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151.
Nga H. Nguyen Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2011,49(5):1235-1247
Computational studies on the heterolytic bond dissociation energies and electron affinities of methyl 2‐bromopropionate (MBP) and ethyl 2‐bromoisobutyrate (EBiB) in the dissociative electron transfer (DET) step of single electron transfer living radical polymerization (SET‐LRP) of methyl acrylate (MA) combined with kinetic experiments were performed in an effort to design the most efficient initiation system. This study suggests that EBiB is more effective than MBP in the SET‐LRP of acrylates catalyzed by Cu(0) wire, thus being a true electronic mimic of the dormant PMA species. EBiB allows for a more predictable dependence of the molecular weight evolution and distribution. This is exemplified by the absence of a deviation in the PMA molecular weight from theoretical values at low conversions, as a result of a faster SET activation with EBiB than with MBP. The enhanced control over molecular weight evolution was also observed in the SET‐LRP of MA initiated with bifunctional initiators similar in structure to MBP and EBiB, suggesting a higher reactivity than MBP in the SET activation, which matches closely that of the polymer dormant chains. The use of bifunctional initiators in conjunction with activated Cu(0) wire in SET‐LRP allows for dramatically accelerated polymerizations, although still providing for exceptional control of the molecular weight evolution and distribution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
152.
V. Franco A. Conde V. Provenzano R.D. Shull 《Journal of magnetism and magnetic materials》2010,322(2):218-223
The field dependence of the magnetic entropy change has been studied for a series of doped Gd5Si2Ge2 alloys, which possess a magnetic phase transition that is either entirely second order or a combination of primarily second-order mixed to a very minor degree with a first-order transition arising from a magneto-structural phase change. By analyzing the field scaling of the refrigerant capacity as well as of the reference temperatures used for constructing a universal scaling curve, a procedure for estimating the values of the critical exponents for the alloys was developed. For the cases where the transition is entirely second order, the results obtained from this procedure are comparable to the values obtained from the Kouvel–Fisher method. For the case of Fe-doped alloys which partially possess a first-order phase change, the Kouvel–Fisher method is inapplicable. However, their critical exponents determined by our developed procedure can be used to estimate the Curie temperature of the orthorhombic majority phase. 相似文献
153.
Sven Fleischmann Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2010,48(5):1190-1196
Single Electron Transfer‐Living Radical Polymerization (SET‐LRP) represents a robust and versatile method for the rapid synthesis of macromolecules with well defined topology. In SET‐LRP, certain combinations of solvents and ligands facilitate the disproportionation of in situ generated Cu(I) species into “nascent” Cu(0) and Cu(II) species. A combination of heterogeneous and “nascent” Cu(0) activation yields polymers with very high chain end functionality. Under suitable conditions the tolerance toward oxygen must be increased since Cu(0), the activator in SET‐LRP, acts as an oxygen scavenger in all inert gas purification systems. Here we demonstrate that SET‐LRP of methyl acrylate can be conducted in the presence of air. The addition of a small amount of reducing agent hydrazine hydrate to the reaction mixture reduces Cu2O generated by the oxidation of Cu(0) with air, regenerating Cu(0) and allowing for the synthesis of polymers with predictable molecular weight and perfect retention of chain end functionality. The kinetics plots obtained under these conditions were identical to these generated by degassed samples. High conversions were achieved within a very short reaction time. In these SET‐LRP experiments, the reagents were not deoxygenated or subjected to standard degassing procedures such as freeze‐pump‐thaw or nitrogen sparging. This simple SET‐LRP procedure provides an efficient and economical approach to the synthesis of functional macromolecules. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1190–1196, 2010 相似文献
154.
Jorge F. J. Coelho Erica Y. Carvalho Dina S. Marques Anatoliy V. Popov Virgil Percec Pedro M. F. O. Gonçalves M. H. Gil 《Journal of polymer science. Part A, Polymer chemistry》2008,46(2):421-432
Living radical polymerization of ethyl acrylate was achieved by single‐electron‐transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionite. The plots of number‐average molecular weight versus conversion and ln[M]0/[M] versus time are linear, indicating a controlled polymerization. This method leads to the preparation of α,ω‐di(iodo)poly(ethyl acrylate) (α,ω‐di(iodo)PEtA) macroinitiator that can be further functionalized. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering, a differential viscometer and refractive index. The method studied in this work represents a possible route to prepare well‐tailored macromolecules made of ethyl acrylate in environmental friendly reaction medium. To the best of our knowledge there is no previous report dealing with the synthesis of PEtA by any LRP approach in aqueous medium. Furthermore, the method described in this article was successfully applied in pilot scale reactions under industrial production conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 421–432, 2008 相似文献
155.
Leowanawat P Zhang N Safi M Hoffman DJ Fryberger MC George A Percec V 《The Journal of organic chemistry》2012,77(6):2885-2892
trans-Chloro(1-naphthyl)bis(triphenylphosphine)nickel(II) complex/PCy(3) system has been successfully applied as catalyst for the Suzuki-Miyaura cross-coupling of aryl and heteroaryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates in THF at room temperature. This cross-coupling reaction tolerates various functional groups, including keto, imino, ester, ether, and cyano. Together with the nickel-catalyzed, one-pot, two-step neopentylglycolborylation, this bench stable and inexpensive Ni(II)-based catalyst can be utilized as an alternative to Ni(COD)(2)/PCy(3) to provide an inexpensive, robust, and convenient synthesis of biaryl and heterobiaryl compounds. 相似文献
156.
