全文获取类型
收费全文 | 157篇 |
免费 | 3篇 |
专业分类
化学 | 111篇 |
力学 | 4篇 |
数学 | 5篇 |
物理学 | 31篇 |
综合类 | 9篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2020年 | 2篇 |
2019年 | 1篇 |
2018年 | 2篇 |
2015年 | 3篇 |
2013年 | 2篇 |
2012年 | 10篇 |
2011年 | 7篇 |
2010年 | 6篇 |
2009年 | 5篇 |
2008年 | 13篇 |
2007年 | 14篇 |
2006年 | 14篇 |
2005年 | 9篇 |
2004年 | 9篇 |
2003年 | 3篇 |
2002年 | 3篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1990年 | 3篇 |
1987年 | 1篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1957年 | 2篇 |
1929年 | 2篇 |
1895年 | 2篇 |
排序方式: 共有160条查询结果,搜索用时 15 毫秒
91.
Ramsahye NA Maurin G Bourrelly S Llewellyn PL Loiseau T Serre C Férey G 《Chemical communications (Cambridge, England)》2007,(31):3261-3263
Grand Canonical Monte Carlo simulations have explained the breathing of a metal-organic framework upon CO(2) adsorption, first suggested by microcalorimetry. 相似文献
92.
AM Cardoso SM Alexandre CM Barros AJ Correia NM Nibbering 《Rapid communications in mass spectrometry : RCM》1999,13(19):1885-1888
The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
93.
94.
Kurella Sreenivasulu Pramod S. Chaudhari Srinivas Achanta Abhishek Sud Vilas Dahanukar Christopher J. Cobley Fiona Llewellyn‐Beard Rakeshwar Bandichhor 《化学:亚洲杂志》2020,15(10):1605-1608
An alternate formal synthesis of Sitagliptin phosphate is disclosed from 2,4,5‐trifluorobenzadehyde in 8 linear steps with an overall yield of 31%. The chiral β‐amino acid moiety present in sitaglitpin is installed via an asymmetric hydrogenation followed by a stereoselective Hofmann rearrangement as the key steps. The key chiral intermediate Boc‐amino acid 1 prepared by this novel route was further converted to Sitagliptin phosphate following the known literature protocol. 相似文献
95.
Dr. Viktor Moberg Robin Duquesne Dr. Simone Contaldi Oliver Röhrs Jonny Nachtigall Llewellyn Damoense Dr. Alan T. Hutton Dr. Michael Green Prof. Magda Monari Daniela Santelia Prof. Matti Haukka Dr. Ebbe Nordlander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12458-12478
The new clusters [H4Ru4(CO)10(μ‐1,2‐P‐P)], [H4Ru4(CO)10(1,1‐P‐P)] and [H4Ru4(CO)11(P‐P)] (P‐P=chiral diphosphine of the ferrocene‐based Josiphos or Walphos ligand families) have been synthesised and characterised. The crystal and molecular structures of eleven clusters reveal that the coordination modes of the diphosphine in the [H4Ru4(CO)10(μ‐1,2‐P‐P)] clusters are different for the Josiphos and the Walphos ligands. The Josiphos ligands bridge a metal–metal bond of the ruthenium tetrahedron in the “conventional” manner, that is, with both phosphine moieties coordinated in equatorial positions relative to a triangular face of the tetrahedron, whereas the phosphine moieties of the Walphos ligands coordinate in one axial and one equatorial position. The differences in the ligand size and the coordination mode between the two types of ligands appear to be reflected in a relative propensity for isomerisation; in solution, the [H4Ru4(CO)10(1,1‐Walphos)] clusters isomerise to the corresponding [H4Ru4(CO)10(μ‐1,2‐Walphos)] clusters, whereas the Josiphos‐containing clusters show no tendency to isomerisation in solution. The clusters have been tested as catalysts for asymmetric hydrogenation of four prochiral α‐unsaturated carboxylic acids and the prochiral methyl ester (E)‐methyl 2‐methylbut‐2‐enoate. High conversion rates (>94 %) and selectivities of product formation were observed for almost all catalysts/catalyst precursors. The observed enantioselectivities were low or nonexistent for the Josiphos‐containing clusters and catalyst (cluster) recovery was low, suggesting that cluster fragmentation takes place. On the other hand, excellent conversion rates (99–100 %), product selectivities (99–100 % in most cases) and good enantioselectivities, reaching 90 % enantiomeric excess (ee) in certain cases, were observed for the Walphos‐containing clusters, and the clusters could be recovered in good yield after completed catalysis. Results from high‐pressure NMR and IR studies, catalyst poisoning tests and comparison of catalytic properties of two [H4Ru4(CO)10(μ‐1,2‐P‐P)] clusters (P‐P=Walphos ligands) with the analogous mononuclear catalysts [Ru(P‐P)(carboxylato)2] suggest that these clusters may be the active catalytic species, or direct precursors of an active catalytic cluster species. 相似文献
96.
Soubeyrand-Lenoir E Vagner C Yoon JW Bazin P Ragon F Hwang YK Serre C Chang JS Llewellyn PL 《Journal of the American Chemical Society》2012,134(24):10174-10181
The uptake and adsorption enthalpy of carbon dioxide at 0.2 bar have been studied in three different topical porous MOF samples, HKUST-1, UiO-66(Zr), and MIL-100(Fe), after having been pre-equilibrated under different relative humidities (3, 10, 20, 40%) of water vapor. If in the case of microporous UiO-66, CO(2) uptake remained similar whatever the relative humidity, and correlations were difficult for microporous HKUST-1 due to its relative instability toward water vapor. In the case of MIL-100(Fe), a remarkable 5-fold increase in CO(2) uptake was observed with increasing RH, up to 105 mg g(-1) CO(2) at 40% RH, in parallel with a large decrease in enthalpy measured. Cycling measurements show slight differences for the initial three cycles and complete reversibility with further cycles. These results suggest an enhanced solubility of CO(2) in the water-filled mesopores of MIL-100(Fe). 相似文献
97.
