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61.
Virgil Percec Cristian Grigoras Hyoung-J. Kim 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):505-513
TERMINI stands for irreversible terminator multifunctional initiator and represents a new concept elaborated in our laboratory for the design of novel macromolecules with complex architecture from a diversity of commercial monomers. TERMINI is a masked multifunctional initiator that quantitatively interrupts a living polymerization. After demasking, the TERMINI-derived repeat unit provides access to a quantitative reinitiation of the same living polymerization in more than one direction, thus becoming a branching point. In this article, with a combination of self-regulated metal-catalyzed living radical polymerization and TERMINI, we demonstrate a new method for the divergent synthesis of dendritic poly(methyl methacrylate) containing a bifunctional core at its focal point. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 505–513, 2004 相似文献
62.
Dr. Dong Heon Nam Dr. Jenny Z. Zhang Virgil Andrei Dr. Nikolay Kornienko Dr. Nina Heidary Andreas Wagner Kenichi Nakanishi Katarzyna P. Sokol Barnaby Slater Dr. Ingo Zebger Prof. Stephan Hofmann Dr. Juan C. Fontecilla‐Camps Prof. Chan Beum Park Prof. Erwin Reisner 《Angewandte Chemie (International ed. in English)》2018,57(33):10595-10599
Hydrogenases (H2ases) are benchmark electrocatalysts for H2 production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p‐type Si photocathode for optimal loading and wiring of H2ase through the introduction of a hierarchical inverse opal (IO) TiO2 interlayer. This proton‐reducing Si|IO‐TiO2|H2ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias‐free) water splitting by wiring Si|IO‐TiO2|H2ase to a modified BiVO4 photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO‐TiO2|H2ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z‐scheme that replaces the non‐complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode. 相似文献
63.
Traian Zaharescu Virgil Marinescu Edyta Hebda Krzysztof Pielichowski 《Journal of Thermal Analysis and Calorimetry》2018,131(1):49-55
Through temperature-programmed pyrolysis, the physicochemical properties of Pteria martensii (PM) before and after calcination are investigated. Our results show that the mass loss is 11.02% from room temperature to 600 °C with an average mass loss rate of 0.19% per min. The decomposition of organics coupling with the phase transition of calcium carbonate from aragonite to calcite occurs in the range of 367.4–423.0 °C, as confirmed by X-ray diffraction and Fourier transform infrared spectroscopy analyses. The decomposition pores and channels are changed forming complex porous structures. The surface of sample shows a much rougher fracture, with higher C, O and N element concentrations. At the stage of decomposition and phase transition of organics, the average activation energy value is 118.78 kJ mol?1. This study provides valuable information on the calcination process and calcined PM for use in medicines. 相似文献
64.
Virgil Percec James H. Wang Yoshi Oishi 《Journal of polymer science. Part A, Polymer chemistry》1991,29(7):949-964
4,4′-Bis(phenoxy)diphenyl sulfone ( 1 ), 4,4′-bis(phenylthio)diphenyl sulfone ( 2 ), and 1 substituted with various electron-donating groups in the phenoxy units were synthesized and polymerized under oxidative reaction conditions. The presence of methyl, tert-butyl, and methoxy groups as substituents on the phenoxy groups of 1 increases both the yield and the solubility of the resulting polymers. The structure-reactivity relationship of the monomers and of the growing species were discussed based on a radical-cation mechanism of polymerization. Monomers of high nucleophilicity and resonance stabilized radical-cation growing species are crucial to achieve polymers of high molecular weight. The structure of the polymers and in several cases of their chain ends were determined by 1H-NMR spectroscopy. The mechanism of termination and the side reactions occuring during this polymerization process were discussed based on the structure of the resulting polymers. 相似文献
65.
Virgil Percec Shigeru Okita 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):923-932
The nucleophilic substitution reactions of 1,4-dichlorobenzene chromium tricarbonyl ( 1 ) with the phenoxide anion were investigated. The substitution of the first chlorine was very fast and gave the mono-substituted product in high yield. The substitution of the second chlorine group was significantly retarded by the presence of the phenoxy group incorporated during the first reaction and also due to the competing decomplexation reaction. The application of 1,4-dichlorobenzene chromium tricarbonyl ( 1 ) to the synthesis of new monomers was demonstrated by the preparation of 2,2′-bis[4-(4-chlorophenoxy)phenyl]propane ( 9 ). 2,2′-Bis[4-(4-chlorophenoxyl)phenyl]propane ( 9 ) was synthesized by a nucleophilic substitution reaction of 4,4′-isopropylidenediphenolate with 1,4-dichlorobenzene chromium tricarbonyl ( 1 ) followed by decomplexation with I2. 2,2′-Bis[4-(4-chlorophenoxy)-phenyl]propane ( 9 ) was also synthesized via a three-step reaction starting from the nucleophilic substitution reaction of 4,4′-isopropylidenediphenol ( 7a ) with 1-chloro-4-nitrobenzene ( 10 ). 2,2′-Bis[4-(4-chlorophenoxy)phenyl]propane ( 9 ) was polymerized by a Ni(0)-catalyzed reaction to yield amorphous aromatic polyethers with number-average molecular weights of up to 11,200 g/mol. © 1993 John Wiley & Sons, Inc. 相似文献
66.
