全文获取类型
收费全文 | 3879篇 |
免费 | 219篇 |
国内免费 | 7篇 |
专业分类
化学 | 2615篇 |
晶体学 | 7篇 |
力学 | 80篇 |
数学 | 669篇 |
物理学 | 734篇 |
出版年
2023年 | 54篇 |
2022年 | 46篇 |
2021年 | 85篇 |
2020年 | 101篇 |
2019年 | 114篇 |
2018年 | 67篇 |
2017年 | 49篇 |
2016年 | 177篇 |
2015年 | 141篇 |
2014年 | 152篇 |
2013年 | 203篇 |
2012年 | 250篇 |
2011年 | 279篇 |
2010年 | 155篇 |
2009年 | 106篇 |
2008年 | 178篇 |
2007年 | 156篇 |
2006年 | 167篇 |
2005年 | 153篇 |
2004年 | 118篇 |
2003年 | 94篇 |
2002年 | 95篇 |
2001年 | 54篇 |
2000年 | 36篇 |
1999年 | 30篇 |
1998年 | 37篇 |
1997年 | 34篇 |
1996年 | 44篇 |
1995年 | 33篇 |
1994年 | 38篇 |
1993年 | 55篇 |
1992年 | 46篇 |
1991年 | 32篇 |
1990年 | 37篇 |
1989年 | 35篇 |
1988年 | 37篇 |
1987年 | 41篇 |
1986年 | 33篇 |
1985年 | 37篇 |
1984年 | 36篇 |
1983年 | 26篇 |
1982年 | 23篇 |
1981年 | 21篇 |
1980年 | 30篇 |
1979年 | 14篇 |
1978年 | 22篇 |
1977年 | 13篇 |
1976年 | 19篇 |
1974年 | 25篇 |
1966年 | 13篇 |
排序方式: 共有4105条查询结果,搜索用时 0 毫秒
71.
Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111) 总被引:2,自引:0,他引:2
Barth JV Weckesser J Trimarchi G Vladimirova M De Vita A Cai C Brune H Günter P Kern K 《Journal of the American Chemical Society》2002,124(27):7991-8000
We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems. 相似文献
72.
Alexander Sandvoß Henning Maag Constantin G. Daniliuc Dieter Schollmeyer Johannes M. Wahl 《Chemical science》2022,13(21):6297
Identification of an electron poor trifluoroacetophenone allows the formation of uniquely stable hemiketals from prochiral oxetanols. When exposed to a cobalt(ii) catalyst, efficient ring-opening to densely functionalized dioxolanes is observed. Mechanistic studies suggest an unprecedented redox process between the cobalt(ii) catalyst and the hemiketal that initiates the oxetane-opening. Based on this observation, a dynamic kinetic resolution of the transient hemiketals is explored that uses a Katsuki-type ligand for stereoinduction (up to 99 : 1 dr and 96 : 4 er) and allows a variety of 1,3-dioxolanes to be accessed (20 examples up to 98% yield).Desymmetrization of prochiral oxetanols via an electron-deficient hemiketal intermediate is achieved. Key to this process is the catalyst''s chiral recognition of one of the two hemiketal enantiomers enabling an efficient dynamic kinetic resolution. 相似文献
73.
Johannes Wellmann Beate Hartmann Esther-Corinna Schwarze Silke Hillebrand Stephan I. Brueckner Jakob Ley Gerold Jerz Peter Winterhalter 《Molecules (Basel, Switzerland)》2022,27(11)
Previously, different Hydrangea macrophylla ssp. serrata cultivars were investigated by untargeted LC-MS analysis. From this, a list of tentatively identified and unknown compounds that differ significantly between these cultivars was obtained. Due to the lack of reference compounds, especially for dihydro-isocoumarins, we aimed to isolate and structurally characterise these compounds from the cultivar ‘Yae-no-amacha’ using NMR and LC-MS methods. For purification and isolation, counter-current chromatography was used in combination with reversed-phase preparative HPLC as an orthogonal and enhanced purification workflow. Thirteen dihydro-isocoumarins in combination with other metabolites could be isolated and structurally identified. Particularly interesting was the clarification of dihydrostilbenoid glycosides, which were described for the first time in H. macrophylla ssp. serrata. These results will help us in further studies on the biological interpretation of our data. 相似文献
74.
