全文获取类型
收费全文 | 7803篇 |
免费 | 189篇 |
国内免费 | 17篇 |
专业分类
化学 | 5124篇 |
晶体学 | 97篇 |
力学 | 177篇 |
数学 | 1143篇 |
物理学 | 1468篇 |
出版年
2020年 | 82篇 |
2019年 | 65篇 |
2016年 | 130篇 |
2015年 | 134篇 |
2014年 | 129篇 |
2013年 | 277篇 |
2012年 | 252篇 |
2011年 | 344篇 |
2010年 | 206篇 |
2009年 | 210篇 |
2008年 | 260篇 |
2007年 | 251篇 |
2006年 | 288篇 |
2005年 | 253篇 |
2004年 | 278篇 |
2003年 | 221篇 |
2002年 | 215篇 |
2001年 | 141篇 |
2000年 | 157篇 |
1999年 | 122篇 |
1998年 | 98篇 |
1997年 | 112篇 |
1996年 | 128篇 |
1995年 | 116篇 |
1994年 | 111篇 |
1993年 | 115篇 |
1992年 | 124篇 |
1991年 | 97篇 |
1990年 | 90篇 |
1989年 | 100篇 |
1988年 | 112篇 |
1987年 | 96篇 |
1986年 | 110篇 |
1985年 | 107篇 |
1984年 | 111篇 |
1983年 | 109篇 |
1982年 | 98篇 |
1981年 | 140篇 |
1980年 | 125篇 |
1979年 | 123篇 |
1978年 | 146篇 |
1977年 | 103篇 |
1976年 | 115篇 |
1975年 | 82篇 |
1974年 | 84篇 |
1973年 | 96篇 |
1972年 | 61篇 |
1971年 | 61篇 |
1970年 | 60篇 |
1968年 | 50篇 |
排序方式: 共有8009条查询结果,搜索用时 828 毫秒
81.
Rongbiao?WangEmail author Herbert?Schmiedel Bernd-Reiner?Paulke 《Colloid and polymer science》2004,283(1):91-97
Isothermal titration calorimetry (ITC) measurements of the mixture of the cationic surfactant cetyl trimethyl ammonium bromide (CTAB) with negatively charged, hairy copolymer latices (poly-(2,3-epoxypropylmethacrylate-co-methacrylic acid) in different ratio) at high water excess indicate a monomer adsorption mechanism of CTAB by the polymer particles. The number of adsorbed CTAB molecules at saturation corresponds approximately to the number of negative elementary charges bound at the surface of the latices. The mixing enthalpy is the sum of demicellization and sorption enthalpies. At 25 °C for CTAB the demicellization enthalpy amounts to 10 kJ/mol, whereas the adsorption enthalpy varies from –7 kJ/mol (surface charge density of the latices
=–0.37 C/m2) to +3 kJ/mol (=–0.085 C/m2). The hydrodynamic radius
RH of the latex particles upon titration of cationic detergent and salt (NaBr) decreases by about 2 nm until the onset of aggregation near the isoelectric point. Titration of nonionic or anionic detergents has much less influence on the hydrodynamic radius and produces no measurable adsorption heat. The results are consistent within a model of latex particles with extended negatively charged polymer chains interacting predominantly via Coulombic forces with detergents. 相似文献
82.
S. Patzer N.L. Arthur P. Potzinger H.Gg. Wagner 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):2543-227
The photolysis of Me6Si2 at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me3SiH elimination with the concomitant formation of Me2SiCH2 with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10−3, which results in the formation of Me4Si and Me2Si. The main fate of the excited Me6Si2 molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me3Si and Me2SiCH2, are the same as those found in the photolysis of Me4Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33). 相似文献
83.
84.
85.
A. Mandelis W. Lo R. E. Wagner 《Applied Physics A: Materials Science & Processing》1987,43(2):123-130
The electrical and dielectric properties of mercuric iodide were studied at room temperature under various intensities and colours of light in the frequency range 1 Hz–10 kHz. In the high-frequency region (>40 Hz), the real part of the dielectric constant () is almost constant with frequency (f), colour and intensity of light. At lower frequencies, varies nearly as 1/f and monotonically increases with intensity (I) of the yellow (or green) light, whereas it is almost constant with red light intensity. This behaviour is discussed in the view of the different polarization contributions. The imaginary part of the dielectric constant () was found to vary as 1/f over the frequency range studied. This behaviour was observed whether the crystal was in dark or illuminated implying that the roomtemperature ac dark- or photo-conductivity () is independent of frequency. The observed variation of with intensity of yellow (or green) light was found to follow anI
1/2 dependence and a weaker dependence for the red light. the red light. The conductivity behaviour is discussed in the view of the current theories. 相似文献
86.
