全文获取类型
收费全文 | 854篇 |
免费 | 13篇 |
专业分类
化学 | 525篇 |
晶体学 | 17篇 |
力学 | 36篇 |
数学 | 66篇 |
物理学 | 223篇 |
出版年
2021年 | 6篇 |
2020年 | 11篇 |
2019年 | 6篇 |
2016年 | 12篇 |
2015年 | 8篇 |
2014年 | 14篇 |
2013年 | 31篇 |
2012年 | 41篇 |
2011年 | 30篇 |
2010年 | 18篇 |
2009年 | 18篇 |
2008年 | 32篇 |
2007年 | 43篇 |
2006年 | 35篇 |
2005年 | 34篇 |
2004年 | 20篇 |
2003年 | 23篇 |
2002年 | 21篇 |
2001年 | 23篇 |
2000年 | 26篇 |
1999年 | 11篇 |
1998年 | 15篇 |
1997年 | 13篇 |
1996年 | 26篇 |
1995年 | 30篇 |
1994年 | 19篇 |
1993年 | 19篇 |
1992年 | 16篇 |
1991年 | 8篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 6篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 10篇 |
1980年 | 12篇 |
1978年 | 16篇 |
1977年 | 16篇 |
1976年 | 9篇 |
1975年 | 8篇 |
1974年 | 6篇 |
1973年 | 7篇 |
1972年 | 10篇 |
1970年 | 10篇 |
1957年 | 4篇 |
1935年 | 4篇 |
排序方式: 共有867条查询结果,搜索用时 31 毫秒
131.
Alaerts L Maes M Jacobs PA Denayer JF De Vos DE 《Physical chemistry chemical physics : PCCP》2008,10(20):2979-2985
The capacity and selectivity of the metal-organic framework MIL-47 for liquid phase adsorption are shown to heavily depend on the pretreatment of the material, as illustrated in detail by the particular case of selective xylene adsorption. By totally removing the uncoordinated terephthalic acid from the pores and simultaneously avoiding oxidation to nonporous V(2)O(5), pore volume and uptake of xylenes can be maximized. The presence of uncoordinated terephthalic acid in the pores improves the selectivity between p- and m-xylene. Calcination bed thickness and oven geometry influence the optimal calcination procedure. The physicochemical modifications of MIL-47 during its activation are investigated in detail with XRD, SEM, nitrogen physisorption, TGA and diffuse reflectance UV-Vis spectroscopy. Using optimally pretreated MIL-47 as adsorbent for xylene, ethyltoluene, dichlorobenzene, toluidine or cresol isomers, the para-isomer is in each case preferred over the meta-isomer in pulse chromatographic and batch experiments. The role of stacking in the selective adsorption of these isomers is discussed. In the case of the dichlorobenzenes, the meta- and para-isomers can be separated in a breakthrough experiment with a selectivity of 5.0. 相似文献
132.
Abstraction of hydrogen atoms by pthalimide-N-oxyl radicals is an important step in the N-hydroxyphthalimide catalyzed autoxidation of hydrocarbons. In this contribution, the temperature dependency of this reaction is evaluated by a detailed transition state theory based kinetic analysis for the case of toluene. Tunneling was found to play a very important role, enhancing the rate constant by a factor of 20 at room temperature. As a result, tunneling, in combination with the existence of two distinct rotamers of the transition state, causes a pronounced temperature dependency of the pre-exponential frequency factor, and, as a consequence, marked curvature of the Arrhenius plot. This explains why earlier experimental studies over a limited temperature range around 300 K found formal Arrhenius activation energies and pre-factors that are 4 kcal mol(-1) and three orders of magnitude smaller than the actual energy barrier and the corresponding frequency factor, respectively. Also as a consequence of tunneling, substitution of a deuterium atom for a hydrogen atom causes a large decrease in the rate constant, in agreement with the measured kinetic isotope effects. The present theoretical analysis, complementary to the experimental rate coefficient data, allows for a reliable prediction of the rate coefficient at higher temperatures, relevant for actual autoxidation processes. 相似文献
133.
Jan Jacobs 《Tetrahedron》2008,64(22):4985-4992
The synthesis of N-substituted 1,2-dihydrobenz[g]isoquinoline-5,10-diones was envisaged as part of our research on structural modifications of pentalongin, the active principle of Pentas longiflora Oliv. Therefore, a synthesis of the 2-aza analogues of this natural pyranonaphthoquinone with an acid-mediated intramolecular cyclization of different N-protected 2-(((2,2-dimethoxyethyl)amino)methyl)-1,4-naphthoquinones in the key step was conducted. The synthesized 1,2-dihydrobenz[g]isoquinoline-5,10-diones represent a new class of compounds, which has been undescribed in organic chemistry. 相似文献
134.
Ghidu VP Wang J Wu B Liu Q Jacobs A Marnett LJ Sulikowski GA 《The Journal of organic chemistry》2008,73(13):4949-4955
Apoptolidins A-D are microbial secondary metabolites shown to be selectively cytotoxic against several cancer cell lines and noncytotoxic against normal cells. Total syntheses of apoptolidinones A and D are reported. The efficient synthetic strategy leading to the apoptolidinones features construction of the common 20-membered macrolactone by an intramolecular Suzuki reaction and stereocontrolled aldol reactions establishing the C19/C20 and C22/C23 stereocenters. In contrast to apoptolidin A, the aglycones apoptolidinone A and D were shown to be noncytotoxic when evaluated against human lung cancer cells (H292). 相似文献
135.
