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961.
Jialin Liu Jingrui Li Mengjin Fan Junying Zhang Jue Cheng 《Journal of Thermal Analysis and Calorimetry》2014,117(2):603-610
Aromatic amine curing agent with flexible unit in backbone, 1,4-bis (4-diaminobenzene-1-oxygen) n-butane (DDBE), was synthesized, and the structure was confirmed by FT-IR and 1H NMR. The curing kinetics of tetraglycidyl methylene dianiline (TGDDM, or AG80) using DDBE and 4,4′-bis-(diaminodiphenyl) methane (DDM) as curing agents, respectively, were comparatively studied by non-isothermal DSC with a model-fitting Málek approach and a model-free advanced isoconversional method of Vyazovkin. The dynamic mechanical properties and thermal stabilities of the cured materials were investigated by DMTA and TG, respectively. The results showed that the activation energy of AG80/DDBE system was slightly higher than that of AG80/DDM system. ?esták-Berggren model can generally simulate well the reaction rates of these two systems. DMTA measurements showed that the storage modulus of cured AG80/DDBE is similar to that of cured AG80/DDM at the temperature below glass transition temperature (T g) and lower than that of cured AG80/DDM at the temperature above glass transition temperature, while T g of cured AG80/DDBE is lower than that of cured AG80/DDM. TG showed that the thermal stabilities of these two cured systems are similar. 相似文献
962.
Biosynthesis of Streptolidine Involved Two Unexpected Intermediates Produced by a Dihydroxylase and a Cyclase through Unusual Mechanisms 下载免费PDF全文
Dr. Chin‐Yuan Chang Syue‐Yi Lyu Dr. Yu‐Chen Liu Ning‐Shian Hsu Dr. Chih‐Chung Wu Dr. Cheng‐Fong Tang Kuan‐Hung Lin Dr. Jin‐Yuan Ho Dr. Chang‐Jer Wu Dr. Ming‐Daw Tsai Dr. Tsung‐Lin Li 《Angewandte Chemie (International ed. in English)》2014,53(7):1943-1948
Streptothricin‐F (STT‐F), one of the early‐discovered antibiotics, consists of three components, a β‐lysine homopolymer, an aminosugar D ‐gulosamine, and an unusual bicyclic streptolidine. The biosynthesis of streptolidine is a long‐lasting but unresolved puzzle. Herein, a combination of genetic/biochemical/structural approaches was used to unravel this problem. The STT gene cluster was first sequenced from a Streptomyces variant BCRC 12163, wherein two gene products OrfP and OrfR were characterized in vitro to be a dihydroxylase and a cyclase, respectively. Thirteen high‐resolution crystal structures for both enzymes in different reaction intermediate states were snapshotted to help elucidate their catalytic mechanisms. OrfP catalyzes an FeII‐dependent double hydroxylation reaction converting L ‐Arg into (3R,4R)‐(OH)2‐L ‐Arg via (3S)‐OH‐L ‐Arg, while OrfR catalyzes an unusual PLP‐dependent elimination/addition reaction cyclizing (3R,4R)‐(OH)2‐L ‐Arg to the six‐membered (4R)‐OH‐capreomycidine. The biosynthetic mystery finally comes to light as the latter product was incorporation into STT‐F by a feeding experiment. 相似文献
963.
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
964.
Phenylene‐Coated Magnetic Nanoparticles that Boost Aqueous Asymmetric Transfer Hydrogenation Reactions 下载免费PDF全文
Dr. Xiaoshuang Gao Rui Liu Dacheng Zhang Meng Wu Tanyu Cheng Prof. Guohua Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1515-1519
Phenylene‐coated organorhodium‐functionalized magnetic nanoparticles are developed through co‐condensation of chiral 4‐(trimethoxysilyl)ethyl)phenylsulfonyl‐1,2‐diphenylethylene‐diamine and 1,4‐bis(triethyoxysilyl)benzene onto Fe3O4 followed complexation with [{Cp*RhCl2}2]. This magnetic catalyst exhibits excellent catalytic activity and high enantioselectivity in asymmetric transfer hydrogenation in aqueous medium. Such activity is attributed to the high hydrophobicity and the confined nature of the chiral organorhodium catalyst. The magnetic catalyst can be easily recovered by using a small external magnet and it can be reused for at least 10 times without loss of its catalytic activity. This characteristic makes it an attractive catalyst for environmentally friendly organic syntheses. 相似文献
965.
