chiş Natalia P. Ivleva Reinhard Niessner Andreas Wieser Christoph Haisch 《Analytical and bioanalytical chemistry》2014,406(13):3051-3058
Based on molecular-specific surface-enhanced Raman scattering (SERS) spectroscopy we were able to discriminate between rough and smooth strains of Escherichia coli and Proteus mirabilis bacteria. For this purpose, bacteria have been immobilized through electrostatic forces by inducing a positive charge on the glass slide. This way, SERS spectra on bacterial biomass and also on single bacteria could be recorded in less than 2 h, by using concentrated silver nanoparticles as SERS-active substrate. Single-bacterium SERS spectral fingerprints showed to be sensitive to the presence of the O-antigen at strain level and to the microorganisms growth phase. By using principal component analysis (PCA) on the SERS spectra recorded from E. coli and P. mirabilis, these two uropathogens could be fairly discriminated. 相似文献
25.
Jannik Brückmann Dr. Carolin Müller Tamar Maisuradze Dr. Alexander K. Mengele Dr. Djawed Nauroozi Sven Fauth Andreas Gruber Prof. Dr. Stefanie Gräfe Prof. Dr. Kerstin Leopold Dr. Stephan Kupfer Prof. Dr. Benjamin Dietzek-Ivanšić Prof. Dr. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202200766
The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)3]2+ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD+ to NADH was achieved, highlighting the potential of this system for photocatalytic applications. 相似文献
26.
Superior laryngeal nerve paresis and paralysis 总被引:1,自引:0,他引:1
Gürsel Dursun Robert Thayer Sataloff Joseph R. Spiegel Steven Mandel Reinhardt J. Heuer Deborah Caputo Rosen 《Journal of voice》1996,10(2):206-211
Superior laryngeal nerve paresis and paralysis are relatively common but often difficult to diagnose with certainty. They are most commonly caused by viral infections, though other etiologies must be considered. A thorough history and physical examination, including strobovideolaryngoscopy and laryngeal electromyography, are needed for definitive diagnosis. It is essential to establish the diagnosis accurately to differentiate an apparent superior laryngeal nerve paresis from other conditions, such as myasthenia gravis. Laryngeal electromyography is used to confirm clinical impressions, as a guide for therapy, and as one measure of recovery. In our experience, accurate and early diagnosis assure the best phonatory outcome by directing therapy that will prevent or eliminate compensatory vocal abuses, which may themselves lead to even more serious vocal injury. 相似文献
27.
We investigate the settling of heavy particles in a steady, two-dimensional random velocity field, and find instances in which particle suspension occurs. This leads to a bimodal velocity distribution that may explain some apparently conflicting results reported in the literature. The bimodal distribution is typically smeared out by a time dependence of the ambient flow but, if the time variation is slow, the settling rates of some particles will be as well. The resulting broadbanded velocity distribution of the settling particles will have significance for processes such as rain drop formation, in which the spread of particle velocities affects the statistics of particle collisions. 相似文献
28.
It is demonstrated that in high quality hydrogenated amorphous silicon films nearly 40% of the contained hydrogen is in the form of hydrogen molecules individually trapped in the amorphous equivalent of tetragonal T sites. The majority of these molecular hydrogens are in the less-clustered component of the contained hydrogen. These results could have major implications for the understanding of light-induced defects and hydrogen mobility. 相似文献
29.
Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 °C in N2-5% H2 gas atmospheres with different dew points −80 and −40 °C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point −80 °C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point −40 °C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal. 相似文献
30.
Leopold M. Simons 《Hyperfine Interactions》1999,119(1-4):281-290
Crystal spectroscopy of the X-rays of exotic atoms started with a series of experiments using transmission spectrometers.
Experiments at lower energies were made possible by the development of reflection spectroscopy. The progress made is illustrated
with a measurement of the pion mass and the determination of strong interaction effects in pionic hydrogen isotopes. Modern
developments aim at a determination of the strong interaction width on the level of %. The way to reach this goal is presented
and the limits of the method and possible future experiments are discussed.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献