Finsy V Verelst H Alaerts L De Vos D Jacobs PA Baron GV Denayer JF 《Journal of the American Chemical Society》2008,130(22):7110-7118
Vapor-phase adsorption and separation of the C8 alkylaromatic components p-xylene, m-xylene, o-xylene, and ethylbenzene on the metal-organic framework MIL-47 have been studied. Low coverage Henry adsorption constants and adsorption enthalpies were determined using the pulse chromatographic technique at temperatures between 230 and 290 degrees C. The four C8 alkylaromatic components have comparable Henry constants and adsorption enthalpies. Adsorption isotherms of the pure components were determined using the gravimetric technique at 70, 110, and 150 degrees C. The adsorption capacity and steepness of the isotherms differs among the components and are strongly temperature dependent. Breakthrough experiments with several binary mixtures were performed at 70-150 degrees C and varying total hydrocarbon pressure from 0.0004 to 0.05 bar. Separation of the different isomers could be achieved. In general, it was found that the adsorption selectivity increases with increasing partial pressure or degree of pore filling. The separation at a high degree of pore filling in the vapor phase is a result of differences in packing modes of the C8 alkylaromatic components in the pores of MIL-47. 相似文献
136.
Sczepanski JT Jacobs AC Greenberg MM 《Journal of the American Chemical Society》2008,130(30):9646-9647
The C4'-oxidized abasic site (C4-AP) is produced in DNA as a result of oxidative stress. A recent report suggests that this lesion forms interstrand cross-links. Using duplexes in which C4-AP is produced from a synthetic precursor, we show that the lesion produces interstrand cross-links in which both strands are in tact and cross-links in which the C4-AP containing strand is cleaved. The yields of these products are dependent upon the surrounding nucleotide sequence. When C4-AP is opposed by dA, cross-link formation occurs exclusively with an adjacent dA on the 5'-side. Moreover, formation of the lower molecular weight cross-link is promoted by an opposing adenine. When the opposing dA is replaced by dT, the activity of the adenine can be rescued by adding the free base. This is a rare example in which DNA promotes its own modification, an observation that is all the more important because of the biological significance of the product produced. 相似文献
137.
Ok KM Sung J Hu G Jacobs RM O'Hare D 《Journal of the American Chemical Society》2008,130(12):3762-3763
A new neutral 1D channel thorium organic framework material (TOF-2) has been synthesized under hydrothermal conditions. TOF-2 exhibits a hexagonal channel structure consisting of eight-coordinate ThO6F2 polyhedra and 1,3,5-benzentricarboxylate ligands. The channels run along the c-axis and are approximately 13 A in diameter. The single-crystal X-ray structure suggests that the amount of void space is 41%. The structure is stable to ca. 400 degrees C. Gas adsorption measurements show deferential gas uptake behavior. 相似文献
138.
A first-principles analysis reveals that the catalytic efficiency of nitroxyl radicals in alkane oxidations is not simply correlated with their reactivity toward the substrate. 相似文献
139.
Bretting H Buck F Jacobs G Meinke S Scheppokat AM Thiem J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(25):7144-7152
Snails from the family Helicidae produce in their albumen glands a highly branched galactan, which consists almost exclusively of D- and L-galactose. The D-Gal residues are glycosydically beta(1-->6)- or beta(1-->3)-linked, whereas the L-Gal moieties are attached alpha(1-->2). Up until the present time, two beta(1-->6)-D-galactosyl transferases and one alpha(1-->2)-L-galactosyl transferase have been identified in a membrane preparation of these glands. These were used to synthesise various oligosaccharides by successive addition of the NDP-activated (NDP=nucleoside-5'-diphosphate) D-Gal or L-Fuc moieties, up to a heptasaccharide by starting from the disaccharide D-Gal-beta(1-->3)-D-Gal-beta(1-->OMe. Even larger oligosaccharides up to a tridecasaccharide were obtained by starting with the hexasaccharide D-Gal-[beta(1-->3)-D-Gal]4-beta(1-->4)-D-Glc as an acceptor substrate. This tandem exploitation process has high potential for the easy introduction of D-Gal and L-Fuc residues into a great variety of oligosaccharides, which can be used in ligand/acceptor studies. 相似文献
140.
The heat capacity of the liquid-liquid mixture nitrobenzene-dodecane has been measured for the first time near its upper critical consolute point using an adiabatic calorimeter. The theoretical expression for the heat capacity near the critical point was applied to our combined data runs. The critical exponent alpha was determined to be 0.124+/-0.006, which was consistent with theoretical predictions. When alpha was fixed at its theoretical value of 0.11, our value for the amplitude ratio A(+)A(-)=0.58+/-0.02 was consistent with experimental determinations and theoretical predictions. However, the two-scale-factor universality ratio X, now consistent among experiments and theories with a value between 0.019 and 0.020, was violated in this system when using a previously published value for the correlation length. 相似文献