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51.
Zhengtian Yu James C. W. Chien 《Journal of polymer science. Part A, Polymer chemistry》1995,33(1):125-135
Stereocontrol energy (ΔE0) is investigated as a measure of enantioselectivity of ansa-zircoocenium catalyst in propylene polymerization; it was calculated with MM2 (molecular mechanics) force field using π complex (°C) and transition state (TS) geometries obtained by ab initio molecular orbital methods. Both rac-ethylenebis (1-η5-indenyl) - ( 1 ) and rac-ethylenebis (1-η5-4,5,7,8-tetrahydroindenyl) ( 2 ) zirconocenium species are isospecific in either the π-complexes or the transition states. The stereoselectivity is greater if there is α-agostic interaction; it is lowered in the cases of β and γ agostic interactions. The 13C-NMR steric pentad distribution indicates the poly(propylene) to be much less stereoregular than that predicted by ΔE0. Following the occurrence of a regiochemical insertion error, the addition of another monomer via any mode is prohibitively unfavorable. The catalyst suffers loss of stereospecificity as temperature of polymerization increases. Insertion via transition states involving different agostic interactions could be one explanation for the observed loss. © 1995 John Wiley & Sons, Inc. 相似文献
52.
You-Xian Chen Marvin D. Rausch James C. W. Chien 《Journal of polymer science. Part A, Polymer chemistry》1995,33(13):2093-2108
Bis(1-indenyl)-di[1′S, 2′R, 5′S)-methoxy]silane ( 1 ) was converted into a mixture of corresponding ansa-diastereomeric zirconocenes. Further purification afforded a single dia-stereomer, di[(1′S, 2′R, 5′S)-methoxy] silylene-bis[η5-1(R, R)-(+)-indenyl] dichlorozirconium ( 2 ), which is optically active and hydrocarbon soluble. Extremely rapid ethylene, propylene, and ethylene-hexene polymerizations were observed both in toluene and n-heptane solutions; for instance, at 50°C, activity for ethylene polymerization reaches ~ 1.5×1010 (g of PE/((mol of Zr) · [C2H4] · h). The “bare” zirconocenium ion generated from 2/TIBA/Ph3CB(C6F5)4 exhibits unusual polymerization behaviors; the polymerization activity increases monotonically with temperature of polymerization (Tp) up to a conventional polymerization condition (50–70°C), and the 13C NMR study shows that the isotactic poly-propylene obtained has fairly high [mmmm] methyl pentad distributions at high Tp (?25°C with [mmmm] ~ 0.93–0.75) and a perfect stereoregularity at low Tp (?0°C with [mmmm] > 0.99). The catalyst precursors 2 and Et(Ind)2ZrCl2 ( 3 ) supported on silica by different approaches produced poly(olefins) of different molecular weights and stereoregularities, and a methylaluminokane and Ph3CB(C6F5)4 free silica-supported zirconocene system was found to be activated by triisobutylaluminum. © 1995 John Wiley & Sons, Inc. 相似文献
53.
Diastereoselective [3+2] Annulation of Aromatic/Vinylic Amides with Bicyclic Alkenes through Cobalt‐Catalyzed C−H Activation and Intramolecular Nucleophilic Addition 下载免费PDF全文
Dr. Parthasarathy Gandeepan Dr. Pachaiyappan Rajamalli Prof. Dr. Chien‐Hong Cheng 《Angewandte Chemie (International ed. in English)》2016,55(13):4308-4311
A highly diastereoselective method for the synthesis of dihydroepoxybenzofluorenone derivatives from aromatic/vinylic amides and bicyclic alkenes is described. This new transformation proceeds through cobalt‐catalyzed C?H activation and intramolecular nucleophilic addition to the amide functional group. Transition‐metal‐catalyzed C?H activation reactions of secondary amides with alkenes usually lead to [4+2] or [4+1] annulation; to the best of our knowledge, this is the first time that a [3+2] cycloaddition is described in this context. The reaction proceeds under mild conditions and tolerates a wide range of functional groups. Mechanistic studies imply that the C?H bond cleavage may be the rate‐limiting step. 相似文献
54.
