全文获取类型
收费全文 | 289篇 |
免费 | 13篇 |
专业分类
化学 | 196篇 |
晶体学 | 2篇 |
力学 | 8篇 |
数学 | 23篇 |
物理学 | 73篇 |
出版年
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 8篇 |
2019年 | 4篇 |
2018年 | 2篇 |
2017年 | 1篇 |
2016年 | 10篇 |
2015年 | 8篇 |
2014年 | 5篇 |
2013年 | 15篇 |
2012年 | 22篇 |
2011年 | 17篇 |
2010年 | 12篇 |
2009年 | 15篇 |
2008年 | 14篇 |
2007年 | 16篇 |
2006年 | 17篇 |
2005年 | 13篇 |
2004年 | 11篇 |
2003年 | 12篇 |
2002年 | 12篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
1940年 | 1篇 |
排序方式: 共有302条查询结果,搜索用时 15 毫秒
1.
Hermann Grabert Gert-Ludwig Ingold Michel H. Devoret Daniel Estève Hugues Pothier Cristian Urbina 《Zeitschrift für Physik B Condensed Matter》1991,84(1):143-155
The rate of electron tunneling through normal metal tunnel junctions is calculated for the case of ultrasmall junction capacitances. The so-called Coulomb blockade of electron tunneling at low temperatures is shown to be strongly affected by the external electrical circuit. Under the common experimental condition of a low impedance environment the Coulomb blockade is suppressed for single tunnel junctions. However, a Coulomb gap structure emerges for junctions embedded in a high impedance environment. For a double junction setup a Coulomb blockade of tunneling arises even for low impedance environments due to the charge quantization on the metallic island between the junctions. An approach using circuit analysis is presented which allows to reduce the calculation of tunneling rates in multijunction circuits to those of a single junction in series with an effective capacitance. The range of validity of the socalled local rule and global rule rates is clarified. It is found that the tunneling rate tends towards the global rule rate as the number of junctions is increased. Some specific results are given for a one-dimensional array of tunnel junctions. 相似文献
2.
Przemyslaw Los Andrzej Lasia Hugues Mnard Louis Brossard 《Journal of Electroanalytical Chemistry》1993,360(1-2)
The hydrogen evolution reaction (HER) was investigated on a lanthanum-phosphate-bonded nickel (LPBN) powder electrode in 30 wt.% NaOH at 70°C using ac impedance and steady-state polarization techniques. Circuits containing one or two constant-phase elements (CPEs) in parallel with a resistance and corresponding to fractal and porous electrode models were tested in order to interpret the ac impedance data. The experimental impedance spectra were well described by the porous electrode model and the circuit containing two CPEs. The results obtained from the ac impedance and steady-state measurements allowed the mechanism and kinetics of the HER to be evaluated. Comparison of these parameters with those obtained on the polycrystalline nickel electrode in 1 M alkaline solution at 25°C indicates that an increase in activity is principally due to an increase in the real surface area. 相似文献
3.
Antifouling coatings are the most reliable way to prevent biofouling of immersed surfaces. As concerning the high toxicity of organotin paints, the tendency is the development of coatings, which do not present environmental risks. In this work, we prepare binders from modification of acrylic copolymers containing free carboxylic acid groups. Biocides chosen are tertiary ammonium salts; alkyl chain substituents with different length are considered. The chemical modifications of resins are carried out via a single step reaction. Modification extents are monitored through proton nuclear magnetic resonance and thermogravimetric analysis and the modified resins are characterised by Fourier transform infrared spectroscopy. The glass transition temperature of the acrylate systems is assessed by dynamical mechanical analysis (pin point method) and compared with data obtained by differential scanning calorimetry. The erosion and antifouling properties of the binders are followed during an exposure to marine environment by a visual observation. 相似文献
4.
