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71.
SAXS and WAXD study of periodical structure for polyacrylonitrile fiber during coagulation 下载免费PDF全文
Small angle X‐ray scattering (SAXS) and wide angle X‐ray diffraction (WAXD) were adopted to investigate the formation and development of high order structure within polyacrylonitrile (PAN) precursor during coagulation. The scattering signal came from the microvoids and long period structure was separated reasonably by the analog computation method of decomposition of the one‐dimensional profile. Based on the established methodology, the statistic parameters of long period structure, such as length of the long period structure, crystalline region and amorphous region, were obtained by the analysis of correlation function. The results indicated that during the coagulation, the length of long period of the nascent coagulated fiber was 56.1 nm (meridional direction) and 35.6 nm (equatorial direction), respectively. The evolution of the long period during the coagulation was also discussed by combining WAXD data. With the processing of coagulation, the long period was decreased since the crystallinity increased. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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73.
Intermolecular Dynamic Kinetic Resolution Cooperatively Catalyzed by an N‐Heterocyclic Carbene and a Lewis Acid 下载免费PDF全文
Zijun Wu Fangyi Li Prof. Dr. Jian Wang 《Angewandte Chemie (International ed. in English)》2015,54(5):1629-1633
The ubiquitous structure of δ‐lactones makes the development of new methods for their enantioselective and stereoselective synthesis an important ongoing challenge. The intermolecular dynamic kinetic resolution (DKR) of β‐halo‐α‐ketoesters cooperatively catalyzed by an N‐heterocyclic carbene and a Lewis acid generates two contiguous stereocenters with remarkable diastereoselectivity through an oxidation/lactonization sequence. 相似文献
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75.
A Combined Experimental and Theoretical Study on the Stereodynamics of Monoaza[5]helicenes: Solvent‐Induced Increase of the Enantiomerization Barrier in 1‐Aza‐[5]helicene 下载免费PDF全文
Prof. Dr. Tullio Caronna Prof. Dr. Andrea Mele Prof. Dr. Antonino Famulari Dr. Daniele Mendola Prof. Dr. Francesca Fontana Dr. Markus Juza Dr. Matthias Kamuf Dr. Kerstin Zawatzky Prof. Dr. Oliver Trapp 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13919-13924
Helicenes and heterohelicenes are attractive compounds with great potential in materials sciences to be used in optoelectronics as ligand backbones in enantioselective catalysis and as chiral sensors. The properties of these materials are related to the stereodynamics of these helical chiral compounds. However, little is known about features controlling stereodynamics in helicenes; in particular, for heterohelicenes the position of the heteroatom could be relevant in this respect. Herein the complete stereodynamic characterization of monoaza[5]helicenes is shown by enantioselective dynamic HPLC and DFT calculations. At variance with previous theoretical calculations, 1‐aza[5]helicene shows a surprisingly high enantiomerization barrier, which is triggered by specific solvent interactions. 相似文献
76.
Dynamic Covalent Organocatalysts Discovered from Catalytic Systems through Rapid Deconvolution Screening 下载免费PDF全文
Fredrik Schaufelberger Prof. Olof Ramström 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(36):12735-12740
The first example of a bifunctional organocatalyst assembled through dynamic covalent chemistry (DCC) is described. The catalyst is based on reversible imine chemistry and can catalyze the Morita–Baylis–Hillman (MBH) reaction of enones with aldehydes or N‐tosyl imines. Furthermore, these dynamic catalysts were shown to be optimizable through a systemic screening approach, in which large mixtures of catalyst structures were generated, and the optimal catalyst could be directly identified by using dynamic deconvolution. This strategy allowed one‐pot synthesis and in situ evaluation of several potential catalysts without the need to separate, characterize, and purify each individual structure. The systems were furthermore shown to catalyze and re‐equilibrate their own formation through a previously unknown thiourea‐catalyzed transimination process. 相似文献
77.
Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes 下载免费PDF全文
Qing Ji Ha T. M. Le Dr. Xiqu Wang Dr. Yu‐Sheng Chen Dr. Tatyana Makarenko Prof. Allan J. Jacobson Prof. Ognjen Š. Miljanić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17205-17209
Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m2 g?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation. 相似文献
78.
通过两步水热法合成了一种新型的还原氧化石墨烯(RGO)修饰的Bi2WO6(Bi2WO6-RGO), 结果表明其在可见光下的光催化性能得到了显著的提高. 研究了RGO在Bi2WO6-RGO中的含量对其光催化性能的影响, 从而确定出RGO相对于Bi2WO6的最佳掺杂质量比值为1%. 通过扫描电镜(SEM)研究发现, RGO并没有改变Bi2WO6光催化剂的结构和形貌. Bi2WO6-RGO在可见光下的光催化性能得以提高可以归功于RGO. 其可能的机理是石墨烯的存在有利于光生载流子(激子)的分离, 从而导致产生更多的O2·-用于有机染料污染物(如罗丹明B (RhB))的降解. RhB分子在石墨烯上的有效吸附可能也是导致Bi2WO6-RGO光催化性能提高的另一原因. 相似文献
79.
Marie‐Laure Louillat‐Habermeyer Rongwei Jin Prof. Dr. Frederic W. Patureau 《Angewandte Chemie (International ed. in English)》2015,54(13):4102-4104
A method was developed for the direct dehydrogenative construction of C? N bonds between unprotected phenols and a series of cyclic anilines without resorting to any kind of metal activation of either substrate and without the use of halides. The resulting process relies on the exclusively organic activation of molecular oxygen and the subsequent oxidation of the aniline substrate. This allows the coupling of ubiquitous phenols, thus furnishing aminophenols through an atom‐economical and most sustainable dehydrogenative amination method. This new reactivity, which relies on the intrinsic organic reactivity of cumene in what can be seen as a modified Hock activation process of oxygen, is expected to have a large impact on the formation of C? N bonds in organic synthesis. 相似文献
80.
Thomas Heuser Elisabeth Weyandt Dr. Andreas Walther 《Angewandte Chemie (International ed. in English)》2015,54(45):13258-13262
Switchable self‐assemblies respond to external stimuli with a transition between near‐equilibrium states. Although being a key to present‐day advanced materials, these systems respond rather passively, and do not display autonomous dynamics. For autonomous behavior, approaches must be found to orchestrate the time domain of self‐assemblies, which would lead to new generations of dynamic and self‐regulating materials. Herein, we demonstrate catalytic control of the time domain of pH‐responsive peptide hydrogelators in a closed system. We program transient acidic pH states by combining a fast acidic activator with the slow, enzymatic, feedback‐driven generation of a base (dormant deactivator). This transient state can be programmed over orders of magnitude in time. It is coupled to dipeptides to create autonomously self‐regulating, dynamic gels with programmed lifetimes, which are used for fluidic guidance, burst release, and self‐erasing rapid prototyping. 相似文献