Wagner F Gruber O Lackner K Murmann HD Speth E Becker G Bosch HS Brocken H Cattanei G Dorst D Eberhagen A Elsner A Erckmann V Fussmann G Gehre O Gernhardt J Gierke Gv Glock E Grieger G Grigull P Haas G Hacker H Hartfuss HJ Jäckel H Jaenicke R Janeschitz G Junker J Karger F Kasparek W Keilhacker M Kick M Klüber O Kornherr M Kroiss H Kuehner M Lenoci M Lisitano G Maassberg M Mahn C Marlier S Mayer HM McCormick K Meisel D Mertens V Müller ER Müller Müller G Niedermeyer H Ohlendorf W 《Physical review letters》1986,56(20):2187-2190
87.
The tetraphosphides (tBu3Si)3P4M3 (M = Li, Na) and (tBu2PhSi)3P4Na3 have been synthesized in high yield from the reaction of 3 equivalents of the silanides tBu3SiM (M = Li, Na) and tBu2PhSiNa with P4 in benzene. (tBu3Si)3P4M3 (M = Li, Na) are transformed into the unsaturated triphosphides (tBu3Si)2P3M (M = Li, Na) and tBu3SiPM2 in tetrahydrofuran at ambient temperature. 相似文献
88.
For the assignment of the configuration at C(8) and C(15) of the natural oviposition-deterring pheromone 1 in Rhagoletis cerasi L., the four possible stereoisomers of 1 are synthesized. By condensing the C6 building blocks (5R)- 4 and (5S)- 4 with the boron enolates of the C10 building blocks (4S)- 13 and (4R)- 13 , followed by decarboxylative dehydration, all stereoisomers of 16 are available (Scheme 5). Glucosylation of 16 followed by formation of the taurin amide gives, after deprotection, the four stereoisomers (8R,15S)- 1 , (8R,15R)- 1 , (8R,15S) -1 , and (8S,15S)- 1 (Scheme 6). 相似文献
89.
Würthwein EU Lang G Schappele LH Mayr H 《Journal of the American Chemical Society》2002,124(15):4084-4092
A literature survey on the kinetics of hydride abstractions from CH-groups by carbocations reveals a general phenomenon: Variation of the hydride acceptor affects the rates of hydride transfer to a considerably greater extent than an equal change of the thermodynamic driving force caused by variation of the hydride donor. The origin of this relationship was investigated by quantum chemical calculations on various levels of ab initio and DFT theory for the transfer of an allylic hydrogen from 1-mono- and 1,1-disubstituted propenes (XYC=CH-CH(3)) to the 3-position of 1-mono- and 1,1-disubstituted allyl cations (XYC=CH-CH(2)(+)). The discussion is based on the results of the MP2/6-31+G(d,p)//RHF/6-31+G(d,p) calculations. Electron-releasing substituents X and Y in the hydride donors increase the exothermicity of the reaction, while electron-releasing substituents in the hydride acceptors decrease exothermicity. In line with Hammond's postulate, increasing exothermicity shifts the transition states on the reaction coordinate toward reactants, as revealed by the geometry parameters and the charge distribution in the activated complexes. Independent of the location of the transition state on the reaction coordinate, a value of 0.72 is found for Hammond-Leffler's alpha = deltaDeltaG/deltaDelta(r)G degrees when the hydride acceptor is varied, while alpha = 0.28 when the hydride donor is varied. The value of alpha thus cannot be related with the position of the transition state. Investigation of the degenerate reactions XYC=CH-CH(3) + XYC=CH-CH(2)(+) indicates that the migrating hydrogen carries a partial positive charge in the transition state and that the intrinsic barriers increase with increasing electron-releasing abilities of X and Y. Substituent variation in the donor thus influences reaction enthalpy and intrinsic barriers in the opposite sense, while substituent variation in the acceptor affects both terms in the same sense, in accord with the experimental findings. Marcus theory is employed to treat these effects quantitatively. 相似文献
90.
Arseniyadis S Subhash PV Valleix A Wagner A Mioskowski C 《Chemical communications (Cambridge, England)》2005,(26):3310-3312
The high-yielding synthesis and application of the first polymer supported reagent for the kinetic resolution (KR) of amines through enantioselective acetylation is described; this new supported chiral reagent allows the KR of primary amines with excellent selectivities at room temperature; moreover, this supported approach is highly efficient as the Merrifield-supported chiral scaffold can be quantitatively recovered and recycled. 相似文献