全文获取类型
收费全文 | 10970篇 |
免费 | 477篇 |
国内免费 | 88篇 |
专业分类
化学 | 7136篇 |
晶体学 | 93篇 |
力学 | 267篇 |
综合类 | 1篇 |
数学 | 1740篇 |
物理学 | 1640篇 |
无线电 | 658篇 |
出版年
2023年 | 92篇 |
2022年 | 122篇 |
2021年 | 213篇 |
2020年 | 223篇 |
2019年 | 267篇 |
2018年 | 178篇 |
2017年 | 174篇 |
2016年 | 411篇 |
2015年 | 306篇 |
2014年 | 344篇 |
2013年 | 639篇 |
2012年 | 656篇 |
2011年 | 685篇 |
2010年 | 479篇 |
2009年 | 429篇 |
2008年 | 629篇 |
2007年 | 651篇 |
2006年 | 523篇 |
2005年 | 575篇 |
2004年 | 464篇 |
2003年 | 371篇 |
2002年 | 358篇 |
2001年 | 176篇 |
2000年 | 164篇 |
1999年 | 103篇 |
1998年 | 110篇 |
1997年 | 118篇 |
1996年 | 120篇 |
1995年 | 103篇 |
1994年 | 91篇 |
1993年 | 112篇 |
1992年 | 79篇 |
1991年 | 87篇 |
1990年 | 77篇 |
1989年 | 66篇 |
1988年 | 52篇 |
1987年 | 59篇 |
1986年 | 72篇 |
1985年 | 104篇 |
1984年 | 102篇 |
1983年 | 82篇 |
1982年 | 69篇 |
1981年 | 74篇 |
1980年 | 68篇 |
1979年 | 67篇 |
1978年 | 68篇 |
1977年 | 42篇 |
1976年 | 40篇 |
1975年 | 53篇 |
1974年 | 55篇 |
排序方式: 共有10000条查询结果,搜索用时 17 毫秒
141.
Horváth-Szabó G Czarnecki J Masliyah JH 《Journal of colloid and interface science》2002,253(2):427-434
Equilibrium liquid crystal (LC) layer on an interface between crude oils and water was observed at high pH. This layer is composed mainly of sodium naphthenates produced in situ at the water/oil interface. Transient LC layer was also evolved at the interface of aqueous phase of sodium hydroxide solutions and oleic phase of naphthenic acid (NA) solutions as result of a chemical reaction between NaOH and NA. This chemical reaction causes transport process resulting in a disturbance of the interface. Optical observation of this interface disturbance reviled that the interface covered with LC shows considerably lower flexibility as compared to LC free interface. The LC layer eventually dissolves in the water phase at low oil-to-water ratio, while at high oil-to-water ratio it can form an equilibrium phase, which spreads spontaneously at the oil-water interface. 相似文献
142.
Diastereopure monofluorinated cyclopropanoid nucleosides were synthesized for biological studies. As key intermediates cis- and trans-(+/-)-[1-fluoro-2-(acetoxymethyl)cyclopropyl]methanol were prepared starting from diastereopure fluorinated cyclopropanecarboxylates. The latter were synthesized by copper(i)-catalyzed cyclopropanation of [small alpha]-fluorostyrene with ethyl diazoacetate. After reduction and O-acetylation the diastereomeric (2-fluoro-2-phenylcyclopropyl)methyl acetates were obtained. Oxidative degradation using RuO(4) and reduction of the formed carboxyl group with borane gave the fluorinated alcohols, which were coupled with different nucleobases. After deprotection, the corresponding cyclopropanoid nucleosides of adenine, cytosine, guanine, thymine and uracil were obtained. Antiviral tests revealed for the cis-configured guanosine a low, but specific activity against HSV-1 and HSV-2. In addition low affinities of the adenine derivatives to adenosine receptors were detected. 相似文献
143.
Piotr Michorczyk Piotr Kutrowski Lucjan Chmielarz Jan Ogonowski 《Reaction Kinetics and Catalysis Letters》2004,82(1):121-130
Different Fe-containing catalysts (pure Fe2O3, Fe2O3 supported on active carbon or g-Al2O3, and hydrotalcite derived Mg-Fe oxides) were examined in the dehydrogenation of propane performed in an Ar or CO2 atmosphere at 873 K. A promoting effect of carbon dioxide was found for the Fe2O3 and Fe2O3/AC samples. The catalytic results are discussed in terms of redox properties of the catalysts determined by temperature-programmed
reduction (TPR).
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
144.
Berezkin Victor G. Mardanov Robert G. Moiseew Aleksey A. Malinowska Irena Różyło Jan K. 《平面色谱法杂志一现代薄层色谱法》2002,15(5):377-379
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
145.