Chien‐Kuo Hsieh Feng‐Chun Lo Gene‐Hsiang Lee Shie‐Ming Peng Wen‐Feng Liaw 《中国化学会会志》2000,47(1):103-107
Complex fac‐[Fe(CO)3(TePh)3]? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)3Mn(μ‐TePh)3Fe(CO)3 obtained in a one‐step synthesis by treating fac‐[Fe(CO)3(TePh)3]? with fac‐[Mn‐(CO)3(CH3CN)3]+. It seems reasonable to conclude that the d6 Fe(II) [(CO)3Fe(TePh)3]? fragment is isolobal with the d6 Mn(I) [(CO)3Mn(TePh)3]2? fragment in complex (CO)3Mn(μ‐TePh)3Fe(CO)3. Addition of fac‐[Fe(CO)3(TePh)3]? to the CpNi(I)(PPh3) in THF resulted in formation of the neutral CpNi(TePh)(PPh3) also obtained from reaction of CpNi(I)(PPh3) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)3(TePh)3]? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)3(SePh)3]? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)3(TePh)3]? in the syntheses of heterometallic chalcogenolate complexes. 相似文献
55.
In this study, a novel method was used to synthesize the poly(N-isopropylacrylamide-co-acrylic acid)/Fe3O4 (poly(NIPAAm-AA)/Fe3O4) magnetic composite latex. The crosslinked poly(NIPAAm-AA) polymer latex particles were first synthesized by the method of soapless emulsion polymerization, then Fe2+ and Fe3+ ions were introduced to bond with the -COOH groups of AA segments in poly(NIPAAm-AA) polymer latex particles. Further by a reaction with NH4OH, Fe3O4 nanoparticles were generated in situ. The concentrations of acrylic acid (AA), crosslinking agent (N,N′-methylene bisacrylamide (MBA)), and Fe3O4 nanoparticles were important factors to influence the morphology and lower critical solution temperature (LCST) of poly(NIPAAm-AA)/Fe3O4 magnetic composite latex particles. The poly(NIPAAm-AA)/Fe3O4 latex particles were used as a thermosensitive drug carrier to load caffeine. The control release of caffeine was studies. Morphology-based schematic models were proposed to explain the control release behavior of the composite particles with different compositions. Moreover, the protein (albumin, acetylated from bovine serum (BSA)) was bound on the surface of poly(NIPAAm-AA)/Fe3O4 composite latex particles. The effects of AA, crosslinking agent and Fe3O4 contents on the amount of BSA binding were investigated at different temperatures and pH values. The composition-morphology-BSA conjugation relationship was established. 相似文献
56.
Chih-Chieh Wang Ciao-Shin Tsai Gene-Hsiang Lee Su-Ying Chien Bo-Hao Chen Yu-Chun Chuang 《中国化学会会志》2023,70(5):1155-1167
Two d10 M(II) (M = Cd and Zn) coordination polymers (CPs) with chemical formulas, {[Cd(L1)(NCS)2(H2O)]⋅C2H5OH}n (1) , and {[Zn(L1)(NCS)2]⋅C2H5OH⋅0.5H2O}n (2) (L1 = 1,3,5-tris(4-pyridylsulfanylmethyl)-2,4,6-trimethylbenzene) were synthesized and structurally characterized by single-crystal x-ray diffraction method. In compound 1 , the coordination environment of Cd(II) ion is distorted octahedral bonded to three nitrogen donors from three L1 ligands located in a facial-position, two nitrogen donors from NCS− and one water molecule. The L1 acts as a bridge ligand with tris-monodentate coordination mode in a cis-cis-cis structural conformation, connecting the Cd(II) to form a two-dimensional (2D) zigzag-like layered metal-organic frameworks. Adjacent 2D layers are then arranged orderly in an ABAB manner to complete its three-dimensional (3D) supramolecular architecture. In compound 2 , the coordination environment of Zn(II) ion is distorted tetrahedral bonded to two nitrogen donors from two L1 ligands and two nitrogen donors from two NCS− ligands. The L1 acts as a bridge ligand with bis-monodentate coordination mode in a cis-cis-cis structural conformation, connecting the Zn(II) ions to form a one-dimensional (1D) zigzag-like polymeric chain. Adjacent chains are arranged orderly in an alternate ABAB manner to generate a 2D framework and then further arranged in an AAA manner to complete its 3D supramolecular architecture. The structural characterization as well as thermal-stability and solvents de-/ad-sorption behavior of 1 and 2 are studied and discussed in details. 相似文献
57.
