全文获取类型
收费全文 | 1491篇 |
免费 | 57篇 |
国内免费 | 8篇 |
专业分类
化学 | 969篇 |
晶体学 | 23篇 |
力学 | 36篇 |
数学 | 128篇 |
物理学 | 269篇 |
无线电 | 131篇 |
出版年
2023年 | 9篇 |
2022年 | 12篇 |
2021年 | 18篇 |
2020年 | 23篇 |
2019年 | 27篇 |
2018年 | 16篇 |
2017年 | 16篇 |
2016年 | 23篇 |
2015年 | 29篇 |
2014年 | 27篇 |
2013年 | 78篇 |
2012年 | 86篇 |
2011年 | 94篇 |
2010年 | 53篇 |
2009年 | 42篇 |
2008年 | 83篇 |
2007年 | 76篇 |
2006年 | 74篇 |
2005年 | 78篇 |
2004年 | 62篇 |
2003年 | 56篇 |
2002年 | 52篇 |
2001年 | 22篇 |
2000年 | 26篇 |
1999年 | 25篇 |
1998年 | 16篇 |
1997年 | 19篇 |
1996年 | 21篇 |
1995年 | 15篇 |
1994年 | 21篇 |
1993年 | 23篇 |
1992年 | 13篇 |
1991年 | 11篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1985年 | 16篇 |
1984年 | 16篇 |
1982年 | 16篇 |
1981年 | 11篇 |
1980年 | 21篇 |
1979年 | 14篇 |
1978年 | 13篇 |
1977年 | 15篇 |
1976年 | 19篇 |
1975年 | 15篇 |
1974年 | 12篇 |
1973年 | 34篇 |
1972年 | 10篇 |
排序方式: 共有1556条查询结果,搜索用时 15 毫秒
81.
82.
Siaka Yusuf Melinda Krahenbuhl Bryan Haskins Mike Hartman 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):23-26
To measure the gold content of a catalyst accurately, neutron activation analysis (NAA) is one of the methods of choice. NAA is preferred for such heterogeneous catalysts because: (1) it requires minimal sample preparation; (2) NAA provides consistent and accurate results; and (3) in most cases results are obtained much quicker than competing methods. NAA is also used as a referee for the other elemental techniques when results do not fall within expected statistical uncertainties. However, at very high gold concentrations, applying NAA to determine the gold in a heterogeneous catalyst is more challenging than a routine NAA procedure. On the one hand, the neutron absorption cross section for gold is very high, resulting in significant self-shielding related errors. On the other hand, gold exhibits low energy resonance neutron absorptions. In this application the self-shielding minimization effort was handled more rigorously than the classic suppression of neutron flux within a specimen. This non-routine approach was used because: (1) for most applications, high accuracy, <3 % relative, is desired, (2) the low energy resonances of gold make its neutron reaction rate complex and (3) the TRIGA reactor flux profile used in this study contains both thermal and significant epithermal neutron fluxes. Accuracy and precision, using this new approach, are expected to improve from 15 % to better than 3 % relative uncertainty. This has been accomplished through a rigorous assessment of the observed effects of low energy resonance on the neutron flux spectral shape within the sample and designing an experiment to minimize the effects. 相似文献
83.
Kathryn M. Kuivila Bryan E. Jennings 《International journal of environmental analytical chemistry》2013,93(13-14):897-911
Temporal patterns of pesticide inputs to San Francisco Bay were identified and correlated with timing of application and transport mechanism. Fluxes were calculated from measured concentrations and estimated flow. Persistence of the pesticides under typical riverine or estuarine conditions were estimated from laboratory experiments. Simazine was detected most frequently and had the highest flux into the Bay, which could be explained by its continuous use and long half-life. In comparison, diazinon was detected at lower concentrations and had a lower flux which corresponded to its lower use and shorter half-life. The order-of-magnitude lower fluxes of carbofuran and methidathion corresponded to their lower use and expected hydrolysis. Molinate was detected at the highest concentration but its flux was lower than expected, considering its very high use and persistence in the laboratory experiments. Additional loss of molinate is likely to occur from volatilization and photodegradation on the rice fields. Although thiobencarb had the second highest use, it had the lowest flux of the six pesticides, which can be attributed to its loss via hydrolysis, photodegradation, volatilization, and sorption to sediments. Fluxes into San Francisco Bay were equal to or greater than those reported for other estuaries, except for the Gulf of Mexico. 相似文献
84.
Narayanan Parthasarathy David DeShazer Sharon J. Peacock Vanaporn Wuthiekanun Marilyn J. England Sarah L. Norris 《Journal of carbohydrate chemistry》2013,32(1):32-40
Burkholderia pseudomallei is the causative agent of melioidosis, a bacterial infection endemic in tropical regions including southeast Asia and northern Australia. B. pseudomallei contains structurally unique polysaccharides (capsular polysaccharide and O?antigen saccharides of lipopolysaccharide). A polysaccharide microarray platform was developed by immobilizing these polysaccharides onto glass slides. Employing this microarray, we were able to demonstrate the presence of antibodies to these polysaccharide antigens in the sera of melioidosis patients, but not in serum from nonmelioidosis human subjects. The advantages of this polysaccharide microarray technology over the conventional tests for the serodiagnosis of melioidosis are discussed. 相似文献
85.