Conformational Control of Oligo(p‐phenyleneethynylene)s with Intrinsic Substituent Electronic Effects: Origin of the Twist in Pentiptycene‐Containing Systems 下载免费PDF全文
Che‐Jen Lin Dr. Sandip Kumar Kundu Dr. Cheng‐Kai Lin Prof. Jye‐Shane Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14826-14833
Dependence of the backbone planarity of oligo(p‐phenyleneethynylene)s (OPEs) on the intrinsic electronic character of substituents and on the nature of the solvent has been experimentally demonstrated with a series of center‐symmetrical five‐ring systems, pentiptycene‐pentiptycene‐arene‐pentiptycene‐pentiptycene, differing in the substituents on the central arene. In frozen 2‐methyltetrahydrofuran (MTHF), the adjacent pentiptycene units prefer to be in a mutually twisted orientation when the substituents are electron‐withdrawing (F and amido), resulting in a TPPT or TTTT conformation, whereas a planarized PPPP backbone is favored in the case of electron‐donating substituents (alkyl and alkoxy). The propensity to adopt the PPPP form is generally enhanced by replacing MTHF with either methylcyclohexane or mixed ethanol/methanol as solvent. These observations reveal that the twist between adjacent pentiptycene units in OPEs is a consequence of the electronic rather than steric effects of iptycenyl substituents. The electronic effect of iptycenyl substituents is manifested in decreased phenylene π polarizability as the net effect of both electron‐donating hyperconjugation and an electron‐withdrawing inductive effect. Variable‐temperature electronic absorption and emission spectroscopies are the critical tools for this work. Our findings provide important guidelines for conformational and electronic engineering of OPEs and for the design of novel iptycene‐based organic electronic materials. 相似文献
966.
Direct X‐ray Observation of Trapped CO2 in a Predesigned Porphyrinic Metal–Organic Framework 下载免费PDF全文
Jacob A. Johnson Dr. Shuang Chen Tyler C. Reeson Dr. Yu‐Sheng Chen Prof. Xiao Cheng Zeng Prof. Jian Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7632-7637
Metal–organic frameworks (MOFs) are emerging microporous materials that are promising for capture and sequestration of CO2 due to their tailorable binding properties. However, it remains a grand challenge to pre‐design a MOF with a precise, multivalent binding environment at the molecular level to enhance CO2 capture. Here, we report the design, synthesis, and direct X‐ray crystallographic observation of a porphyrinic MOF, UNLPF‐2, that contains CO2‐specific single molecular traps. Assembled from an octatopic porphyrin ligand with [Co2(COO)4] paddlewheel clusters, UNLPF‐2 provides an appropriate distance between the coordinatively unsaturated metal centers, which serve as the ideal binding sites for in situ generated CO2. The coordination of CoII in the porphyrin macrocycle is crucial and responsible for the formation of the required topology to trap CO2. By repeatedly releasing and recapturing CO2, UNLPL‐2 also exhibits recyclability. 相似文献
967.
Magnetically Encoded Luminescent Composite Nanoparticles through Layer‐by‐Layer Self‐Assembly 下载免费PDF全文
Prof. Dr. Erqun Song Weiye Han Hongyan Xu Yunfei Jiang Dan Cheng Prof. Dr. Yang Song Prof. Dr. Mark T. Swihart 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14642-14649
Sensitive and rapid detection of multiple analytes and the collection of components from complex samples are important in fields ranging from bioassays/chemical assays, clinical diagnosis, to environmental monitoring. A convenient strategy for creating magnetically encoded luminescent CdTe@SiO2@n Fe3O4 composite nanoparticles, by using a layer‐by‐layer self‐assembly approach based on electrostatic interactions, is described. Silica‐coated CdTe quantum dots (CdTe@SiO2) serve as core templates for the deposition of alternating layers of Fe3O4 magnetic nanoparticles and poly(dimethyldiallyl ammonium chloride), to construct CdTe@SiO2@n Fe3O4 (n=1, 2, 3, …?) composite nanoparticles with a defined number (n) of Fe3O4 layers. Composite nanoparticles were characterized by zeta‐potential analysis, fluorescence spectroscopy, vibrating sample magnetometry, and transmission electron microscopy, which showed that the CdTe@SiO2@n Fe3O4 composite nanoparticles exhibited excellent luminescence properties coupled with well‐defined magnetic responses. To demonstrate the utility of these magnetically encoded nanoparticles for near‐simultaneous detection and separation of multiple components from complex samples, three different fluorescently labeled IgG proteins, as model targets, were identified and collected from a mixture by using the CdTe@SiO2@n Fe3O4 nanoparticles. 相似文献
968.
