全文获取类型
收费全文 | 439篇 |
免费 | 19篇 |
专业分类
化学 | 373篇 |
力学 | 1篇 |
数学 | 25篇 |
物理学 | 59篇 |
出版年
2022年 | 8篇 |
2021年 | 8篇 |
2020年 | 18篇 |
2019年 | 4篇 |
2018年 | 6篇 |
2017年 | 10篇 |
2016年 | 8篇 |
2015年 | 10篇 |
2014年 | 15篇 |
2013年 | 25篇 |
2012年 | 23篇 |
2011年 | 44篇 |
2010年 | 18篇 |
2009年 | 21篇 |
2008年 | 19篇 |
2007年 | 18篇 |
2006年 | 30篇 |
2005年 | 13篇 |
2004年 | 15篇 |
2003年 | 10篇 |
2002年 | 10篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1997年 | 8篇 |
1996年 | 3篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 3篇 |
1991年 | 6篇 |
1989年 | 2篇 |
1987年 | 2篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 7篇 |
1974年 | 5篇 |
1973年 | 2篇 |
1971年 | 4篇 |
1958年 | 2篇 |
1944年 | 2篇 |
1933年 | 2篇 |
1927年 | 3篇 |
排序方式: 共有458条查询结果,搜索用时 78 毫秒
431.
We have studied the correlation between field evaporated atoms during an atom probe tomography experiment. The evaporated atoms have been shown to be highly correlated both in time and in space. This correlation can be explained by the dynamic distribution of the electric field at the surface of the sample. The evaporation sequence follows the distribution of zones where the electric field intensity is higher. The distance of correlation between successively evaporated atoms corresponds to the mean size of these zones and the time of correlation corresponds to the mean time necessary to evaporate the entire zone. 相似文献
432.
The processes by which individuals can construct proofs based on visual arguments are poorly understood. We investigated this issue by presenting eight mathematicians with a task that invited the construction of a diagram, and examined how they used this diagram to produce a formal proof. The main findings were that participants varied in the extent of their diagram usage, it was not trivial for participants to translate an intuitive argument into a formal proof, and participants’ reasons for using diagrams included noticing mathematical properties, verifying logical deductions, representing ideas or assertions, and suggesting proof approaches. 相似文献
433.
Kelly E Matthews Yvonne Hodgson Cristina Varsavsky 《International Journal of Mathematical Education in Science & Technology》2013,44(6):782-795
There is international agreement that quantitative skills (QS) are an essential graduate competence in science. QS refer to the application of mathematical and statistical thinking and reasoning in science. This study reports on the use of the Science Students Skills Inventory to capture final year science students’ perceptions of their QS across multiple indicators, at two Australian research-intensive universities. Statistical analysis reveals several variables predicting higher levels of self-rated competence in QS: students’ grade point average, students’ perceptions of inclusion of QS in the science degree programme, their confidence in QS, and their belief that QS will be useful in the future. The findings are discussed in terms of implications for designing science curricula more effectively to build students’ QS throughout science degree programmes. Suggestions for further research are offered. 相似文献
434.
A stannane-free hydrodehalogenation of 4-halotetrahydropyran under very mild conditions has been developed. This methodology allows selective one-pot dehalogenation and/or debenzylation depending on the type of halide-substrate used. The applicability of this methodology is well demonstrated in the synthesis of a key intermediate toward the enantioselective synthesis of (+)-SCH 351448. 相似文献
435.
Dienes Y Durben S Kárpáti T Neumann T Englert U Nyulászi L Baumgartner T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(26):7487-7500
The systematic extension of the pi-conjugated system of strongly blue-luminescent dithieno[3,2-b:2',3'-d]phospholes has been investigated with the goal of obtaining different emission colors. Functionalization of the 2- and 6-position of the dithienophosphole scaffold with halogen substituents provided functional building blocks for subsequent cross-coupling experiments with various homo- and heteroaryls to selectively decrease the band gap of the materials. By this strategy materials with different emission colors ranging from green via yellow to orange could be obtained. This feature supports their suitability for organic light-emitting diodes with respect to an application in full-color flat-panel displays. The experimental results were nicely supported by theoretical DFT calculations providing a deeper understanding of the electronic structure in the extended materials, and also allowing for the design of future materials based on a dithienophosphole core. Furthermore, the phosphorus center in the extended molecular materials can efficiently be fine-tuned in subsequent simple chemical functionalizations. This allows for a tailoring of the optoelectronic properties of the extended dithienophospholes to suit the requirements of potential applications. 相似文献
436.