75.
Markus Follmann Nils Griebenow Michael G. Hahn Ingo Hartung Franz‐Josef Mais Joachim Mittendorf Martina Schfer Hartmut Schirok Johannes‐Peter Stasch Friederike Stoll Alexander Straub Peter Jeschke Ralf Nauen Michael Edmund Beck Hans‐Wilhelm Engels Hans‐Georg Pirkl Reinhard Albers Rolf W. Albach Jens Krause Andreas Hoffmann Holger Casselmann Jeff Dormish 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(36):9503-9503
76.
Prof. Dr. Axel G. Griesbeck Dr. Johannes Uhlig Dr. Thomas Sottmann Dr. Lhoussaine Belkoura Prof. Dr. Reinhard Strey 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(50):16161-16165
Pluronic F‐127 hydrogels are highly efficient microenvironments for photochemical reactions, as demonstrated for singlet oxygen reactions of monoalkenes. Nonpolar substrates are localized in the nanosized polymer compartment, which can be visualized by neutron scattering. The efficiency of 1O2 reactions is strongly increased for tiglate derivatives and the regioselectivity of the ene reaction of trisubstituted alkenes is completely switched in comparison with solution phase and inverted in comparison with intrazeolite photo‐oxygenations. 相似文献
77.
Dr. Nicole M. G. Franssen Dr. Bernd Ensing Maruti Hegde Prof. Dr. Theo J. Dingemans Ben Norder Prof. Dr. Stephen J. Picken Gert O. R. Alberda van Ekenstein Dr. Ernst R. H. van Eck Dr. Johannes A. A. W. Elemans Mark Vis Prof. Dr. Joost N. H. Reek Prof. Dr. Bas de Bruin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11457-11457
78.
79.
Johannes Barth Michael Buback Christopher Barner‐Kowollik Thomas Junkers Gregory T. Russell 《Journal of polymer science. Part A, Polymer chemistry》2012,50(22):4740-4748
The termination of model mid‐chain radicals (MCRs), which mimic radicals that occur in acrylate polymerization over a broad range of reaction conditions, has been studied by single‐pulse pulsed laser polymerization (SP‐PLP) in conjunction with electron paramagnetic resonance spectroscopy. The model radicals were generated by initiator‐fragment addition to acrylic macromonomers that were preformed prior to the kinetic experiments, thus enabling separation of termination from the propagation reaction, for these model radicals propagate sparingly, if at all, on the timescale of SP‐PLP experiments. Termination rate coefficients of the MCRs were determined in the temperature range of 0–60°C in acetonitrile and butyl propionate solution as well as in bulk macromonomer over the range of 0–100 °C. Termination rate coefficients slightly below those of the corresponding secondary radicals were deduced, demonstrating the relatively high termination activity of this species, even when undergoing MCR–MCR termination. For chain length of 10, a reduction by a factor of 6 is observed. Unusually high activation energies were found for the termination rate coefficient in these systems, with 35 kJ mol?1 being determined for bulk macromonomer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
80.
Johannes W. R. Martini Martin Schlather G. Matthias Ullmann 《Journal of mathematical chemistry》2013,51(2):696-714
In the first part of this work we formulated the decoupled sites representation for two different types of ligands and highlighted special properties of the case of n binding sites for ligand L 1 and one binding site for ligand L 2. Moreover, for this case, we identified the microstate constants as unique components all decoupled molecules share. In the second part on hand, we investigate the cases with (n, 2) and (n, 3) binding sites. As it is difficult to solve the system of equations occurring when a molecule with more than one binding site for both ligands shall be decoupled, we present applicable calculation methods which exploit the special structure of the system of equations. Moreover, we investigate which unique properties all decoupled molecules share and show that for two different decoupled molecules with the same binding polynomial, not all microstate constants of a certain macrostate are permutations of the microstate constants of the other molecule. 相似文献