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951.
Elemental Sulfur Disproportionation in the Redox Condensation Reaction between o‐Halonitrobenzenes and Benzylamines 下载免费PDF全文
Dr. Thanh Binh Nguyen Dr. Ludmila Ermolenko Dr. Pascal Retailleau Dr. Ali Al‐Mourabit 《Angewandte Chemie (International ed. in English)》2014,53(50):13808-13812
The disproportionation of elemental sulfur at moderate temperatures is investigated in the redox condensation involving o‐halonitrobenzenes 1 and benzylamines 2 . As a redox moderator, elemental sulfur plays the dual role of both electron donor and acceptor, generating its lowest and highest oxidation states: S?2 (sulfide equivalent) in benzothiazole 3 and S+6 (sulfate equivalent) in sulfamate 4 , and filling the electron gap of the global redox condensation process. Along with this process, a cascade of reactions of reduction of the nitro group of 1 , oxidation of the aminomethyl group of 2 , metal‐free aromatic halogen substitution, and condensation finally led to 2‐arylbenzothiazoles 3 . 相似文献
952.
Dr. Cheng‐Chung Lee Dr. Manuel Maestre‐Reyna Dr. Kai‐Cheng Hsu Prof. Dr. Hao‐Ching Wang Prof. Dr. Chia‐I Liu Prof. Dr. Wen‐Yih Jeng Li‐Ling Lin Richard Wood Dr. Chia‐Cheng Chou Prof. Dr. Jinn‐Moon Yang Prof. Dr. Andrew H.‐J. Wang 《Angewandte Chemie (International ed. in English)》2014,53(48):13054-13058
Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization. 相似文献
953.
Phosphorescent Cyclometalated Iridium(III) Complexes That Contain Substituted 2‐Acetylbenzo[b]thiophen‐3‐olate Ligand for Red Organic Light‐Emitting Devices 下载免费PDF全文
Chen Yang Dr. Shiu‐Lun Lai Dr. Sharon Lai‐Fung Chan Dr. Kam‐Hung Low Dr. Gang Cheng Kwan‐Ting Yeung Dr. Chi‐Chung Kwok Prof. Dr. Chi‐Ming Che 《化学:亚洲杂志》2014,9(12):3572-3585
We report the synthesis of a new class of thermally stable and strongly luminescent cyclometalated iridium(III) complexes 1 – 6 , which contain the 2‐acetylbenzo[b]thiophene‐3‐olate (bt) ligand, and their application in organic light‐emitting diodes (OLEDs). These heteroleptic iridium(III) complexes with bt as the ancillary ligand have a decomposition temperature that is 10–20 % higher and lower emission self‐quenching constants than those of their corresponding complexes with acetylacetonate (acac). The luminescent color of these iridium(III) complexes could be fine‐tuned from orange (e.g., 2‐phenyl‐6‐(trifluoromethyl)benzo[d]thiazole (cf3bta) for 4 ) to pure red (e.g., lpt (Hlpt=4‐methyl‐2‐(thiophen‐2‐yl)quinolone) for 6 ) by varying the cyclometalating ligands (C‐deprotonated C^N). In particular, highly efficient OLEDs based on 6 as dopant (emitter) and 1,3‐bis(carbazol‐9‐yl)benzene (mCP) as host that exhibit stable red emission over a wide range of brightness with CIE chromaticity coordinates of (0.67, 0.33) well matched to the National Television System Committee (NTSC) standard have been fabricated along with an external quantum efficiency (EQE) and current efficiency of 9 % and 10 cd A?1, respectively. A further 50 % increase in EQE (>13 %) by replacing mCP with bis[4‐(6H‐indolo[2,3‐b]quinoxalin‐6‐yl)phenyl]diphenylsilane (BIQS) as host for 6 in the red OLED is demonstrated. The performance of OLEDs fabricated with 6 (i.e., [(lpt)2Ir(bt)]) was comparable to that of the analogous iridium(III) complex that bore acac (i.e., [(lpt)2Ir(acac)]; 6 a in this work) [Adv. Mater. 2011 , 23, 2981] fabricated under similar conditions. By using ntt (Hnnt=3‐hydroxynaphtho[2,3‐b]thiophen‐2‐yl)(thiophen‐2‐yl)methanone) ligand, a substituted derivative of bt, the [(cf3bta)2Ir(ntt)] was prepared and found to display deep red emission at around 700 nm with a quantum yield of 12 % in mCP thin film. 相似文献
954.