Cerium‐Based M4L4 Tetrahedra as Molecular Flasks for Selective Reaction Prompting and Luminescent Reaction Tracing 下载免费PDF全文
Yang Jiao Dr. Jian Wang Dr. Pengyan Wu Liang Zhao Dr. Cheng He Jing Zhang Prof. Chunying Duan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2224-2231
The application of metal–organic polyhedra as “molecular flasks” has precipitated a surge of interest in the reactivity and property of molecules within well‐defined spaces. Inspired by the structures of the natural enzymatic pockets, three metal–organic neutral molecular tetrahedral, Ce‐TTS, Ce‐TNS and Ce‐TBS (H6TTS: N′,N′′,N′′′‐nitrilotris‐4,4′,4′′‐(2‐hydroxybenzylidene)‐benzohydrazide; H6TNS: N′,N′′,N′′′‐nitrilotris‐6,6′,6′′‐(2‐hydroxybenzylidene)‐2‐naphthohydrazide; H6TBS: 1,3,5‐ phenyltris ‐4,4′,4′′‐(2‐hydroxybenzylidene)benzohydrazide), which exhibit different size of the edges and cavities, were achieved through self‐assembly by incorporating robust amide‐containing tridentate chelating sites into the fragments of the ligands. They acted as molecular flasks to prompt the cyanosilylation of aldehydes with excellent selectivity towards the substrates size. The amide groups worked as trigger sites and catalytic driven forces to achieve efficient guest interactions, enforcing the substrates proximity within the cavity. Experiments on catalysts with the different cavity radii and substrates with the different molecular size demonstrated that the catalytic performance exhibited enzymatical catalytic mechanism and occurred in the molecular flask. These amides were also able to amplify guest‐bonding events into the measurable outputs for the detection of concentration variations of the substrates, providing the possibility for metal–organic hosts to work as smart molecular flasks for the luminescent tracing of catalytic reactions. 相似文献
969.
Dr. Shihui Li Dr. Meiyan Wang Bo Liu Lei Li Prof. Jianhua Cheng Dr. Chunji Wu Dr. Dongtao Liu Prof. Dr. Jingyao Liu Prof. Dr. Dongmei Cui 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15493-15498
The first four‐coordinate methanediide/alkyl lutetium complex (BODDI)Lu2(CH2SiMe3)2(μ2‐CHSiMe3)(THF)2 (BODDI=ArNC(Me)CHCOCHC(Me)NAr, Ar=2,6‐iPr2C6H3) ( 1 ) was synthesized by a thermolysis methodology through α‐H abstraction from a Lu–CH2SiMe3 group. Complex 1 reacted with equimolar 2,6‐iPrC6H3NH2 and Ph2C?O to give the corresponding lutetium bridging imido and oxo complexes (BODDI)Lu2(CH2SiMe3)2(μ2‐N‐2,6‐iPr2C6H3)(THF)2 ( 2 ) and (BODDI)Lu2(CH2SiMe3)2(μ2‐O)(THF)2 ( 3 ). Treatment of 3 with Ph2C?O (4 equiv) caused a rare insertion of Lu–μ2‐O bond into the C?O group to afford a diphenylmethyl diolate complex 4 . Reaction of 1 with PhN=C?O (2 equiv) led to the migration of SiMe3 to the amido nitrogen atom to give complex (BODDI)Lu2(CH2SiMe3)2‐μ‐{PhNC(O)CHC(O)NPh(SiMe3)‐κ3N,O,O}(THF) ( 5 ). Reaction of 1 with tBuN?C formed an unprecedented product (BODDI)Lu2(CH2SiMe3){μ2‐[η2:η2‐tBuNC(=CH2)SiMe2CHC?NtBu‐κ1N]}(tBuN?C)2 ( 6 ) through a cascade reaction of N?C bond insertion, sequential cyclometalative γ‐(sp3)‐H activation, C?C bond formation, and rearrangement of the newly formed carbene intermediate. The possible mechanistic pathways between 1 , PhN?C?O, and tBuN?C were elucidated by DFT calculations. 相似文献
970.
Changduo Pan Ablimit Abdukader Jie Han Prof. Dr. Yixiang Cheng Prof. Dr. Chengjian Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3606-3609
A ruthenium‐catalyzed direct C7 amidation of indoline C?H bonds with sulfonyl azides was developed. This procedure allows the synthesis of a variety of 7‐amino‐substituted indolines, which are useful in pharmaceutical. The good functional tolerances, as well as the mild conditions, are prominent feature of this method. 相似文献