全文获取类型
收费全文 | 191篇 |
免费 | 30篇 |
专业分类
化学 | 154篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 37篇 |
物理学 | 27篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 4篇 |
2016年 | 12篇 |
2015年 | 14篇 |
2014年 | 11篇 |
2013年 | 9篇 |
2012年 | 17篇 |
2011年 | 19篇 |
2010年 | 6篇 |
2009年 | 6篇 |
2008年 | 10篇 |
2007年 | 5篇 |
2006年 | 16篇 |
2005年 | 13篇 |
2004年 | 9篇 |
2003年 | 4篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1997年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1972年 | 1篇 |
1971年 | 4篇 |
1970年 | 4篇 |
1958年 | 1篇 |
1928年 | 2篇 |
1921年 | 1篇 |
排序方式: 共有221条查询结果,搜索用时 31 毫秒
11.
Toni Neuwirth Dr. Anne-Catrin Letzel Cedric Tank Dr. Keishi Ishida Michael Cyrulies Dr. Lisa Schmölz Prof. Dr. Stefan Lorkowski Prof. Dr. Christian Hertweck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15855-15858
The anaerobe Clostridium acetobutylicum belongs to the most important industrially used bacteria. Whereas genome mining points to a high potential for secondary metabolism in C. acetobutylicum, the functions of most biosynthetic gene clusters are cryptic. We report that the addition of supra-physiological concentrations of cysteine triggered the formation of a novel natural product, clostrisulfone ( 1 ). Its structure was fully elucidated by NMR, MS and the chemical synthesis of a reference compound. Clostrisulfone is the first reported natural product with a diphenylsulfone scaffold. A biomimetic synthesis suggests that pentamethylchromanol-derived radicals capture sulfur dioxide to form 1 . In a cell-based assay using murine macrophages a biphasic and dose-dependent regulation of the LPS-induced release of nitric oxide was observed in the presence of 1 . 相似文献
12.
A novel approach for the syntheses of carbene adduct 4 is reported. A ring-enlargement strategy was employed for the synthesis of precursors 5 and 6 and established the mechanism of the formation of azulene derivative 6. Synthesis of target precursor 13, a novel precursor for the synthesis of new mesogenic materials, and its various halogenated derivatives (14–16) was carried out. 相似文献
13.
The ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) was successfully used as alternative solvent for native chemical ligation of peptide fragments to produce model peptide LYRAXCRANK (X = G, A, L, N, Q, K, and F). The commonly used buffer system including thiol additives such as thiophenol and benzyl mercaptan can be replaced by the nontoxic ionic liquid [C2mim][OAc]. In addition to improving the solubility of the peptides in [C2mim][OAc], yields and rates of the ligation reactions were found to be efficiently enhanced. 相似文献
14.
Evgeny Bulatov Toni Eskelinen Alexander Yu. Ivanov Prof. Peter M. Tolstoy Elina Kalenius Pipsa Hirva Prof. Matti Haukka 《Chemphyschem》2021,22(20):2044-2049
Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions. 相似文献
15.
16.
Metal‐Catalyzed Reductive Coupling Reactions of Organic Halides with Carbonyl‐Type Compounds
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Toni Moragas Dr. Arkaitz Correa Prof. Dr. Ruben Martin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8242-8258
Metal‐catalyzed reductive coupling reactions of aryl halides and (pseudo)halides with carbonyl‐type compounds have undergone an impressive development within the last years. These methodologies have shown to be a powerful alternate strategy, practicality aside, to the use of stoichiometric, well‐defined, and, in some cases, air‐sensitive organometallic species. In this Minireview, the recent findings in this field are summarized, with particular emphasis on the mechanistic interpretation of the results and future aspects of this area of expertise. 相似文献
17.
Tandem mass spectrometric analysis of S‐ and N‐linked glutathione conjugates of pulegone and menthofuran and identification of P450 enzymes mediating their formation
下载免费PDF全文
![点击此处可从《Rapid communications in mass spectrometry : RCM》网站下载免费的PDF全文](/ch/ext_images/free.gif)
18.
A system of determining entrance surface doses (ESDs) from diagnostic X-ray examination is described. It is shown that the radiation yield calibrations of X-ray units (μGym2mAs−1) can be based on very simple measurements with TL dosimeters. Comparisons of determined ESDs with the guidelines of international organizations are carried out with the aim of demonstrating the idea of how these values can be utilized in limiting patient doses. 相似文献
19.
Virta P Holmström T Roslund MU Mattjus P Kronberg L Sjöholm R 《Organic & biomolecular chemistry》2004,2(6):821-827
Four novel derivatives of 2-amino-9-(beta-D-ribofuranosyl)purine (1) were synthesised and fully characterised. When 1 was reacted with chloroacetaldehyde (a), 2-chloropropanal (b), bromomalonaldehyde (c) and a mixture of chloroacetaldehyde + malonaldehyde (d), 3-(beta-D-ribofuranosyl)-imidazo-[1,2a]purine (2), 3-(beta-D-ribofuranosyl)-5-methylimidazo-[1,2a]purine (3), 3-(beta-D-ribofuranosyl)-5-formylimidazo-[1,2a]purine (4) and 9-(beta-D-ribofuranosyl)-2-(3,5-diformyl-4-methyl-1,4-dihydro-1-pyridyl)purine (5) were formed, respectively. The products were isolated, purified by chromatography and characterised by MS, complete NMR assignment as well as fluorescence and UV spectroscopy. The yields of these reactions were moderate (14-20%). The fluorescence properties differed from those of the starting compound and the quantum yields were considerably lower. 相似文献
20.
Frank Langhans Stefan Kiefer Carsten Hartmann Toni Markurt Tobias Schulz Christo Guguschev Martin Naumann Sandro Kollowa Andrea Dittmar Jürgen Wollweber Matthias Bickermann 《Crystal Research and Technology》2016,51(2):129-136
In order to evaluate the possible involvement of crucible materials in the growth of AlN bulk crystals grown by physical vapor transport, we applied growth conditions with a high vertical thermal gradient and hence high supersaturation of aluminum vapor. Under these conditions, precipitates formed causing diffuse grayish substructures at the initial growth interface and in the crystal body, decorating dislocations. Electron microscopy studies revealed that the precipitates are elongated, single‐phase particles with sizes of 50–500 nm of commensurate structure, oriented along the <110> direction. Chemical analysis of the precipitates showed tungsten as well as carbon and oxygen. The lattice parameters of the precipitates are in close agreement to hexagonal tungsten hemicarbide (W2C). The possible transport from the tungsten parts and its conversion into tungsten hemicarbide precipitates is discussed. We thus conclude that the W2C precipitates may contribute to the decoration of dislocations, even in growth with moderate thermal gradients. 相似文献