全文获取类型
收费全文 | 599篇 |
免费 | 52篇 |
国内免费 | 2篇 |
专业分类
化学 | 493篇 |
晶体学 | 2篇 |
力学 | 11篇 |
数学 | 70篇 |
物理学 | 77篇 |
出版年
2023年 | 17篇 |
2022年 | 9篇 |
2021年 | 14篇 |
2020年 | 23篇 |
2019年 | 21篇 |
2018年 | 13篇 |
2017年 | 8篇 |
2016年 | 35篇 |
2015年 | 27篇 |
2014年 | 23篇 |
2013年 | 43篇 |
2012年 | 44篇 |
2011年 | 56篇 |
2010年 | 33篇 |
2009年 | 16篇 |
2008年 | 44篇 |
2007年 | 49篇 |
2006年 | 32篇 |
2005年 | 49篇 |
2004年 | 25篇 |
2003年 | 21篇 |
2002年 | 14篇 |
2001年 | 10篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1991年 | 1篇 |
排序方式: 共有653条查询结果,搜索用时 15 毫秒
451.
Dr. Fredj Ben Bdira Dr. Christopher A. Waudby Dr. Alexander N. Volkov Dr. Sybrin P. Schröder Dr. Eiso AB Prof. Dr. Jeroen D. C. Codée Prof. Dr. Hermen S. Overkleeft Prof. Dr. Johannes M. F. G. Aerts Dr. Hugo van Ingen Prof. Dr. Marcellus Ubbink 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20689-20695
The single-domain GH11 glycosidase from Bacillus circulans (BCX) is involved in the degradation of hemicellulose, which is one of the most abundant renewable biomaterials in nature. We demonstrate that BCX in solution undergoes minimal structural changes during turnover. NMR spectroscopy results show that the rigid protein matrix provides a frame for fast substrate binding in multiple conformations, accompanied by slow conversion, which is attributed to an enzyme-induced substrate distortion. A model is proposed in which the rigid enzyme takes advantage of substrate flexibility to induce a conformation that facilitates the acyl formation step of the hydrolysis reaction. 相似文献
452.
Jeroen A. Rombouts Janneke Ravensbergen Dr. Raoul N. Frese Dr. John T. M. Kennis Dr. Andreas W. Ehlers Dr. J. Chris Slootweg Dr. Eelco Ruijter Prof. Dr. Koop Lammertsma Prof. Dr. Romano V. A. Orru 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10285-10291
In search of supramolecular antenna systems for light‐harvesting applications, we report on a short and effective synthesis of a fused NDI–zinc–salphen‐based chromophore (salphen = bis‐salicylimide phenylene) and its photophysical properties. A supramolecular recognition motif is embedded into the chromophoric π‐system of this compound. The fused π‐chromophore behaves as one pigment, absorbs light between 600 and 750 nm and displays a modest Stokes shift. Upon binding pyridines, the compound ( DATZnS ) does not change its redox potentials, does not undergo any internal excited state quenching and does not appreciably alter its excited state lifetime. These notable properties define DATZnS as an alternative to porphyrin‐based components used in supramolecular light‐harvesting architectures. 相似文献
453.
454.
455.
Stijn F. M. van Dongen Madhavan Nallani Dr. Jeroen J. L. M. Cornelissen Dr. Roeland J. M. Nolte Prof. Dr. Jan C. M. van Hest Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(5):1107-1114
Porous polymersomes based on block copolymers of isocyanopeptides and styrene have been used to anchor enzymes at three different locations, namely, in their lumen (glucose oxidase, GOx), in their bilayer membrane (Candida antarctica lipase B, CalB) and on their surface (horseradish peroxidase, HRP). The surface coupling was achieved by click chemistry between acetylene-functionalised anchors on the surface of the polymersomes and azido functions of HRP, which were introduced by using a direct diazo transfer reaction to lysine residues of the enzyme. To determine the encapsulation and conjugation efficiency of the enzymes, they were decorated with metal-ion labels and analysed by mass spectrometry. This revealed an almost quantitative immobilisation efficiency of HRP on the surface of the polymersomes and a more than statistical incorporation efficiency for CalB in the membrane and for GOx in the aqueous compartment. The enzyme-decorated polymersomes were studied as nanoreactors in which glucose acetate was converted by CalB to glucose, which was oxidised by GOx to gluconolactone in a second step. The hydrogen peroxide produced was used by HRP to oxidise 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) to ABTS.+. Kinetic analysis revealed that the reaction step catalysed by HRP is the fastest in the cascade reaction. 相似文献
456.