Mamdouh W Uji-I H Dulcey AE Percec V De Feyter S De Schryver FC 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7678-7685
We have investigated the two-dimensional ordering of chiral and achiral monodendrons at the liquid-solid interface. The chiral molecules self-assemble into extended arrays of dimers. As expected, the R enantiomer forms the mirror image type pattern of the chiral two-dimensional structure formed by the S enantiomer. A racemic mixture applied from solution onto the substrate undergoes spontaneous segregation: the enantiomers separate on the surface and appear in different domains. In contrast to the chiral molecules, the achiral analogue self-assembles into cyclic tetramers. Moreover, the pattern formed by the achiral molecule strongly depends on the solvent used. In the case of 1-phenyloctane, solvent molecules are coadsorbed in a 2:1 (dendron:solvent) ratio whereas in 1-octanol, no solvent molecules are coadsorbed. By the appropriate solvent choice, the distance between the potential "supramolecular containers" can be influenced. 相似文献
67.
Timothy D. Shaffer Mustafah Jamaludin Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》1986,24(1):15-27
Random and alternating thermotropic liquid-crystalline copolyethers have been synthesized from 4,4′-dihydroxybiphenyl and a 1/1 mol ratio of 1,5-dibromopentane and α,ω-dibromoalkanes by a two-phase (organic solvent-aqueous NaOH) phase-transfer-catalyzed polyetherification. Random copolyethers were prepared from α,ω-dibromoalkanes having six to twelve methylene units. Their phase behavior was compared with those of the perfectly alternating copolyethers containing five methylene units in one spacer and eight, nine, or eleven methylene units in the other, respectively. An odd-even dependence in thermal transitions has been observed in both oligomeric systems. In all cases, alternating copolyethers, even though comparatively lower in molecular weight, have given rise to higher melting and isotropization temperatures. Since the increase in the melting temperature is larger than the increase in the isotropization temperature, the thermal stability range of the mesophase has narrowed for alternating copolyethers with respect to their random copolyether counterparts. 相似文献
68.
Rapp A Schnell I Sebastiani D Brown SP Percec V Spiess HW 《Journal of the American Chemical Society》2003,125(43):13284-13297
Advanced solid-state NMR methods under fast magic-angle spinning (MAS) are used to study the structure and dynamics of large supramolecular systems, which consist of a polymer backbone with dendritic side groups and self-assemble into a columnar structure. The NMR experiments are performed on as-synthesized samples, i.e., no isotopic enrichment is required. The analysis of (1)H NMR chemical-shift effects as well as dipolar (1)H-(1)H or (1)H-(13)C couplings provide site-specific insight into the local structure and the segmental dynamics, in particular, of phenyl rings and -CH(2)O- linking units within the dendrons. Relative changes of (1)H chemical shifts (of up to -3 ppm) serve as distance constraints and allow protons to be positioned relative to aromatic rings. Together with dipolar spinning sideband patterns, pi-pi packing phenomena and local order parameters (showing variations between 30% and 100%) are selectively and precisely determined, enabling the identification of the dendron cores as the structure-directing moieties within the supramolecular architecture. The study is carried out over a representative selection of systems which reflect characteristic differences, such as different polymer backbones, sizes of dendritic side groups, or length and flexibility of linking units. While the polymer backbone is found to have virtually no effect on the overall structure and properties, the systems are sensitively affected by changing the generation or the linkage of the dendrons. The results help to understand the self-assembly process of dendritic moieties and aid the chemical design of self-organizing molecular structures. 相似文献
69.
Christoph Elschenbroich Fabian Gerson Virgil Boekelheide 《Helvetica chimica acta》1975,58(5):1245-1253
The radical anion of trans-10b, 10c-dihydropyrene (V), which is formed upon reduction of the isomeric [2.2]metacyclophane-1,9-diene (III) with solvated electrons, has been identified by its ESR.-spectrum. The large coupling constant (19.1 Gauss), due to the two equivalent β-protons in the alkyl bridge, gives evidence of an important hyperfine interaction between the σ-MO's of the C(sp3)-H bonds and the singly occupied π-MO of the fourteen-membered perimeter. This finding supports the assumption that the unexpected energy sequence of the lowest antibonding perimeter MO's in the dihydropyrene V and its 10b, 10c-dimethyl derivative (VI) is determined by hyperconjugation rather than by the inductive effect of the alkyl bridge. When the solution of V○ in 1,2-dimethyoxyethane (DME) is brought in contact with an alkali metal mirror, an immediate conversion of VΦ into the radical anion of pyrene (IV) occurs. The anion IVΦ also results from reduction of [2.2.2](1,3,5)cyclophane-1,9,17-triene (VIII) with potassium in DME, whereas the radical anions of 4,5,9,10-tetrahydropyrene (II) and its 2,7-dimethyl-derivative (IX) are obtained by corresponding reactions of [2.2]metacyclophane (I) and [2.2.2](1,3,5)cyclophane (VII), respectively. 相似文献
70.
Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride 总被引:1,自引:0,他引:1
Percec V Popov AV Ramirez-Castillo E Monteiro M Barboiu B Weichold O Asandei AD Mitchell CM 《Journal of the American Chemical Society》2002,124(18):4940-4941
This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5. 相似文献