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961.
Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations 下载免费PDF全文
Dr. Marie‐Alexandra Neouze Martin Kronstein Dr. Marco Litschauer Dr. Michael Puchberger Dr. Cristina Coelho Prof. Christian Bonhomme Prof. Christel Gervais Dr. Frederik Tielens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15188-15196
A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. 11B and 31P HETCOR CP MAS experiments were recorded. Calculated 19F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain. 相似文献
962.
Mechanistic Insights into RNA Transphosphorylation from Kinetic Isotope Effects and Linear Free Energy Relationships of Model Reactions 下载免费PDF全文
Haoyuan Chen Dr. Timothy J. Giese Dr. Ming Huang Prof. Dr. Kin‐Yiu Wong Prof. Dr. Michael E. Harris Prof. Dr. Darrin M. York 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14336-14343
Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate‐controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition‐state structure and bonding optimally requires the use of theoretical models. In this work, we apply density‐functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2′‐O‐transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well‐studied series of phosphate and phosphorothioate mono‐, di‐ and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non‐enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate–KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of building up knowledge of mechanism through the systematic study of model systems to provide insight into more complex biological systems such as phosphoryl transfer enzymes and ribozymes. 相似文献
963.
Synthesis of Single‐Crystalline Spinel LiMn2O4 Nanorods for Lithium‐Ion Batteries with High Rate Capability and Long Cycle Life 下载免费PDF全文
Xiuqiang Xie Dr. Dawei Su Dr. Bing Sun Jinqiang Zhang Prof. Dr. Chengyin Wang Prof. Dr. Guoxiu Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17125-17131
The long‐standing challenge associated with capacity fading of spinel LiMn2O4 cathode material for lithium‐ion batteries is investigated. Single‐crystalline spinel LiMn2O4 nanorods were successfully synthesized by a template‐engaged method. Porous Mn3O4 nanorods were used as self‐sacrificial templates, into which LiOH was infiltrated by a vacuum‐assisted impregnation route. When used as cathode materials for lithium‐ion batteries, the spinel LiMn2O4 nanorods exhibited superior long cycle life owing to the one‐dimensional nanorod structure, single‐crystallinity, and Li‐rich effect. LiMn2O4 nanorods retained 95.6 % of the initial capacity after 1000 cycles at 3C rate. In particular, the nanorod morphology of the spinel LiMn2O4 was well‐preserved after a long‐term cycling, suggesting the ultrahigh structural stability of the single crystalline spinel LiMn2O4 nanorods. This result shows the promising applications of single‐crystalline spinel LiMn2O4 nanorods as cathode materials for lithium‐ion batteries with high rate capability and long cycle life. 相似文献
964.
CuII/TEMPO‐Promoted One‐Pot Synthesis of Highly Substituted Pyrimidines from Amino Acid Esters 下载免费PDF全文
Dr. Nini Zhou Tao Xie Zhongle Li Prof. Dr. Zhixiang Xie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17311-17314
A novel, Cu(OAc)2/TEMPO promoted one‐step approach for the preparation of fully substituted pyrimidines from readily available amino acid esters has been described. In this reaction, the amino acid esters act as the only N?C sources for the construction of corresponding pyrimidines. The mechanism of this process includes oxidative dehydrogenation, the generation of an imine radical, and a formal [3+3] cycloaddition. This methodology proves to be a high atom‐economic and straightforward strategy for the synthesis of pyrimidines and diverse substrates which are substituted by various functional groups have been afforded in moderate to good yield. 相似文献
965.
Chemical Fixation of CO2 and Other Heterogeneous Catalytic Studies by Employing a Layered Cu‐Porphyrin Prepared Through Single‐Crystal to Single‐Crystal Exchange of a Zn Analogue 下载免费PDF全文
A solvothermal reaction of Zn(NO3)2 ? 6 H2O, tetra‐(4‐pyridyl)porphyrin (H2TPyP), and 4,4′‐oxybis(benzoic acid) (H2OBA) resulted in a new two‐dimensional Zn‐ porphyrin metal–organic framework compound, [Zn2(C40H24N8)0.5(C14H8O5)(DMA)](DMA)(H2O)6 ( 1 ; DMA=N,N‐dimethylacetamide). The ZnII ions present in 1 could be exchanged by using a solution of Cu(NO3)2 ? 3 H2O in DMA at room temperature to give [Cu2(C40H24N8)0.5(C14H8O5)(DMA)](DMA)(H2O)3 ( Cu∈1 ). The extra‐framework solvent molecules have been shown to be reversibly removed or exchanged without collapse of the framework. Solvent‐free Cu∈1 was explored as an active heterogeneous catalyst towards three different organic reactions: 1) the chemical fixation of CO2 into cyclic carbonate at room temperature and 1 atm; 2) the nitroaldol reaction under solvent‐free conditions, and 3) the three‐component coupling of aminopyridine, benzaldehyde, and aryl alkynes followed by 5‐exo‐dig cyclization to produce the important pharmacophore imidazopyridine. 相似文献
966.