Zieba AA Richardson C Lucero C Dieng SD Gindt YM Schelvis JP 《Journal of the American Chemical Society》2011,133(20):7824-7836
Proton-coupled electron-transfer (PCET) is a mechanism of great importance in protein electron transfer and enzyme catalysis, and the involvement of aromatic amino acids in this process is of much interest. The DNA repair enzyme photolyase provides a natural system that allows for the study of PCET using a neutral radical tryptophan (Trp(?)). In Escherichia coli photolyase, photoreduction of the flavin adenine dinucleotide (FAD) cofactor in its neutral radical semiquinone form (FADH(?)) results in the formation of FADH(-) and (306)Trp(?). Charge recombination between these two intermediates requires the uptake of a proton by (306)Trp(?). The rate constant of charge recombination has been measured as a function of temperature in the pH range from 5.5 to 10.0, and the data are analyzed with both classical Marcus and semi-classical Hopfield electron transfer theory. The reorganization energy associated with the charge recombination process shows a pH dependence ranging from 2.3 eV at pH ≤ 7 and 1.2 eV at pH(D) 10.0. These findings indicate that at least two mechanisms are involved in the charge recombination reaction. Global analysis of the data supports the hypothesis that PCET during charge recombination can follow two different mechanisms with an apparent switch around pH 6.5. At lower pH, concerted electron proton transfer (CEPT) is the favorable mechanism with a reorganization energy of 2.1-2.3 eV. At higher pH, a sequential mechanism becomes dominant with rate-limiting electron-transfer followed by proton uptake which has a reorganization energy of 1.0-1.3 eV. The observed 'inverse' deuterium isotope effect at pH < 8 can be explained by a solvent isotope effect that affects the free energy change of the reaction and masks the normal, mass-related kinetic isotope effect that is expected for a CEPT mechanism. To the best of our knowledge, this is the first time that a switch in PCET mechanism has been observed in a protein. 相似文献
437.
Ilboudo O Tapsoba I Bonzi-Coulibaly YL Gerbaux P 《European journal of mass spectrometry (Chichester, England)》2011,17(6):557-572
Flavonoids are ubiquitous molecules in nature and are found in almost all plants, including fruits and vegetables. Although flavonoids are structurally similar, subtle differences in their structures lead to important changes in their biological activities. Over years, mass spectrometry has become an ideal tool for the characterization of those important molecules. In particular to overcome the challenge of structure assignment, tandem mass spectrometry was used in numerous studies. In the present study, we submitted selected flavonoid 7- O-diglycosides to electrospray ionization to prepare different kinds of flavonoid ions, i.e. protonated, sodium- cationized and copper-cationized molecules. Most of the investigated reactions are already described in the literature in several papers and the aim of the present study is to present concise and coherent relations between CID reactions, cationizing agents and flavonoid 7-O-diglycoside structures. Some insights in the reaction mechanisms and the role of the cationizing particles will also be attempted. 相似文献
438.
Gianluca Pastorelli Jane Richter Yvonne Shashoua 《Polymer Degradation and Stability》2011,96(11):1996-2001
The aim of this study was to provide evidence about the interaction between Baltic amber and daylight behind window glass, essential to understanding the mechanisms by which the material degrades in museum environments and to propose techniques for preventive conservation based on the control of environmental parameters where amber objects are stored or displayed. To investigate the photodegradation of Baltic amber, the methodology consisted of artificial ageing, in order to initiate degradation of model amber samples, and non-destructive analytical techniques, in order to identify and quantify changes in colour and chemical properties. Prism-shaped samples, obtained from a large amber piece, were exposed to different microclimatic conditions, subjected to accelerated photoageing and analysed by spectrocolorimetry, infrared spectroscopy and Raman spectroscopy. The experiments provided results about surface discolouration, oxidation of the molecular structure and breakdown of unsaturated carbon-carbon bonds in various environmental conditions, confirming the degrading role of daylight behind window glass. The conclusions of this study can be applied to the development of techniques for preventive conservation of museum collections containing amber objects. 相似文献
439.
Malkov AV Barłóg M Jewkes Y Mikusek J Kocovský P 《The Journal of organic chemistry》2011,76(11):4800-4804
α,β-Unsaturated aldehydes 6a-j undergo an enantioselective allylation with allylic trichlorosilanes 2a,b in the presence of METHOX (4) as a Lewis basic catalyst (≤10 mol %) to produce the homoallylic alcohols 7a-l at good to high enantioselectivity (83-96% ee). This study shows that the reactivity scope of METHOX can be extended from aromatic to nonaromatic aldehydes. 相似文献
440.
New methodology for the stereoselective synthesis of trisubstituted olefins is presented. The use of ortho-diphenylphosphanyl benzoate (o-DPPB) as a directing leaving group for copper-mediated allylic substitution with Grignard reagents allowed for the stereoselective construction of a wide range of E olefins, without the need for an adjacent electron-withdrawing group. Our modular three-step approach toward trisubstituted alkenes commenced with geminal α-methylene aldehydes. Addition of an organometallic reagent and introduction of the o-DPPB group by esterification was followed by the o-DPPB-directed copper-mediated allylic substitution with a Grignard reagent to furnish stereodefined trisubstituted olefins. Additionally, incorporation of a stereocenter from the chiral pool allowed the preparation of an enantiomerically pure olefin that bore three alkyl substituents in high E/Z selectivity. 相似文献