We report a mild and efficient method for introducing deuterium into a range of heterocycles by reacting readily available halide analogues in a deuterodehalogenation reaction using D8-IPA or Et3SiD under palladium-catalysed conditions. 相似文献
86.
Shiga Tânia M. Yang Haibing Penning Bryan W. Olek Anna T. McCann Maureen C. Carpita Nicholas C. 《Cellulose (London, England)》2021,28(9):5305-5319
Cellulose - A modified TEMPO-catalyzed oxidation of the solvent-exposed glucosyl units of cellulose to uronic acids, followed by carboxyl reduction with NaBD4 to 6-deutero- and... 相似文献
87.
Evan S. O'Brien Brian Fuglestad Henry J. Lessen Matthew A. Stetz Danny W. Lin Bryan S. Marques Kushol Gupta Karen G. Fleming A. Joshua Wand 《Angewandte Chemie (International ed. in English)》2020,59(27):11108-11114
The internal motions of integral membrane proteins have largely eluded comprehensive experimental characterization. Here the fast side‐chain dynamics of the α‐helical sensory rhodopsin II and the β‐barrel outer membrane protein W have been investigated in lipid bilayers and detergent micelles by solution NMR relaxation techniques. Despite their differing topologies, both proteins have a similar distribution of methyl‐bearing side‐chain motion that is largely independent of membrane mimetic. The methyl‐bearing side chains of both proteins are, on average, more dynamic in the ps–ns timescale than any soluble protein characterized to date. Accordingly, both proteins retain an extraordinary residual conformational entropy in the folded state, which provides a counterbalance to the absence of the hydrophobic effect. Furthermore, the high conformational entropy could greatly influence the thermodynamics underlying membrane‐protein functions, including ligand binding, allostery, and signaling. 相似文献
88.
Nika Mahne Sara E. Renfrew Prof. Bryan D. McCloskey Dr. Stefan A. Freunberger 《Angewandte Chemie (International ed. in English)》2018,57(19):5529-5533
Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal‐O2 batteries, and are believed to form and decompose reversibly in metal‐O2/CO2 cells. In these cathodes, Li2CO3 decomposes to CO2 when exposed to potentials above 3.8 V vs. Li/Li+. However, O2 evolution, as would be expected according to the decomposition reaction 2 Li2CO3→4 Li++4 e?+2 CO2+O2, is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen (1O2) forms upon oxidizing Li2CO3 in an aprotic electrolyte and therefore does not evolve as O2. These results have substantial implications for the long‐term cyclability of batteries: they underpin the importance of avoiding 1O2 in metal‐O2 batteries, question the possibility of a reversible metal‐O2/CO2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition‐metal cathodes with residual Li2CO3. 相似文献
89.
A Scalable Biomimetic Synthesis of Resveratrol Dimers and Systematic Evaluation of their Antioxidant Activities
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Bryan S. Matsuura Mitchell H. Keylor Bo Li YuXuan Lin Shelby Allison Prof. Dr. Derek A. Pratt Prof. Dr. Corey R. J. Stephenson 《Angewandte Chemie (International ed. in English)》2015,54(12):3754-3757
An efficient synthetic route to the resveratrol oligomers quadrangularin A and pallidol is reported. It features a scalable biomimetic oxidative dimerization that proceeds in excellent yield and with complete regioselectivity. A systematic evaluation of the natural products and their synthetic precursors as radical‐trapping antioxidants has revealed that, contrary to popular belief, this mode of action is unlikely to account for their observed biological activity. 相似文献
90.
Nicholas J. Youngman Matthew R. Lewin Rebecca Carter Arno Naude Bryan G. Fry 《Molecules (Basel, Switzerland)》2022,27(5)
Snakebite remains a significant public health burden globally, disproportionately affecting low-income and impoverished regions of the world. Recently, researchers have begun to focus on the use of small-molecule inhibitors as potential candidates for the neutralisation of key snake venom toxins and as potential field therapies. Bitis vipers represent some of the most medically important as well as frequently encountered snake species in Africa, with a number of species possessing anticoagulant phospholipase A2 (PLA2) toxins that prevent the prothrombinase complex from inducing clot formation. Additionally, species within the genus are known to exert pseudo-procoagulant activity, whereby kallikrein enzymatic toxins cleave fibrinogen to form a weak fibrin clot that rapidly degrades, thereby depleting fibrinogen levels and contributing to the net anticoagulant state. Utilising well-validated coagulation assays measuring time until clot formation, this study addresses the in vitro efficacy of three small molecule enzyme inhibitors (marimastat, prinomastat and varespladib) in neutralising these aforementioned activities. The PLA2 inhibitor varespladib showed the greatest efficacy for the neutralisation of PLA2-driven anticoagulant venom activity, with the metalloproteinase inhibitors prinomastat and marimastat both showing low and highly variable degrees of cross-neutralisation with PLA2 anticoagulant toxicity. However, none of the inhibitors showed efficacy in neutralising the pseudo-procoagulant venom activity exerted by the venom of B. caudalis. Our results highlight the complex nature of snake venoms, for which single-compound treatments will not be universally effective, but combinations might prove highly effective. Despite the limitations of these inhibitors with regards to in vitro kallikrein enzyme pseudo-procoagulant venom activity, our results further support the growing body of literature indicating the potential use of small molecule inhibitors to enhance first-aid treatment of snakebite envenoming, particularly in cases where hospital and thus antivenom treatment is either unavailable or far away. 相似文献