全文获取类型
收费全文 | 1197篇 |
免费 | 43篇 |
国内免费 | 3篇 |
专业分类
化学 | 1038篇 |
晶体学 | 5篇 |
力学 | 19篇 |
数学 | 60篇 |
物理学 | 121篇 |
出版年
2023年 | 6篇 |
2022年 | 6篇 |
2021年 | 12篇 |
2020年 | 15篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2017年 | 10篇 |
2016年 | 26篇 |
2015年 | 31篇 |
2014年 | 24篇 |
2013年 | 56篇 |
2012年 | 86篇 |
2011年 | 103篇 |
2010年 | 46篇 |
2009年 | 36篇 |
2008年 | 72篇 |
2007年 | 108篇 |
2006年 | 89篇 |
2005年 | 88篇 |
2004年 | 62篇 |
2003年 | 49篇 |
2002年 | 43篇 |
2001年 | 21篇 |
2000年 | 18篇 |
1999年 | 14篇 |
1998年 | 27篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 7篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 7篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1975年 | 3篇 |
1973年 | 5篇 |
1972年 | 4篇 |
1969年 | 2篇 |
1968年 | 8篇 |
1967年 | 3篇 |
排序方式: 共有1243条查询结果,搜索用时 15 毫秒
91.
An evaluation of alpha-aryl-alpha-diazodiones in tandem carbonyl ylide formation-enantioselective [3 + 2]-cycloaddition reactions is described. Such substrates were designed to allow investigation of the electronic characteristics of the dipole upon asymmetric induction. Intramolecular cycloadditions (with a tethered alkene dipolarophile) were found to occur in good to quantitative yields, with a difference in ee exhibited by the two electronically different diazodiones 8 and 9. Intermolecular cycloadditions using diazodiones 12 and 13 with DMAD and arylacetylenes 16-18 again demonstrated that electronics play a key role in determining the outcome of the cycloaddition reactions. Enantioselectivities of up to 76% were observed. 相似文献
92.
Ashcroft AE 《Natural product reports》2003,20(2):202-215
Proteomics encompasses several disciplines in the quest to unravel the science of life. Mass spectrometry plays a key r?le in proteomics-associated analyses and this review describes that function in terms of the instrumentation used, the results generated, data interpretation and the advances in analytical techniques being made to deal with the production of highly specific, high throughput data. The review has 151 references. 相似文献
93.
Hervé G Hahn DU Hervé AC Goodworth KJ Hill AM Hailes HC 《Organic & biomolecular chemistry》2003,1(2):427-435
Methodologies to access water soluble large ringed calixarenes in good yield using efficient synthetic procedures have been investigated. Symmetrical partial functionalisations at the lower rim are described using activated [n]ethylene glycol chains and the addition behaviour contrasted with that of bromoalkanenitriles which proceeds with no observed regioselectivity. Full functionalisations of the calixarenes bearing hydrophilic groups are then investigated and a two-step procedure established which appears to be generally applicable for the addition of different [n]ethylene glycol chains. Furthermore, difunctionalisation under different reaction conditions are described. Throughout, strategies for the characterisation of these high mass compounds are outlined. 相似文献
94.
The response to drying and storage at -20 degrees C or in liquid nitrogen was studied in seeds of the freshwater aquatic plant Najas flexilis. The seeds of this species show some desiccation sensitivity, although post-harvest storage in water at 16 degrees C resulted in improvements in desiccation tolerance. There was 63% germination of seeds dried to 9.5% moisture content (30% RH) following this maturation period. Optimum moisture contents for seeds stored at -20 degrees C for 3 months and in liquid nitrogen for 1 week were ~11% and ~15%, respectively. 相似文献
95.
96.
Hay‐Yan J. Wang Cheng Bin Liu Hsuan‐Wen Wu Jr Shin Kuo 《Rapid communications in mass spectrometry : RCM》2010,24(14):2057-2064
Stroke, a deleterious cerebrovascular event, is caused by a critical reduction in the blood flow to the brain parenchyma that leads to brain injury and loss of brain functions. The inflammatory responses following ischemia often aggravate the neurological damage. Several pro‐inflammatory mediators released after stroke are closely related to the metabolism of phospholipids. In this study we directly profiled the changes in phospholipids in the infarcted rat cerebral cortex 24 hours after middle cerebral artery occlusion (MCAO) using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). Several phosphatidylcholine (PC) species and sphingomyelin (SM) were significantly decreased after infarction. The cationization pattern of the remaining PCs showed a prominent shift from a mostly potassiated or protonated form to a predominantly sodiated pattern. Stroke also elevated the lysophosphatidylcholines (LPCs) and heme in tissue. The isobaric pairs in PC and LPC classes were resolved by masses through their respective alkali metal adducts in the presence of CsCl. The major fatty acyl LPC species were also structurally confirmed by MALDI‐MS/MS. Overall, the results described the changes in PC and LPC species in the infarcted rat cortex. The elevated tissue levels of LPCs and heme signify the ongoing pathological lipid breakdown and the state of parenchymal inflammation. The elevated LPC level in tissue suggests a means of intervention through lysophospholipid metabolism that could potentially benefit the management of stroke and other acute neurological injuries. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
97.
Yuli Xie Yidong Liu Alison Rinderspacher Donald W. Landry 《Tetrahedron letters》2008,49(14):2320-2323
An efficient synthesis of a series of N-8-quinolinyl benzenesultams as novel NF-κB inhibitors was described via diazotization-induced cyclization of easily accessible N-8-quinolinyl-2-aminobenzenesulfonamides. 相似文献
98.
Corey L. Jones Colan E. Hughes Hamish H.-M. Yeung Alison Paul Kenneth. D. M. Harris Timothy L. Easun 《Chemical science》2021,12(4):1486
The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase 1H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol−1) and growth (72.9 ± 8.6 kJ mol−1) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.A new in situ NMR methodology for studying the formation processes of MOFs is reported, supported by SAXS and PXRD experiments. Synthesis of a phosphonate-based MOF is described, from molecular aggregation through to nucleation and crystallisation. 相似文献
99.
A new cyclic nitrone spin trap, [4-(3′,3′-dibutyl-2′-oxy-3′H-isoindol-5′-yloxy)butyl]triphenylphosphonium bromide (MitoSpin), bearing a lipophilic cation has been prepared by a route that involves a novel Parham-type lithiation-cyclization of an isocyanate to give the isoindolinone core. MitoSpin accumulates in a membrane potential dependent way in energized mitochondria and its oxidation could potentially be used in the study of oxidative stress resulting from reactive oxygen species generated in mitochondria. 相似文献
100.