Hexanuclear Gold(I) Phosphide Complexes as Platforms for Multiple Redox‐Active Ferrocenyl Units 下载免费PDF全文
Dr. Terence Kwok‐Ming Lee Dr. Eddie Chung‐Chin Cheng Dr. Nianyong Zhu Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):304-310
The synthesis, X‐ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ3‐ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au6(P?P)n(Fc‐CH2‐P)2][PF6]2 (n=3, P?P=dppm (bis(diphenylphosphino)methane) ( 1 ), dppe (1,2‐bis(diphenylphosphino)ethane) ( 2 ), dppp (1,3‐bis(diphenylphosphino)propane) ( 3 ), Ph2PN(C3H7)‐PPh2 ( 4 ), Ph2PN(Ph‐CH3‐p)PPh2 ( 5 ), dppf (1,1′‐bis(diphenylphosphino)ferrocene) ( 6 ); n=2, P?P=dpepp (bis(2‐diphenylphosphinoethyl)phenylphosphine) ( 7 )), as platforms for multiple redox‐active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ3‐ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au6P2 cluster core, providing an understanding of the electronic properties of the hexanuclear AuI cluster linkage. The present complexes also serve as an ideal system for the design of multi‐electron reservoir and molecular battery systems. 相似文献
955.
Chemical Probing of the Human Sirtuin 5 Active Site Reveals Its Substrate Acyl Specificity and Peptide‐Based Inhibitors 下载免费PDF全文
Claudia Roessler Theresa Nowak Martin Pannek Dr. Melanie Gertz Giang T. T. Nguyen Michael Scharfe Dr. Ilona Born Prof. Dr. Wolfgang Sippl Prof. Dr. Clemens Steegborn Prof. Dr. Mike Schutkowski 《Angewandte Chemie (International ed. in English)》2014,53(40):10728-10732
Sirtuins are NAD+‐dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide‐based inhibitors that interact with the NAD+ binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X‐ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5. 相似文献
956.
Multi‐Species Multi‐Channel (MSMC): An Ab Initio‐based Parallel Thermodynamic and Kinetic Code for Complex Chemical Systems 下载免费PDF全文
Multi‐Species Multi‐Channel (MSMC) is an ab initio parallel program to calculate thermodynamic quantities (e.g., , , , and , time‐dependent species profiles, and rate coefficients as functions of temperature and pressure for complex chemical reaction systems, which consist of multiple stable species and multiple reaction channels interconnecting them. Thermodynamic properties of the species involved are calculated using statistical mechanics with molecular information from electronic structure calculations. Temperature‐ and pressure‐dependent behaviors are rigorously characterized within the eigenpair master equation/Rice–Ramsperger–Kassel–Marcus (ME/RRKM) framework. Corrections, e.g., for hindered internal rotation and tunneling treatment, are included. With the implementation of an ultra‐high precision package and rigorous matrix setup, MSMC is able to correctly mimic real behaviors of different types of chemical systems. Different eigenpair‐based approaches to extract phenomenological/macroscopic rate coefficients are implemented for different applications. Moreover, a friendly and platform‐independent graphical‐user‐interface (GUI) is provided to facilitate the use of MSMC and the pre‐/postcalculation data visualization/analysis on the fly. The program can be freely downloaded at https://sites.google.com/site/msmccode/ . 相似文献
957.