Erika Wikberg Jeroen J. Verhage Camilla Viklund Knut Irgum 《Journal of separation science》2009,32(12):2008-2016
Porous silica particles of 3 μm diameter and 100 Å nominal pore size were first activated for vinylic polymerization by functionalization with 3-methacryloyloxypropyl trimethoxysilane (MAPTMS) and thereafter dressed with zwitterionic grafts of the sulfoalkylbetaine type in the “grafting through” fashion by polymerizing 3-(2-(N-methacryloyloxyethyl)-N,N-dimethylammonio)propane sulfonate (SPE), using either free radical polymerization or controlled reversible addition fragmentation chain transfer polymerization (RAFT). Particles polymerized using RAFT had a lower overall coating which seemed to be more evenly distributed in the pore volume. Both approaches resulted in columns with similar separation properties in HILIC mode. 相似文献
457.
Zeyou Pan Allen Puente-Urbina Andras Bodi Jeroen A. van Bokhoven Patrick Hemberger 《Chemical science》2021,12(9):3161
The catalytic pyrolysis mechanism of the initial lignin depolymerization products will help us develop biomass valorization strategies. How does isomerism influence reactivity, product formation, selectivities, and side reactions? By using imaging photoelectron photoion coincidence (iPEPICO) spectroscopy with synchrotron radiation, we reveal initial, short-lived reactive intermediates driving benzenediol catalytic pyrolysis over H-ZSM-5 catalyst. The detailed reaction mechanism unveils new pathways leading to the most important products and intermediates. Thanks to the two vicinal hydroxyl groups, catechol (o-benzenediol) is readily dehydrated to form fulvenone, a reactive ketene intermediate, and exhibits the highest reactivity. Fulvenone is hydrogenated on the catalyst surface to phenol or is decarbonylated to produce cyclopentadiene. Hydroquinone (p-benzenediol) mostly dehydrogenates to produce p-benzoquinone. Resorcinol, m-benzenediol, is the most stable isomer, because dehydration and dehydrogenation both involve biradicals owing to the meta position of the hydroxyl groups and are unfavorable. The three isomers may also interconvert in a minor reaction channel, which yields small amounts of cyclopentadiene and phenol via dehydroxylation and decarbonylation. We propose a generalized reaction mechanism for benzenediols in lignin catalytic pyrolysis and provide detailed mechanistic insights on how isomerism influences conversion and product formation. The mechanism accounts for processes ranging from decomposition reactions to molecular growth by initial polycyclic aromatic hydrocarbon (PAH) formation steps to yield, e.g., naphthalene. The latter involves a Diels–Alder dimerization of cyclopentadiene, isomerization, and dehydrogenation.Detection of reactive intermediates with synchrotron radiation and photoelectron photoion coincidence methods reveals new mechanistic insights into lignin catalytic pyrolysis. Here we focus on how the isomerism changes the conversion and product formation. 相似文献
458.
459.
We generalize the Existential Divisibility Lemma by Th. Pheidas [7] to all global fields K of characteristic not 2, and for all sets of primes that are inert in a quadratic extension L of K. We also remove the conditions in real and ramifying primes, which were present in Pheidas’ version. As a Corollary, we recover
the known fact that the set of integral elements at a prime in a global field is existentially definable.
The first author is a Research Assistant of the Research Foundation – Flanders (FWO – Vlaanderen).
Work partially supported by the European Community’s Human Potential Programme under contract HPRN-CT-2002-00287. 相似文献
460.