E. Pedroso A. Grandas M.A. Saralegui E. Giralt C. Granier J. van Rietschoten 《Tetrahedron》1982,38(9):1183-1192
Convergent solid phase peptide synthesis has been applied to yield LHRH. The segments 1–6 and 7–10 of LHRH were synthesized on a hydroxymethylphenyloxymethyl resin using the base labile Fmoc protecting group on the α-amines. The side chains were protected by HF labile groups. Purification of the segments was performed on Sephadex LH-20 columns and by HPLC on Silica Gel 60 columns. The two segments were then assembled on an α-aminobenzyl resin to yield entire sequence of LHRH. After HF treatment and standard purification on Sephadex G-15 and carboxymethylcellulose CM-52 the desired LHRH was obtained. Synthesis of the segments by the same strategy on carbazoyloxymethylphenyloxymethyl resin showed up unexpected difficulties. 相似文献
5.
Antoine Meunier Michael L. Singleton Brice Kauffmann Thierry Granier Guillaume Lautrette Yann Ferrand Ivan Huc 《Chemical science》2020,11(44):12178
As metalloproteins exemplify, the chemical and physical properties of metal centers depend not only on their first but also on their second coordination sphere. Installing arrays of functional groups around the first coordination sphere of synthetic metal complexes is thus highly desirable, but it remains a challenging objective. Here we introduce a novel approach to produce tailored second coordination spheres. We used bioinspired artificial architectures based on aromatic oligoamide foldamers to construct a rigid, modular and well-defined environment around a metal complex. Specifically, aza-aromatic monomers having a tethered [2Fe–2S] cluster have been synthesized and incorporated in conical helical foldamer sequences. Exploiting the modularity and predictability of aromatic oligoamide structures allowed for the straightforward design of a conical architecture able to sequester the metal complex in a confined environment. Even though no direct metal complex–foldamer interactions were purposely designed in this first generation model, crystallography, NMR and IR spectroscopy concurred to show that the aromatic oligoamide backbone alters the structure and fluxional processes of the metal cluster.Wrapping a [2Fe–2S] metal complex in an aromatic foldamer helix is introduced as a new approach to tailor a second coordination sphere. 相似文献
6.
Graeme Cooke Hugues A de Cremiers Florence M.A DuclairoirJulie Leonardi Georgina RosairVincent M Rotello 《Tetrahedron》2003,59(18):3341-3347
We describe the electrochemically controlled hydrogen bonding interactions between the isobutyl flavin/2,6-diferrocenylamidopyridine (2·5) and 9,10-phenanthrenequinone/1-ferrocenyl-3-hexylurea (4·6) dyads. Cyclic and square wave voltammetry studies have shown that the binding efficiencies between these moieties can be electrochemically actuated in non-polar (CH2Cl2 for 2·5) or polar (DMF for 4·6) organic solvents between three distinct states. 相似文献
7.
8.
Fort S Birikaki L Dubois MP Antoine T Samain E Driguez H 《Chemical communications (Cambridge, England)》2005,(20):2558-2560
Oligosaccharidic moieties of GM(2) and GM(3) gangliosides bearing an allyl or a propargyl aglycon, are efficiently biosynthesized on the gram scale by growing metabolically engineered Escherichia coli cells in the presence of the corresponding lactoside acceptors and sialic acid. 相似文献
9.
Hugues Randriambololona 《Israel Journal of Mathematics》2013,195(1):171-186
Building on previous results of Xing, we give new lower bounds on the rate of linear intersecting codes over large alphabets. The proof is constructive, and uses algebraic geometry (although nothing beyond the basic theory of linear systems on curves). Then, using these new bounds within a concatenation argument, we construct binary (2,1)-separating systems of asymptotic rate exceeding the one given by the probabilistic method, which was the best lower bound available up to now. This answers (negatively) the question of whether this probabilistic bound was exact, which has remained open for more than 30 years. 相似文献
10.
Tony Chave Sergei I. Nikitenko Dominique Granier Thomas Zemb 《Ultrasonics sonochemistry》2009,16(4):481-487
Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al2O3) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm?2, Waq = 0.67 W mL?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al2O3 dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al2O3. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)3. Silent hydrolysis of m-Al2O3 yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment. 相似文献