Dr. Georgian Melinte Dr. Veselina Georgieva Dr. Marie‐Anne Springuel‐Huet Dr. Andreï Nossov Prof. Ovidiu Ersen Dr. Flavien Guenneau Prof. Antoine Gedeon Dr. Ana Palčić Dr. Krassimir N. Bozhilov Dr. Cuong Pham‐Huu Prof. Shilun Qiu Dr. Svetlana Mintova Dr. Valentin Valtchev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18316-18327
The principle aspects and constraints of the dynamics and kinetics of zeolite nucleation in hydrogel systems are analyzed on the basis of a model Na‐rich aluminosilicate system. A detailed time‐series EMT‐type zeolite crystallization study in the model hydrogel system was performed to elucidate the topological and temporal aspects of zeolite nucleation. A comprehensive set of analytical tools and methods was employed to analyze the gel evolution and complement the primary methods of transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectroscopy. TEM tomography reveals that the initial gel particles exhibit a core–shell structure. Zeolite nucleation is topologically limited to this shell structure and the kinetics of nucleation is controlled by the shell integrity. The induction period extends to the moment when the shell is consumed and the bulk solution can react with the core of the gel particles. These new findings, in particular the importance of the gel particle shell in zeolite nucleation, can be used to control the growth process and properties of zeolites formed in hydrogels. 相似文献
958.
Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions 下载免费PDF全文
Luca Assumma Cristina Iojoiu Régis Mercier Sandrine Lyonnard Huu Dat Nguyen Emilie Planes 《Journal of polymer science. Part A, Polymer chemistry》2015,53(16):1941-1956
Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H+/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by 1H and 19F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956 相似文献
959.
Feng-Yun Wang Soofin Cheng Chen-Hung Chung Ben-Zu Wan 《Journal of Solid State Electrochemistry》2006,10(11):879-885
Electrolytes of Ce1-x-y
Y
x
Mg
y
O2-0.5x-y
were prepared with citrate method and were characterized by inductively coupled plasma-atomic emission spectrometry, energy dispersive spectrometry, powder X-ray diffraction, and impedance spectroscopy. The effect of composition on the structure, conductivity, and stability of the electrolytes were investigated. When 0≤x≤ about 0.2 and 0≤y≤ about 0.05, the electrolytes were all single phase materials of ceria-based solid solution. However, when y> about 0.05, the electrolytes became two-phase materials, Y3+ and Mg2+ co-doped ceria-based solid solution and free MgO. The sample with nominal composition of Ce0.815Y0.065Mg0.12O2-d
showed ionic conductivity at 973 K close to or even a little higher than that of similarly prepared Ce0.9Gd0.1O1.95, but had lower cost of raw materials and a little better stability in reducing atmosphere. The existing of free MgO improved the stability of the electrolytes in reducing atmosphere, but too much free MgO reduced the conductivity. 相似文献
960.
Ngo Quang Huy Trinh Thi Bich Nguyen Van Suc 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(1):129-133
Summary The paper presents a procedure to prepare soil samples for U and Th isotope measurement by alpha-spectrometry after coprecipitation
with LaF3. In this procedure the reduction of U(VI) to U(IV) was performed by Zn metal in 4M HCl solution. The recoveries of chemical
separation equal to eU-chemistry = 78±4% for uranium and eTh-chemistry = 82±4% for thorium. Canberra alpha-spectrometer was used with PIPS detectors of A-1200-37-AM Model of 1200 mm2 active area. The counting efficiency of the measuring system equals to ecounting = 18% and the total efficiencies were eU = ecounting .eU-chemistry = 14.0±0.7% for uranium and eTh = ecounting .eTh-chemistry = 14.7±0.7% for thorium. The recoveries of chemical separation were rather high (about 80%), that leads to the use of a small
weight of soil sample (about 0.5 g). The efficiencies were also stable, that allows analyzing the soil sample without using
radiotracers. They are advantages of the sample preparation procedure of this work. 相似文献