Studies on the photooxidation mechanism of polymers. I. Photolysis and photooxidation of polystyrene
A new mechanism has been proposed for the photooxidation of polystyrene as film and in benzene. The initial stage of the photooxidative degradation may involve reactions of singlet oxygen with polystyrene molecules. Singlet oxygen may be formed in the reaction between excited benzene ring in polystyrene molecule and molecular oxygen. The addition of singlet oxygen quenchers such as 1,3-cyclohexadiene or β-carotene reduces the rate of polymer degradation in benzene solution. The mechanisms of the photolysis of polystyrene as film and in benzene solution, in vacuo and in the presence of oxygen, are discussed and interpretations proposed. The pronounced yellowing of polystyrene during the photooxidation process is interpreted as a reaction involving benzene ring-opening photooxidation in polystyrene molecule. These results were obtained by comparing ultraviolet and infrared spectra in experiments of photooxidation of pure liquid benzene and polystyrene film. 相似文献
146.
Summary The calculation of vibrational states using a gradient extremal path is discussed. Gradient extremal paths are defined by local criteria, which lead to stable solutions. This has certain advantages in comparison with a steepest-descent path, which is often difficult to determine accurately. For cases where a reaction path formalism is applicable, a path based on the gradient extremal concept gives results in close agreement with those obtained using traditional steepest-descent methods. We present algorithms for carrying out such calculations and also give some numerical results. 相似文献
147.
148.
Crich D Mataka J Zakharov LN Rheingold AL Wink DJ 《Journal of the American Chemical Society》2002,124(21):6028-6036
A series of four S-allyl D-thiopyranosides, alpha- and beta-manno and xylo, were oxidized with MCPBA at low temperature to give seven of the eight possible sulfoxides, whose configuration at sulfur was determined either directly by X-ray crystallography or by correlation with closely related structures. For the axial thioglycosides oxidation leads very predominantly to the (R)(S)-diastereomer in the xylo series and exclusively so in the manno series; the configuration at C2 is of little importance in determining the stereoselectivity of oxidation of axial thioglycopyranosides. In the equatorial series the configuration at C2 has a significant effect on the outcome of the reaction as, although both series favored the (S)(S)-sulfoxide, selectivity was significantly higher in the case of the beta-mannoside than of the beta-xyloside. The two alpha-xylo sulfoxides have different conformations of the pyranoside ring with the (R)(S)-isomer adopting the (1)C(4) chair and the (S)(S)-diastereomer the (4)C(1). Each pair of diastereomeric sulfoxides was thermally equilibrated in C(6)D(6) and in CD(3)OD. In the mannose series the kinetic isomers are also thermodynamically preferred. In the xylose series, on the other hand, the nature of the thermodynamic isomer in both the alpha- and beta-anomers is a function of solvent with a switch observed on going from C(6)D(6) to CD(3)OD. The results are rationalized in terms of the exo-anomeric effect, steric shielding provided by H3 and H5 in the axial series, the interaction of the C2-O2 and sulfoxide dipoles, and increased steric interactions on hydrogen bonding of the sulfoxides to CD(3)OD. 相似文献
149.
Mona Wells Michael Gösch Hauke Harms Jan Roelof van der Meer 《Mikrochimica acta》2005,151(3-4):209-216
This paper describes the development of an analytical technique for arsenic analyses that is based on genetically-modified
bioreporter bacteria bearing a gene encoding for the production of a green fluorescent protein (gfp). Upon exposure to arsenic
(in the aqueous form of arsenite), the bioreporter production of the fluorescent reporter molecule is monitored spectroscopically.
We compared the response measured as a function of time and concentration by steady-state fluorimetry (SSF) to that measured
by epi-fluorescent microscopy (EFM). SSF is a bulk technique; as such it inherently yields less information, whereas EFM monitors
the response of many individual cells simultaneously and data can be processed in terms of population averages or subpopulations.
For the bioreporter strain used here, as well as for the literature we cite, the two techniques exhibit similar performance
characteristics. The results presented here show that the EFM technique can compete with SSF and shows substantially more
promise for future improvement; it is a matter of research interest to develop optimized methods of EFM image analysis and
statistical data treatment. EFM is a conduit for understanding the dynamics of individual cell response vs. population response, which is not only a matter of research interest, but is also promising in the practical terms of developing
micro-scale analysis. 相似文献
150.
The title compound 3g is obtained via two different routes, either in a multistep synthesis starting from 2-amino-2-methylpropionic acid (methylalanine) or by light-induced, oxidative dealkylation of the corresponding N-isopropyl derivative 3c . 相似文献