全文获取类型
收费全文 | 152篇 |
免费 | 13篇 |
专业分类
化学 | 96篇 |
晶体学 | 1篇 |
力学 | 14篇 |
数学 | 20篇 |
物理学 | 34篇 |
出版年
2022年 | 3篇 |
2021年 | 7篇 |
2020年 | 1篇 |
2019年 | 2篇 |
2018年 | 7篇 |
2017年 | 1篇 |
2016年 | 5篇 |
2015年 | 11篇 |
2014年 | 17篇 |
2013年 | 5篇 |
2012年 | 18篇 |
2011年 | 12篇 |
2010年 | 4篇 |
2009年 | 3篇 |
2008年 | 15篇 |
2007年 | 7篇 |
2006年 | 5篇 |
2005年 | 3篇 |
2004年 | 8篇 |
2003年 | 4篇 |
2002年 | 6篇 |
2001年 | 6篇 |
1999年 | 2篇 |
1995年 | 2篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有165条查询结果,搜索用时 15 毫秒
1.
2.
3.
4.
Iijima T Vignon SA Tseng HR Jarrosson T Sanders JK Marchioni F Venturi M Apostoli E Balzani V Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6375-6392
In pursuit of a neutral bistable [2]rotaxane made up of two tetraarylmethane stoppers--both carrying one isopropyl and two tert-butyl groups located at the para positions on each of three of the four aryl rings--known to permit the slippage of the pi-electron-donating 1,5-dinaphtho[38]crown-10 (1/5DNP38C10) at the thermodynamic instigation of pi-electron-accepting recognition sites, in this case, pyromellitic diimide (PmI) and 1,4,5,8-naphthalenetetracarboxylate diimide (NpI) units separated from each other along the rod section of the rotaxane's dumbbell component, and from the para positions of the fourth aryl group of the two stoppers by pentamethylene chains, a modular approach was employed in the synthesis of the dumbbell-shaped compound NpPmD, as well as of its two degenerate counterparts, one (PmPmD) which contains two PmI units and the other (NpNpD) which contains two NpI units. The bistable [2]rotaxane NpPmR, as well as its two degenerate analogues PmPmR and NpNpR, were obtained from the corresponding dumbbell-shaped compounds NpPmD, PmPmD, and NpNpD and 1/5DNP38C10 by slippage. Dynamic 1H NMR spectroscopy in CD2Cl2 revealed that shuttling of the 1/5DNP38C10 ring occurs in NpNpR and PmPmR, with activation barriers of 277 K of 14.0 and 10.9 kcal mol(-1), respectively, reflecting a much more pronounced donor-acceptor stabilizing interaction involving the NpI units over the PmI ones. The photophysical and electrochemical properties of the three neutral [2]rotaxanes and their dumbbell-shaped precursors have also been investigated in CH2Cl2. Interactions between 1/5DNP38C10 and PmI and NpI units located within the rod section of the dumbbell components of the [2]rotaxane give rise to the appearance of charge-transfer bands, the energies of which correlate with the electron-accepting properties of the two diimide moieties. Comparison between the positions of the visible absorption bands in the three [2]rotaxanes shows that, in NpPmR, the major translational isomer is the one in which 1/5DNP38C10 encircles the NpI unit. Correlations of the reduction potentials for all the compounds studied confirm that, in this non-degenerate [2]rotaxane, one of the translational isomers predominates. Furthermore, after deactivation of the NpI unit by one-electron reduction, the 1/5DNP38C10 macrocycle moves to the PmI unit. Li+ ions have been found to strengthen the interaction between the electron-donating crown ether and the electron-accepting diimide units, particularly the PmI one. Titration experiments show that two Li+ ions are involved in the strengthening of the donor-acceptor interaction. Addition of Li+ ions to NpPmR induces the 1/5DNP38C10 macrocycle to move from the NpI to the PmI unit. The Li+-ion-promoted switching of NpPmR in a 4:1 mixture of CD2Cl2 and CD3COCD3 has also been shown by 1H NMR spectroscopy to involve the mechanical movement of the 1/5DNP38C10 macrocycle from the NpI to the PmI unit, a process that can be reversed by adding an excess of [12]crown-4 to sequester the Li+ ions. 相似文献
5.
Thibaut Van Acker Stijn J.M. Van Malderen Marjolein Van Heerden James Eric McDuffie Filip Cuyckens Frank Vanhaecke 《Analytica chimica acta》2016
Two-dimensional elemental mapping (bioimaging) via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on 5 μm thick formalin-fixed, paraffin-embedded kidney tissue sections from Cynomolgus monkeys administered with increasing pharmacological doses of cisplatin. Laterally resolved pixels of 1 μm were achieved, enabling elemental analysis on a (sub-)cellular level. Zones of high Pt response were observed in the renal cortex, where proximal tubules are present, the epithelium of which is responsible for partial reabsorption of cisplatin. Histopathological evaluation, of hematoxylin and eosin-stained serial sections, adjacent to the sections probed via LA-ICP-MS, revealed minimal to mild cisplatin-related lesions (<100 μm) in the renal cortex. Necrotic proximal tubules with sloughed epithelial cells in their lumen could be linked directly to the areas with the highest accumulation of cisplatin, indicating a direct link between cellular concentration and toxicity, thereby providing more insight into the mechanisms through which renal damage occurs. 相似文献
6.
7.
Of interest here is the influence of loading rate on the stability of structures where inertia is taken into account, with particular attention to the comparison between static and dynamic buckling. This work shows the importance of studying stability via perturbations of the initial conditions, since a finite velocity governs the propagation of disturbances. The method of modal analysis that determines the fastest growing wavelength, currently used in the literature to analyze dynamic stability problems, is meaningful only for cases where the velocity of the perfect structure is significantly lower than the associated wave propagation speeds. 相似文献
8.
9.
A mathematical study via variational convergence of a periodic distribution of classical linearly elastic thin plates softly abutted together shows that it is not necessary to use a different continuum model nor to make constitutive symmetry hypothesis as starting points to deduce the Reissner–Mindlin plate model. 相似文献
10.
Theodore Flack Thibaut Constantin Sylvain Penasse Dr. Jérôme Dejeu Béatrice Gennaro Dr. Muriel Jourdan Aurélien Laguerre Marc Pirrotta Dr. David Monchaud Dr. Nicolas Spinelli Prof. Eric Defrancq 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1760-1767
A water‐soluble template‐assembled synthetic G‐quartet (TASQ) based on the use of a macrocyclodecapeptide scaffold was designed to display stable intramolecular folds alone in solution. The preformation of the guanine quartet, demonstrated by NMR and CD investigations, results in enhanced peroxidase‐type biocatalytic activities and improved quadruplex‐interacting properties. Comparison of its DNAzyme‐boosting properties with the ones of previously published TASQ revealed that, nowadays, it is the best DNAzyme‐boosting agent. 相似文献