全文获取类型
收费全文 | 423篇 |
免费 | 49篇 |
国内免费 | 1篇 |
专业分类
化学 | 404篇 |
力学 | 4篇 |
数学 | 33篇 |
物理学 | 32篇 |
出版年
2024年 | 3篇 |
2023年 | 13篇 |
2022年 | 16篇 |
2021年 | 19篇 |
2020年 | 32篇 |
2019年 | 31篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 32篇 |
2015年 | 32篇 |
2014年 | 33篇 |
2013年 | 23篇 |
2012年 | 42篇 |
2011年 | 41篇 |
2010年 | 20篇 |
2009年 | 11篇 |
2008年 | 24篇 |
2007年 | 23篇 |
2006年 | 14篇 |
2005年 | 13篇 |
2004年 | 5篇 |
2003年 | 3篇 |
2002年 | 2篇 |
2001年 | 6篇 |
2000年 | 1篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1973年 | 1篇 |
1966年 | 3篇 |
1943年 | 1篇 |
排序方式: 共有473条查询结果,搜索用时 0 毫秒
41.
Franziska Schulte Klaus‐Werner Brzezinka Karin Lutzenberger Heike Stege Ulrich Panne 《Journal of Raman spectroscopy : JRS》2008,39(10):1455-1463
Raman microscopy allows a non‐destructive characterisation of inorganic and organic painting materials such as pigments and organic dyestuffs. The objectives of this study are the more recent organic pigments typically present in paintings and other art works from the 20th century. More than 20 organic synthetic pigments from different chemical classes could be identified by Raman spectroscopy using different excitation wavelengths (457.9, 476.5, 487.9, 514.5, 632.8, and 1064 nm). To evaluate the performance for real paint samples, varying paint mixtures of the Hansa Yellow pigment PY 3 and the binding medium Mowilith, a polyvinyl acetate (PVAC) compound, were characterised; PY 3 was determined at a 1 wt% level in the binder. In addition, commercial tube paints containing the quinacridone violet PV 19 were studied. The pigment was clearly identified in all of these more complex oil and acrylic paints. Finally, alizarin (PR 83) and a green copper phthalocyanine pigment (PG 7) could unambiguously be identified by Raman microscopy in the painting ‘Woman with mandolin in yellow and red’ of Max Beckmann dating 1950. The discovery of a red naphthol AS pigment by Raman spectroscopy in a sample from the ‘Three field workers’ by Georg Baselitz (1964/1965) demonstrated that in some cases complementary chromatographic methods are needed for a comprehensive identification of the organic pigments. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
42.
Franziska Doll Annette Buntz Anne‐Katrin Späte Verena F. Schart Alexander Timper Waldemar Schrimpf Prof. Dr. Christof R. Hauck Prof. Dr. Andreas Zumbusch Prof. Dr. Valentin Wittmann 《Angewandte Chemie (International ed. in English)》2016,55(6):2262-2266
Protein glycosylation is a ubiquitous post‐translational modification that is involved in the regulation of many aspects of protein function. In order to uncover the biological roles of this modification, imaging the glycosylation state of specific proteins within living cells would be of fundamental importance. To date, however, this has not been achieved. Herein, we demonstrate protein‐specific detection of the glycosylation of the intracellular proteins OGT, Foxo1, p53, and Akt1 in living cells. Our generally applicable approach relies on Diels–Alder chemistry to fluorescently label intracellular carbohydrates through metabolic engineering. The target proteins are tagged with enhanced green fluorescent protein (EGFP). Förster resonance energy transfer (FRET) between the EGFP and the glycan‐anchored fluorophore is detected with high contrast even in presence of a large excess of acceptor fluorophores by fluorescence lifetime imaging microscopy (FLIM). 相似文献
43.
Membrane receptors control fundamental cellular processes. Binding of a specific ligand to a receptor initiates communication through the membrane and activation of signaling cascades. This activation process often leads to a spatial rearrangement of receptors in the membrane at the molecular level. Single‐molecule techniques contributed significantly to the understanding of receptor organization and rearrangement in membranes. Here, we review four prominent single‐molecule techniques that have been applied to membrane receptors, namely, stepwise photobleaching, Förster resonance energy transfer, sub‐diffraction localization microscopy and co‐tracking. We discuss the requirements, benefits and limitations of each technique, discuss target labeling, present a selection of applications and results and compare the different methodologies. 相似文献
44.
C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations 下载免费PDF全文
Dr. Torsten Bruhn Dipl.‐Chem. Franziska Witterauf Dr. Daniel C. G. Götz Carina T. Grimmer Dipl.‐Chem. Max Würtemberger Prof. Dr. Udo Radius Prof. Dr. Gerhard Bringmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3998-4006
β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins. 相似文献
45.
Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C−Br,C−OTf,and C−Cl Bonds Enabled by a Single Palladium(I) Dimer 下载免费PDF全文
Dr. Sinead T. Keaveney Gourab Kundu Prof. Dr. Franziska Schoenebeck 《Angewandte Chemie (International ed. in English)》2018,57(38):12573-12577
Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0‐catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br‐selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in <10 min), followed by functionalization of the C?Cl site (in <25 min), at room temperature using the same air‐ and moisture‐stable PdI dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds. 相似文献
46.
Catherine Weetman Amelie Porzelt Prasenjit Bag Franziska Hanusch Shigeyoshi Inoue 《Chemical science》2020,11(18):4817
Main group multiple bonds have proven their ability to act as transition metal mimics in the last few decades. However, catalytic application of these species is still in its infancy. Herein we report the second neutral NHC-stabilised dialumene species by use of a supporting aryl ligand (3). Different to the trans-planar silyl-substituted dialumene (3Si), compound 3 features a trans-bent and twisted geometry. The differences between the two dialumenes are explored computationally (using B3LYP-D3/6-311G(d)) as well as experimentally. A high influence of the ligand''s steric demand on the structural motif is revealed, giving rise to enhanced reactivity of 3 enabled by a higher flexibility in addition to different polarisation of the aluminium centres. As such, facile activation of dihydrogen is now achievable. The influence of ligand choice is further implicated in two different catalytic reactions; not only is the aryl-stabilised dialumene more catalytically active but the resulting product distributions also differ, thus indicating the likelihood of alternate mechanisms simply through a change of supporting ligand.Ligand controlled reactivity: a trans-bent and twisted geometry enables dihydrogen activation and enhanced catalytic activity for NHC-stabilised dialumenes. 相似文献
47.
Grant J. Sherborne Avetik G. Gevondian Ignacio Funes-Ardoiz Amit Dahiya Christoph Fricke Prof. Dr. Franziska Schoenebeck 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15673-15678
Selective C –C couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C−BPin, C−SiMe3, C−I, C−Br, C−Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C−Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N2+ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N2+, which requires an alternative photo-redox approach to enable productive couplings. 相似文献
48.
49.
Franziska Emmerling Caroline Röhr 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(10):1127-1128
The two title trialkaline trioxoantimonates(III), tripotassium trioxoantimonate(III), K3[SbO3], (I), and tricaesium trioxoantimonate(III), Cs3[SbO3], (II), crystallize in the cubic Na3[AsS3] structure type in space group P213. The structures show discrete Ψ-tetrahedral [SbO3]3− anions with C3v point-group symmetry. The Sb—O distances are 1.923 (4) Å in (I) and 1.928 (2) Å in (II), and the O—Sb—O bond angles are 99.5 (2)° in (I) and 100.4 (1)° in (II). 相似文献