全文获取类型
收费全文 | 577篇 |
免费 | 13篇 |
国内免费 | 4篇 |
专业分类
化学 | 389篇 |
晶体学 | 4篇 |
力学 | 10篇 |
数学 | 111篇 |
物理学 | 80篇 |
出版年
2023年 | 4篇 |
2022年 | 15篇 |
2021年 | 21篇 |
2020年 | 15篇 |
2019年 | 19篇 |
2018年 | 17篇 |
2017年 | 24篇 |
2016年 | 28篇 |
2015年 | 24篇 |
2014年 | 23篇 |
2013年 | 32篇 |
2012年 | 41篇 |
2011年 | 48篇 |
2010年 | 38篇 |
2009年 | 19篇 |
2008年 | 38篇 |
2007年 | 34篇 |
2006年 | 35篇 |
2005年 | 25篇 |
2004年 | 16篇 |
2003年 | 16篇 |
2002年 | 16篇 |
2001年 | 7篇 |
2000年 | 9篇 |
1999年 | 8篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有594条查询结果,搜索用时 15 毫秒
21.
The reaction of 1-aryl-2-(dimethylaminomethylene)butane-1,3-diones with diethyl oxalate in the presence of sodium hydride in THF gave ethyl 5-aroyl-4-oxo-4H-pyran-2-carboxylates, from which 4-oxo-6-aryl-4H-pyran-2-carboxylic acids (6-arylcomanic acids) were obtained in high yields via acid-catalyzed deformylative rearrangement. 5-Aroyl-4-oxo-4H-pyran-2-carboxylic acids (5-aroylcomanic acids) were prepared via а ring-opening/ring-closure sequence by the reaction of 5-aroyl-2-carbethoxy-4-pyrones with piperidine and subsequent basic hydrolysis and acidification. 相似文献
22.
Vyacheslav I. Supranovich Gennady I. Borodkin Aleksey Yu. Vorob’ev Vyacheslav G. Shubin 《Tetrahedron letters》2014
An unusual cleavage of the Cpy–Cpy bond in the reaction of 2,2′-bipyridine N,N′-diimine and its C-methyl substituted derivatives with acetylenes is described. The effect of the solvent on the yield of 7,7′-bipyrazolo[1,5-a]pyridine-2,2′,3,3′-tetracarboxylates and the products of cleavage of the Cpy–Cpy bond has been studied. The mechanism of the cleavage reaction is discussed on the basis of DFT calculations. 相似文献
23.
Chromones bearing electron-withdrawing substituents at the 2- or 3-position react with nonstabilized azomethine ylides to produce 1-benzopyrano[2,3-c]pyrrolidines in good yields. Reactions of 3-cyanochromones proceed diastereoselectively to give 1-benzopyrano[2,3-c]pyrrolidines and tetrahydro-1H-spiro[chromeno[2,3-c]pyrrol-9,5′-oxazolidine]-9a-carbonitriles, depending on the reactant ratio, as a result of a 1,3-dipolar cycloaddition of the azomethine ylide at the double bond and carbonyl group of the chromone system. The latter undergoes demethylenation and recyclization into a novel hexahydrochromeno[2,3-c:3,4-c′]dipyrrole tetracyclic system on heating with hydrochloric acid. 相似文献
24.
Maxim Polikarpov Irina Snigireva John Morse Vyacheslav Yunkin Sergey Kuznetsov Anatoly Snigirev 《Journal of synchrotron radiation》2015,22(1):23-28
For the first time, single‐crystal diamond planar refractive lenses have been fabricated by laser micromachining in 300 µm‐thick diamond plates which were grown by chemical vapour deposition. Linear lenses with apertures up to 1 mm and parabola apex radii up to 500 µm were manufactured and tested at the ESRF ID06 beamline. The large acceptance of these lenses allows them to be used as beam‐conditioning elements. Owing to the unsurpassed thermal properties of single‐crystal diamond, these lenses should be suitable to withstand the extreme flux densities expected at the planned fourth‐generation X‐ray sources. 相似文献
25.
