全文获取类型
收费全文 | 891篇 |
免费 | 31篇 |
国内免费 | 4篇 |
专业分类
化学 | 745篇 |
晶体学 | 13篇 |
力学 | 9篇 |
数学 | 87篇 |
物理学 | 72篇 |
出版年
2023年 | 4篇 |
2022年 | 19篇 |
2021年 | 37篇 |
2020年 | 20篇 |
2019年 | 19篇 |
2018年 | 7篇 |
2017年 | 19篇 |
2016年 | 39篇 |
2015年 | 19篇 |
2014年 | 36篇 |
2013年 | 45篇 |
2012年 | 78篇 |
2011年 | 66篇 |
2010年 | 51篇 |
2009年 | 29篇 |
2008年 | 61篇 |
2007年 | 58篇 |
2006年 | 41篇 |
2005年 | 49篇 |
2004年 | 54篇 |
2003年 | 39篇 |
2002年 | 45篇 |
2001年 | 11篇 |
2000年 | 5篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有926条查询结果,搜索用时 20 毫秒
111.
Uniform catalytic site in Sn-beta-zeolite determined using X-ray absorption fine structure 总被引:1,自引:0,他引:1
Bare SR Kelly SD Sinkler W Low JJ Modica FS Valencia S Corma A Nemeth LT 《Journal of the American Chemical Society》2005,127(37):12924-12932
The Sn silicate zeolite, Sn-beta, has been shown to be an efficient, selective heterogeneous catalyst for Baeyer-Villiger oxidations. Using primarily a multishell fit to extended X-ray absorption fine structure (EXAFS) data, we show that the Sn does not randomly insert into the beta-zeolite structure but rather occupies identical, specific, crystallographic sites. These sites are the T5/T6 sites in the six-membered rings. Moreover, the Sn is substituted in pairs on opposite sides of these six-membered rings. We believe that it is the specific, uniform crystallographic location of the Sn in the beta crystal structure that leads to sites with uniform catalytic activity, and consequently to the high chemical selectivity demonstrated for this catalyst. This manifests itself in the almost enzyme-like selectivity of this catalyst in Baeyer-Villiger oxidations. This uniform site distribution of the Sn suggests that there is likely a symbiotic relationship between the structure-directing agent in the zeolite synthesis and the Sn heteroatoms during the framework formation. 相似文献
112.
Electrical measurements are easier and faster than traditional methods for evaluating surface sanitation in the food industry. However, the behavior of sublethally damaged bacteria is different in each method. The electrical method is more sensitive to the presence of disinfectant traces in the samples. These issues lead to low correlations between both methods (r2 < 0.7). The use of smaller sample volumes in electrical measurements, together with the addition of a blend of neutralizers to the sample and the subsequent removal by filtration, provide r2 values > 0.9. The developed protocol shows an excellent correlation with traditional methods and facilitates the adaptation of the electrical method to routine monitoring of surface sanitation. It allows for a reduction in holding times and thereby provides the necessary time to make decisions. 相似文献
113.
Edwards HG Villar SE Jehlicka J Munshi T 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(10):2273-2280
Calcium and magnesium carbonates are important minerals found in sedimentary environments. Although sandstones are the most common rock colonized by endolith organisms, the production of calcium and magnesium carbonates is important in survival strategies of organisms and as a source for the removal of oxalate ions. Extremophile organisms in some situations may convert or destroy carbonates of calcium and magnesium, which gives important information about the conditions under which these organisms can survive. The identification on the surface of Mars of 'White Rock' formations, in Juventae Chasma or Sabaea Terra, as possibly carbonate rocks makes the study of these minerals a prerequisite of remote Martian exploration. Here, we show the protocol for the identification by Raman spectroscopy of different calcium and magnesium carbonates and we present a database of relevance in the search for life, extinct or extant, on Mars; this will be useful for the assessment of data obtained from remote, miniaturized Raman spectrometers now proposed for Mars exploration. 相似文献
114.
Ana Brăileanu Susana Mihaiu Margit Bán J. Madarász G. Pokol 《Journal of Thermal Analysis and Calorimetry》2005,80(3):613-618
Summary Oxide materials belonging to the Sn-Ce-O system are very interesting due to their use as solid electrolytes in fuel cells, catalysts, sensors and photoanodes in solar cells. The aim of the present work is to investigate the thermal behaviour of some tin and cerium salt mixtures. Mixtures with different representative Sn:Ce atomic ratio were prepared by classical ceramic method using SnC2O4, Ce(SO4)2·4H2O and (NH4)2Ce(NO3)6 as starting compounds. The samples were investigated by means of TG/DTA methods in flowing and static air atmosphere. SnO2 and/or CeO2 were identified by X-ray diffraction and IR spectroscopy in the final decomposition products, depending on the initial composition of the both series. A different crystallinity degree of the solid products was observed depending on the Ce precursor. 相似文献
115.
116.
José Calhorda M Costa PJ Crespo O Gimeno MC Jones PG Laguna A Naranjo M Quintal S Shi YJ Villacampa MD 《Dalton transactions (Cambridge, England : 2003)》2006,(34):4104-4113
The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane (L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 (1), with crystallographic mirror symmetry, or dinuclear [Ag2(mu-L)2](OTf)2 (2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 (3); Ag, X = OTf 4). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf (5). The gold(I) derivative [Au2(C6F5)2(mu-L)] (6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1-4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework. 相似文献
117.
Hanrahan JR Mewett KN Chebib M Matos S Eliopoulos CT Crean C Kumar RJ Burden P Johnston GA 《Organic & biomolecular chemistry》2006,4(13):2642-2649
A divergent synthesis of both diastereoisomers of (+/-)-(3-aminocyclopentane)alkylphosphinic acid is described. Both diastereoisomers are obtained in 5 steps from the key (+/-)-(3-hydroxycyclopent-1-ene)alkylphosphinate esters which are prepared via a palladium catalysed C-P bond forming reaction. 相似文献
118.
ZDM – Mathematics Education - We report on a study focused on identifying how undergraduate students make use of the Internet as a source of help to solve their mathematical queries. In... 相似文献
119.
120.
Daniela di Serafino Susana Gomez Leopoldo Milano Filippo Riccio Gerardo Toraldo 《Journal of Global Optimization》2010,48(1):41-55
The detection of gravitational waves is a long-awaited event in modern physics and, to achieve this challenging goal, detectors
with high sensitivity are being used or are under development. In order to extract gravitational signals emitted by coalescing
binary systems of compact objects (neutron stars and/or black holes), from noisy data obtained by interferometric detectors,
the matched filter technique is generally used. Its computational kernel is a box-constrained global optimization problem
with many local solutions and a highly nonlinear and expensive objective function, whose derivatives are not available. To
tackle this problem, we designed a real-coded genetic algorithm that exploits characteristic features of the problem itself;
special attention was devoted to the choice of the initial population and of the recombination operator. Computational experiments
showed that our algorithm is able to compute a reasonably accurate solution of the optimization problem, requiring a much
smaller number of function evaluations than the grid search, which is generally used to solve this problem. Furthermore, the
genetic algorithm largely outperforms other global optimization algorithms on significant instances of the problem. 相似文献