Hamon L Heymans N Llewellyn PL Guillerm V Ghoufi A Vaesen S Maurin G Serre C De Weireld G Pirngruber GD 《Dalton transactions (Cambridge, England : 2003)》2012,41(14):4052-4059
Carbon dioxide is the main undesirable compound present in raw natural gas and biogas. Physisorption based adsorption processes such as pressure swing adsorption (PSA) are one of the solutions to selectively adsorb CO(2) from CH(4). Some hybrid crystalline porous materials that belong to the family of metal-organic frameworks (MOFs) show larger CO(2) adsorption capacity compared to the usual industrial adsorbents, such as zeolites and most activated carbons, which makes them potentially promising for such applications. However, their selectivity values have been most often determined using only single gas adsorption measurements combined with simple macroscopic thermodynamic models or by means of molecular simulations based on generic forcefields. The transfer of this systematic approach to all MOFs, whatever their complex physico-chemical features, needs to be considered with caution. In contrast, direct co-adsorption measurements collected on these new materials are still scarce. The aim of this study is to perform a complete analysis of the CO(2)-CH(4) co-adsorption in the mesoporous MIL-100(Cr) MOF (MIL stands for Materials from Institut Lavoisier) by means of a synergic combination of outstanding experimental and modelling tools. This solid has been chosen both for its fundamental interests, given its very large CO(2) adsorption capacities and its complexity with a combination of micropores and mesopores and the existence of unsaturated accessible metal sites. The predictions obtained by means of Grand Canonical Monte Carlo simulations based on generic forcefields as well as macroscopic thermodynamic (IAST, RAST) models will be compared to direct the co-adsorption experimental data (breakthrough curve and volumetric measurements). 相似文献
98.
Erra L Tedesco C Cipolletti VR Annunziata L Gaeta C Brunelli M Fitch AN Knöfel C Llewellyn PL Atwood JL Neri P 《Physical chemistry chemical physics : PCCP》2012,14(1):311-317
The adsorption properties of a new nanoporous organic zeolite with respect to acetylene and Ar were studied by volumetric adsorption analysis, microcalorimetric experiments, and synchrotron high-resolution X-ray powder diffraction. This allowed us to locate the guest molecules inside the host channels and characterize the host-guest interactions. 相似文献
99.
V Moberg R Duquesne S Contaldi O Röhrs J Nachtigall L Damoense AT Hutton M Green M Monari D Santelia M Haukka E Nordlander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12458-12478
The new clusters [H(4) Ru(4) (CO)(10) (μ-1,2-P-P)], [H(4) Ru(4) (CO)(10) (1,1-P-P)] and [H(4) Ru(4) (CO)(11) (P-P)] (P-P=chiral diphosphine of the ferrocene-based Josiphos or Walphos ligand families) have been synthesised and characterised. The crystal and molecular structures of eleven clusters reveal that the coordination modes of the diphosphine in the [H(4) Ru(4) (CO)(10) (μ-1,2-P-P)] clusters are different for the Josiphos and the Walphos ligands. The Josiphos ligands bridge a metal-metal bond of the ruthenium tetrahedron in the "conventional" manner, that is, with both phosphine moieties coordinated in equatorial positions relative to a triangular face of the tetrahedron, whereas the phosphine moieties of the Walphos ligands coordinate in one axial and one equatorial position. The differences in the ligand size and the coordination mode between the two types of ligands appear to be reflected in a relative propensity for isomerisation; in solution, the [H(4) Ru(4) (CO)(10) (1,1-Walphos)] clusters isomerise to the corresponding [H(4) Ru(4) (CO)(10) (μ-1,2-Walphos)] clusters, whereas the Josiphos-containing clusters show no tendency to isomerisation in solution. The clusters have been tested as catalysts for asymmetric hydrogenation of four prochiral α-unsaturated carboxylic acids and the prochiral methyl ester (E)-methyl 2-methylbut-2-enoate. High conversion rates (>94?%) and selectivities of product formation were observed for almost all catalysts/catalyst precursors. The observed enantioselectivities were low or nonexistent for the Josiphos-containing clusters and catalyst (cluster) recovery was low, suggesting that cluster fragmentation takes place. On the other hand, excellent conversion rates (99-100?%), product selectivities (99-100?% in most cases) and good enantioselectivities, reaching 90?% enantiomeric excess (ee) in certain cases, were observed for the Walphos-containing clusters, and the clusters could be recovered in good yield after completed catalysis. Results from high-pressure NMR and IR studies, catalyst poisoning tests and comparison of catalytic properties of two [H(4) Ru(4) (CO)(10) (μ-1,2-P-P)] clusters (P-P=Walphos ligands) with the analogous mononuclear catalysts [Ru(P-P)(carboxylato)(2) ] suggest that these clusters may be the active catalytic species, or direct precursors of an active catalytic cluster species. 相似文献
100.
Yang Q Wiersum AD Llewellyn PL Guillerm V Serre C Maurin G 《Chemical communications (Cambridge, England)》2011,47(34):9603-9605
The ligand functionalization effect on the CO(2)/CH(4) separation performance of the MOF type UiO-66(Zr) was explored computationally. The -SO(3)H and -CO(2)H functionalized forms show the highest selectivity, good working capacity and medium ranged CO(2) adsorption enthalpy that make these materials very promising for physisorption-based processes. 相似文献