Nataliia Yu. Strutynska Marina A. Bondarenko Ivan V. Ogorodnyk Igor V. Zatovsky Nikolay S. Slobodyanik Vyacheslav N. Baumer Anna N. Puzan 《Crystal Research and Technology》2015,50(7):549-555
The interaction in the molten system Rb2O‐P2O5‐TiO2‐NiO was investigated at different molar ratios Rb/P = 0.5‐1.3, fixed Ti/P = 0.15, Ti/Ni = 1.0 at temperature range 1073–953 K. The conditions of formation of complex phosphates RbTi2(PO4)3, Rb2Ni0.5Ti1.5(PO4)3 and RbNiPO4 have been determined. The new phosphate Rb2Ni0.5Ti1.5(PO4)3 (space group P213, a = 9.9386(2) Å) has been obtained and investigated by the single crystal X‐ray diffraction and FTIR‐spectroscopy. It has langbeinite‐like structure, that is built up from mixed (Ni/Ti)O6‐octahedra and РО4‐tetrahedra. Rubidium atoms are located in closed cavities of 3D‐framework. 相似文献
26.
Valerii F. Traven Dmitriy A. Cheptsov Zarina Z. Mamirgova Natalya P. Solovjova Vyacheslav M. Martynenko Sergei M. Dolotov Michail M. Krayushkin Ivan V. Ivanov 《Photochemistry and photobiology》2020,96(4):798-804
Photophysical characteristics of new 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins have been measured. These coumarin derivatives are found to be effective fluorophores and show high values of quantum yields of fluorescence both in nonpolar and in polar solvents. The 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins turned to be photosensitive compounds and undergo photolysis under irradiation in the range of 310–465 nm. Photolysis is suggested to include retro-cyclization and retro-condensation steps. The process is accompanied by a sharp drop of fluorescence that can be of interest for the creation of new media in optical recording of information. 相似文献
27.
Nikita K. Kulachenkov Dapeng Sun Yuri A. Mezenov Andrei N. Yankin Sergey Rzhevskiy Vyacheslav Dyachuk Alexandre Nomin Ghouti Medjahdi Evgeny A. Pidko Valentin A. Milichko 《Angewandte Chemie (International ed. in English)》2020,59(36):15522-15526
We demonstrate herein an all‐optical switch based on stimuli‐responsive and photochromic‐free metal–organic framework (HKUST‐1). Ultrafast near‐infrared laser pulses stimulate a reversible 0.4 eV blue shift of the absorption band with up to 200 s?1 rate due to dehydration and concomitant shrinking of the structure‐forming [Cu2C4O8] cages of HKUST‐1. Such light‐induced switching enables the remote modulation of intensities of photoluminescence of single crystals of HKUST‐1 as well visible radiation passing through the crystal by 2 order of magnitude. This opens up the possibility of utilyzing stimuli‐responsive MOFs for all‐optical data processing devices. 相似文献
28.
29.
Alexandr Kh. Plyamovatyi Raviya M. Mukhamadeeva Vasily A. Milyukov Oleg G. Sinyashin Alexandr E. Vandyukov Roald R. Shagidullin Allan G. Ginzburg Vyacheslav I. Sokolov 《Heteroatom Chemistry》1995,6(2):177-181
FT-IR spectroscopy and a special mathematical program were used for the real-time monitoring of the mechanistic path of the reaction of S-ethyl-N,N-tetraethyldiamidothiophosphite with [CpMn(CO)-2NO]+BFequation/tex2gif-stack-3.gif. The formation of a few intermediates is described. 相似文献
30.
A triangular lattice model for pattern formation by core-shell particles at fluid interfaces is introduced and studied for the particle to core diameter ratio equal to 3. Repulsion for overlapping shells and attraction at larger distances due to capillary forces are assumed. Ground states and thermodynamic properties are determined analytically and by Monte Carlo simulations for soft outer- and stiffer inner shells, with different decay rates of the interparticle repulsion. We find that thermodynamic properties are qualitatively the same for slow and for fast decay of the repulsive potential, but the ordered phases are stable for temperature ranges, depending strongly on the shape of the repulsive potential. More importantly, there are two types of patterns formed for fixed chemical potential—one for a slow and another one for a fast decay of the repulsion at small distances. In the first case, two different patterns—for example clusters or stripes—occur with the same probability for some range of the chemical potential. For a fixed concentration, an interface is formed between two ordered phases with the closest concentration, and the surface tension takes the same value for all stable interfaces. In the case of degeneracy, a stable interface cannot be formed for one out of four combinations of the coexisting phases, because of a larger surface tension. Our results show that by tuning the architecture of a thick polymeric shell, many different patterns can be obtained for a sufficiently low temperature. 相似文献