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51.
Dibyendu Bhattacharya Che‐Hao Chang Yu‐Hsiang Cheng Long‐Li Lai Hsiu‐Yu Lu Ching‐Yao Lin Kuang‐Lieh Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(17):5275-5283
Self‐assembled, hexarhenium(I), triangular metalloprism compound [{(CO)3Re(μ‐ 2 )Re(CO)3}3(μ3‐ 1 )2] ( 3 ) featuring three bis‐chelating pillarlike indigo dianions (μ‐ 2 ), each of which connects two fac‐Re(CO)3 cores, which are interconnected by a tritopic N donor, that is, a 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine (μ3‐ 1 , tPyTz) ligand, has been synthesized in high yield and characterized. Metalloprism 3 exhibits a strong absorption in the near‐infrared (NIR) region. The reversible, multielectron redox properties of the electrogenerated 3 n species, where n=3+, 0, 3?, 4?, 5?, 8?, in the visible and especially in the NIR region were investigated in THF solution by cyclic voltammetry (CV), chronocoulometry, EPR spectroscopy, and thin‐layer UV/Vis/NIR spectroelectrochemistry (SEC). Stepwise, site‐specific electrochemical reductions lead to the formation of a series of highly stable ion (radical) species in which electrons associated with μ‐ 2 or μ3‐ 1 components of the molecule can be clearly distinguished. An EPR investigation revealed interaction of unpaired electrons with the metal nuclei (185,187Re, I=5/2) in the reduced intermediates. The framework has C2 symmetry, and accidental degeneracies suffice. Detailed theoretical calculations by structure‐based DFT confirm that the triply degenerate HOMO has ≥70 % indigo character with a sizable dπ‐Re character, while the LUMO is dominated by the triply degenerate indigo ligands, and the LUMO+1 by doubly degenerate tPyTz ligands. A comparison of 3 and previously reported 2,2′‐bis‐benzimidazolate‐ (BiBzlm) or alkoxy‐pillared ReI metalloprisms indicates a very low switching potential with a potential window of less than 1 V and reversibly accessible optical properties with higher stability of the intermediates. The properties exhibited by 3 appear to be due to the slight tuning of the bridging ligand from N,N? to N,O?. 相似文献
52.
The interaction between fullerene C60 and heparin was studied using a fullerene C60‐coated piezoelectric quartz crystal sensor. The irreversible response of the piezoelectric quartz crystal was found which could be attributed to the quite strong adsorption of heparin onto the C60 molecule. Immobilized fullerene C60‐Heparin was prepared and successfully applied as a good inhibitor for blood clotting. Like solvated heparin, both wet and dry C60‐heparin solid all demonstrated excellent ability of anticoagulation of blood. The blood clotting time with C60‐heparin solid was found to be > 7 days, while only 17.9 min required for blood clotting time in the absence of C60‐heparin solid. Furthermore, the C60‐heparin coated artificial PVC blood vessels were prepared by coating fullerene C60 onto the surface of artificial PVC blood vessels, followed by the adsorption of water solvated heparin onto the fullerene C60 molecule to form C60‐heparin coating. The blood clotting time of blood in artificial PVC blood vessels with C60‐heparin coating was found to be > 30 days, while only ≤ 30 min. of blood clotting time without the C60‐Heparin coating was observed. The C60‐heparin coated artificial PVC blood vessels can be expected to be employed in human body for the anticoagulation of blood. 相似文献
53.
Liang‐Hsiang Chen Pang Lin Choongik Kim Ming‐Chou Chen Peng‐Yi Huang Jia‐Chong Ho Cheng‐Chung Lee 《固体物理学:研究快报》2012,6(2):71-73
This study investigates the correlation between surface energy of polymer dielectrics and the film morphology, microstructure, and thin‐film transistor performance of solution‐processed 5,11‐bis(triethylsilylethynyl) anthradithiophene (TES‐ADT) films. The low surface energy polyimide (PI) dielectric induced large grains with strong X‐ray reflections for spin‐cast TES‐ADT films in comparison to high surface en‐ ergy poly(4‐vinyl phenol) (PVP) dielectric. Furthermore, thin‐film transistors based on spin‐cast TES‐ADT films on PI dielectric exhibited enhanced electrical performance, small hysteresis, and high stability under bias stress with carrier mobility as high as 0.43 cm2/Vs and a current on/off ratio of 107. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
54.
Der‐Jang Liaw Pei‐Nan Hsu Wen‐Hsiang Chen Been‐Yang Liaw 《Journal of polymer science. Part A, Polymer chemistry》2001,39(20):3498-3504
A series of new soluble poly(amide‐imide)s were prepared from the diimide‐dicarboxylic acid 2,2‐bis[4‐(4‐trimellitimidophenoxy)phenyl]hexafluoropropane with various diamines by direct polycondensation in N‐methyl‐2‐pyrrolidinone containing CaCl2 with triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 0.52–0.86 dL · g?1. The poly(amide‐imide)s showed an amorphous nature and were readily soluble in various solvents, such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide, pyridine, and cyclohexanone. Tough and flexible films were obtained through casting from DMAc solutions. These polymer films had tensile strengths of 71–107 MPa and a tensile modulus range of 1.6–2.7 GPa. The glass‐transition temperatures of the polymers were determined by a differential scanning calorimetry method, and they ranged from 242 to 279 °C. These polymers were fairly stable up to a temperature around or above 400 °C, and they lost 10% of their weight from 480 to 536 °C and 486 to 537 °C in nitrogen and air, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3498–3504, 2001 相似文献
55.
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
56.
57.
Peng Zhang Dr. Priyesh Jain Caroline Tsao Dr. Zhefan Yuan Dr. Wenchen Li Bowen Li Kan Wu Dr. Hsiang‐Chieh Hung Dr. Xiaojie Lin Prof. Shaoyi Jiang 《Angewandte Chemie (International ed. in English)》2018,57(26):7743-7747
The commonly used “stealth material” poly(ethylene glycol) (PEG) effectively promotes the pharmacokinetics of therapeutic cargos while reducing their immune response. However, recent studies have suggested that PEG could induce adverse reactions, including the emergence of anti‐PEG antibodies and tissue histologic changes. An alternative stealth material with no or less immunogenicity and organ toxicity is thus urgently needed. We designed a polypeptide with high zwitterion density (PepCB) as a stealth material for therapeutics. Neither tissue histological changes in liver, kidney, or spleen, nor abnormal behavior, sickness or death was induced by the synthesized polymer after high‐dosage administration for three months in rats. When conjugated to a therapeutic protein uricase, the uricase–PepCB bioconjugate showed significantly improved pharmacokinetics and immunological properties compared with uricase–PEG conjugates. 相似文献
58.
The first metal‐carbon bond β‐form paddlewheel complexes containing a Pd24+ core, [Pd(η2‐dithio)]2(μ‐dppa)( μ‐SCNMe2) (dithio = S2P(OEt)2, 2 ; S2COEt, 3 ; S2CNC4H8, 4 ), were prepared by the reactions of the α‐form paddlewheel‐type Pd2+4 dipalladium complex [Pd2 (μ‐Hdppa)2(μ‐SCNMe2)2][Cl]2, 1 with various dithio‐ligands, [NH4][S2P(OEt)2], [K][S2COEt] and [NH4][S2CNC4H8], in methanol at ambient temperature (Hdppa = bis(diphenylphosphino)amine). Electronic spectra and two X‐ray structures of the Pd2+4 species have been determined. 相似文献
59.