Ana‐Maria Gurban Lucian Rotariu Virgil Emanuel Marinescu Camelia Bala 《Electroanalysis》2012,24(12):2371-2379
A ternary composite material based on Prussian blue, single‐walled carbon nanotubes and 1‐butyl‐3‐methylimidazolium hexafluorophosphate was prepared and tested for electrochemical detection of H2O2. The sensor allows amperometric detection of H2O2 at ?0.05 V, with a sensitivity of 137 mA M?1?cm?2. The nanocomposite provides a favorable microenvironment for immobilization of horseradish peroxidase (HRP). Determination of xenoestrogenic compounds was performed by enzymatic oxidation at the surface of modified screen printed biosensor in the presence of H2O2. The developed electrochemical biosensors exhibited high sensitivity, low detection limits, good operational and storage stability, for detection of 4‐t‐butylphenol, 4‐t‐octylphenol, 4‐n‐nonylphenol and 4‐n‐nonylphenol ethoxylate. 相似文献
157.
Xuan Jiang Sven Fleischmann Nga H. Nguyen Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2009,47(21):5591-5605
SET‐LRP requires a combination of ligand and solvent that mediates the disproportionation of Cu(I)X into Cu(0) activator, and Cu(II) deactivator. The solvent also modulates the kinetics of the reaction. More polar solvents, including mixtures of water and organic solvents enhance the rate of polymerization in accord with the Dimroth‐Reichardt parameter. Here, it is demonstrated that a similar effect is observed in binary mixtures of organic solvents, wherein the addition of a more polar solvent to a less polar solvent provides a linear increase in the apparent rate constant of propagation, k. However, this linear relationship does not hold for the entire range of volume fraction for binary mixtures when ethylene carbonate (EC) or MeOH are one of the two components. Results herein, suggest that the kinetics of SET‐LRP in these solvent mixtures is cooperatively and synergistically determined by polarity, degree of disproportionation, and also by another parameter related to the ability of the solvent to stabilize colloidal Cu(0) and determine its particle size. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5591–5605, 2009 相似文献
158.
V. S. Avilkina N. N. Andrianova A. M. Borisov Yu. S. Virgil’ev E. S. Mashkova 《Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques》2012,6(4):631-634
The crystal structure and morphology of the KUP-VM (1D) carbon-carbon fiber composite are investigated upon irradiation with 15- and 30-keV Ne+ ions with high fluences (1018?C1019 ion/cm2) with the purpose of studying fiber crimping. The results are compared with data obtained previously for N 2 + and Ar+ ion irradiation. It is assumed that the formation of regular prismatic topographic elements (crimps) at temperatures near and above the dynamic annealing temperature T a reflects the highly ordered structure of the fiber??s surface shell. The results obtained are discussed within the Bradley-Harper theory. 相似文献
159.
Marin Cernea Gianluca Poli Gheorghe Virgil Aldica Ciceron Berbecaru Bogdan Stefan Vasile Carmen Galassi 《Current Applied Physics》2012,12(4):1100-1105
(Bi0.5Na0.5)TiO3 was doped in situ with 5, 8, and 11 mol% BaTiO3 (BNT-BTx; x = 0.05, 0.08 and 0.11) using a sol-gel technique. The resulting powders from gel precursors showed microstructures consisting of nano-sized grains and crystalline perovskite structure. Spark plasma sintering (SPS) technique was used to prepare high densified (98–99%ρtheor) BNT-BTx ceramics from these nanopowders. The results confirm the spark plasma sintering method applied to nano-scale powders, obtained by sol-gel, as a viable route in producing nanostructured ceramics. The evolution of the structure and electrical properties of the ceramics with BaTiO3 concentration (x) was investigated. The permittivity of BNT-BT0.08 ceramic is higher (εr = 2090, at 100 kHz) than that for x = 0.05 (εr = 1350) and x = 0.11 (εr = 1800). BNT-BT0.08 ceramic shows maximum values for the frequency constants (Np, Nt), piezoelectric charge coefficient (d31) and piezoelectric voltage coefficient (g31), and minimum values for the electromechanical coupling factor (kp) and piezoelectric charge coefficient (d33). The electrical properties of these ceramics are influenced by grains size, oxygen deficiency and non-uniform internal stresses due to these oxygen deficiencies. BNT-BTx ceramics sintered by SPS seem to be good ceramic resonators with high mechanical quality factor (Qm). 相似文献
160.
Peterca M Percec V Dulcey AE Nummelin S Korey S Ilies M Heiney PA 《Journal of the American Chemical Society》2006,128(20):6713-6720
The synthesis of dendritic dipeptides (4-3,4-3,5-4)12G2-CH(2)-Boc-L-Tyr-L-Ala-OMe and (4-3, 4-3,5-4)12G2-CH(2)-Boc-D-Tyr-D-Ala-OMe is described. These dendritic dipeptides self-assemble into porous elliptical and circular columns that in turn self-organize into centered rectangular columnar and hexagonal columnar periodic arrays. The transition from porous elliptical to porous circular columns is mediated in a reversible or irreversible way by the thermal history of the sample. A method to determine the dimensions of hollow elliptical and circular columns by the reconstruction of the small-angle powder X-ray diffractograms of the centered rectangular or hexagonal columnar lattices was elaborated. This technique together with wide-angle X-ray experiments performed on aligned fibers provided access to the structural and retrostructural analysis of elliptical supramolecular pores. This procedure is general and can be adapted for the determination of the dimensions of pores of any columnar shape. 相似文献