A dendrimeric trimer undergoes folding and unfolding in response to a chemical stimulus. The trimer of interest contains a central dendrimer with a butadiyne‐linked zinc porphyrin dimer ((ZnP)2) core, in addition to two terminal dendrimers with zinc porphyrin (ZnP) cores. The obtained absorption spectra indicate that the unfolded form is the exclusive conformer in chloroform, while the addition of 1,4‐diazabicyclo[2.2.2]octane (DABCO) in chloroform leads to transformation from the unfolded to the folded structure containing two DABCO units per trimer; the folded structure originates from the cross‐linking of (ZnP)2 and ZnP with DABCO. Moreover, the addition of excess DABCO promotes the generation of the unfolded structure containing four DABCO units. 相似文献
967.
Prof. Dr. Gang Li Prof. Dr. Jianfeng Zhao Shufan Yang Dr. Yongxin Li Dr. Ganguly Rakesh Prof. Dr. Qichun Zhang 《化学:亚洲杂志》2018,13(3):250-254
Understanding the oxidation mechanism and positions of twistacenes and twistheteroacenes under ambient conditions is very important because such knowledge can guide us to design and synthesize novel, larger stable analogues. Herein, we demonstrated for the first time that a twisted isoquinolinone can decompose under oxygen and light at room temperature. The as‐decomposed product 1 was fully characterized through conventional methods as well as single‐crystal structure analysis. Moreover, the physical properties of the as‐obtained product were carefully investigated and the possible formation mechanism was proposed. 相似文献
968.
Cong Li Rui Zang Pengxin Li Zengming Man Shijian Wang Xuemei Li Yuhan Wu Shuaishuai Liu Prof. Guoxiu Wang 《化学:亚洲杂志》2018,13(3):342-349
Prussian blue and its analogues (PBAs) have been recognized as one of the most promising cathode materials for room‐temperature sodium‐ion batteries (SIBs). Herein, we report high crystalline and Na‐rich Prussian white Na2CoFe(CN)6 nanocubes synthesized by an optimized and facile co‐precipitation method. The influence of crystallinity and sodium content on the electrochemical properties was systematically investigated. The optimized Na2CoFe(CN)6 nanocubes exhibited an initial capacity of 151 mA h g?1, which is close to its theoretical capacity (170 mA h g?1). Meanwhile, the Na2CoFe(CN)6 cathode demonstrated an outstanding long‐term cycle performance, retaining 78 % of its initial capacity after 500 cycles. Furthermore, the Na2CoFe(CN)6 Prussian white nanocubes also achieved a superior rate capability (115 mA h g?1 at 400 mA g?1, 92 mA h g?1 at 800 mA g?1). The enhanced performances could be attributed to the robust crystal structure and rapid transport of Na ions through large channels in the open‐framework. Most noteworthy, the as‐prepared Na2CoFe(CN)6 nanocubes are not only low‐cost in raw materials but also contain a rich sodium content (1.87 Na ions per lattice unit cell), which will be favorable for full cell fabrication and large‐scale electric storage applications. 相似文献
969.
Synthesis of Functionalized (η5‐Indenyl)rhodium(III) Complexes and Their Application to C−H Bond Functionalization 下载免费PDF全文
It has been established that reductive complexation of functionalized benzofulvenes, which are readily prepared from commercially available indene and 2‐methylindene, with RhCl3 in ethanol affords the corresponding indenyl–rhodium(III) dichlorides bearing substituents at the 1‐ (H or CO2Et), 2‐ (H or Me), and 3‐ [CH2Ph or CH2(2‐MeOC6H4)] positions. The indenyl–rhodium(III) complexes bearing one ethoxycarbonyl group showed higher thermal stability and regioselectivity than our previously reported CpERhIII complex toward the oxidative [3+2] annulation of acetanilides with internal alkynes. 相似文献
970.
The development of robust photothermal agents for near‐infrared (NIR) imaging is a great challenge. Herein, we report the design and synthesis of a new photothermal agent, based on the aza‐boron‐dipyrromethene framework (azaBDP). This compound possessed excellent photostability and high photothermal‐conversion efficiency (50 %) under NIR laser irradiation. When the photothermal properties of this compound were utilized for tumor inhibition, stable long‐term fluorescence was observed in living animals. Photothermal treatment efficiently suppressed tumor growth, as evidenced by in vitro and in vivo experiments. Furthermore, NIR emission could be detected by using an imaging system and therapeutic self‐monitoring was achieved by using NIR imaging. 相似文献