Kai‐Hsuan Hsieh Chih‐Ying Hsu I‐Ju Hung Chih‐Ling Yeh Yau‐Hung Chen Chien‐Chung Cheng 《中国化学会会志》2021,68(1):34-38
Liposomes composed of cell‐penetrating peptide derivatives increased transport across the cell membrane. Conjugating rhodamine to a cell‐penetrating peptide increased the toxicity of rhodamine in E. coli and zebrafish embryos. A similar total protein inhibition pattern with different intensities, indicating that the interaction pathways of the rho‐KTTKS‐CONH2 monomer and liposomes were the same. It suggests that the rho‐KTTKS‐CONH2 liposomes showed higher toxicity because better transport across the cell membrane increased the effective concentration inside cells. The staining of zebrafish embryos using rho‐KTTKS‐CONH2 liposomes showed a longer retention time, suggesting that it can penetrate deeper tissues or organs in zebrafish. 相似文献
58.
Sadik Elshani Randal Noriyuki Chien M. Wai N. R. Natale Richard A. Bartsch 《Journal of heterocyclic chemistry》1998,35(4):875-885
Twenty-six new lariat ether carboxylic and hydroxamic acids based upon dibenzo-13-crown-4, dibenzo-14-crown-4, dibenzo-16-crown-5 and dibenzo-19-crown-6 ring systems are synthesized and the solid-state structure for a dibenzo-19-crown-6 lariat ether hydroxamic acid is determined. The efficiency and selectivity for lanthanide ion extraction into chloroform by these proton-ionizable lariat ethers is strongly influenced by the crown ether ring size, lipophilic group attachment site and identity of the acidic function. In general, the lariat ether hydroxamic acids were more efficient and selective lanthanide ion extractants than the corresponding lariat ether carboxylic acids. The 1H nmr and ir binding studies indicate that both the macrocyclic polyether unit and the proton-ionizable group are involved in lanthanide ion complexation. 相似文献
59.
A general strategy is proposed to assign aliphatic side-chain resonances of large 13C,15N-labeled proteins without deuteration, using 4D 13C,15N-edited NOESY and MQ-(H)CCH-TOCSY experiments on the basis of prior assignments of backbone and 13Cbeta resonances. The strategy has been tested on a 214 residue protein (DdCAD-1) and applied to a chain-selectively 13C,15N-labeled hemoglobin (65 kDa). About 96 and 80% aliphatic side-chain spins in DdCAD-1 and hemoglobin have been assigned, respectively. The strategy proposed here will be very useful for the structure determination and dynamics characterization of large proteins by NMR. 相似文献
60.
Masilamani Jeganmohan Dr. Sivakolundu Bhuvaneswari Dr. Chien‐Hong Cheng Prof. Dr. 《化学:亚洲杂志》2010,5(1):153-159
The reaction of benzynes with N‐heteroaromatics including quinolines, isoquinolines, and pyridines and various terminal alkynes or ketones with an α‐hydrogen in the presence of KF and 18‐crown‐6 in THF at room temperature for 8 h gave various N‐arylated 1,2‐dihydroheteroaromatics in good to moderate yields. Some of these product structures are found in various naturally occurring and biologically active heterocyclic compounds. The reaction involves an unusual multiple construction of new C? C, C? N, and C? H bonds and the cleavage of a C? H bond in one pot. It is likely that the three‐component coupling proceeds through the nucleophilic addition of quinoline to benzyne, which generates a zwitterionic species. The latter then attracts a proton from terminal alkyne (or ketone) to generate an N‐arylated quinolinium cation and an acetylide anion. Further reaction of these two ions provides the final substituted 1,2‐dihydroquinolines. In the reaction, the terminal alkyne acts first as a proton donor and then as a nucleophile. The application of a three‐component coupling reaction product, 1,2‐dihydro‐2‐pyridinyl alkyne in a stereospecific [4+2] Diels–Alder cycloaddition reaction with N‐phenyl maleimide to give an isoquinuclidine derivative, an important core present in various natural products, is demonstrated. 相似文献