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11.
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Hendrik De Cooman Tim Desmet Freddy Callens Peter Dubruel 《Journal of polymer science. Part A, Polymer chemistry》2012,50(11):2142-2149
Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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2,2-Dimethyl-4-methoxychromans (1–12) have been converted into 2,2-dimethyl-2H-chromenes (13–24) in acidic media. 相似文献
15.
Jan Rosenboom Dr. Lukas Chojetzki Dr. Tim Suhrbier Dr. Jabor Rabeah Dr. Alexander Villinger Dr. Ronald Wustrack Dr. Jonas Bresien Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202200624
The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)2P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)2P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)2P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)2P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)2P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)2P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)2P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)2P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)2P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity. 相似文献
16.
Felipe J. Llanes-Estrada Tim Van Cauteren Ángel P. Martín 《The European Physical Journal C - Particles and Fields》2007,51(4):945-952
We study the multiple solutions of the truncated propagator Dyson–Schwinger equation for a simple fermion theory with Yukawa
coupling to a scalar field. Upon increasing the coupling constant g, other parameters being fixed, more than one non-perturbative
solution breaking chiral symmetry becomes possible and we find these numerically. These “recurrences” appear as a mechanism
to generate different fermion generations as quanta of the same fundamental field in an interacting field theory, without
assuming any composite structure. The number of recurrences or flavors is reduced to the question of the value of the Yukawa
coupling, and it has no special profound significance in the standard model. The resulting mass function can have one or more
nodes and the measurement that potentially detects them can be thought of as a collider-based test of the virtual dispersion
relation for the charged lepton member of each family. This requires the three independent measurements of the charged lepton’s energy,
three-momentum and off-shellness. We illustrate how this can be achieved for the (more difficult) case of the tau lepton.
PACS 12.15.Ff; 11.30.Rd 相似文献
17.
We apply random matrix theory to compare correlation matrix estimators C obtained from emerging market data. The correlation matrices are constructed from 10 years of daily data for stocks listed on the Johannesburg stock exchange (JSE) from January 1993 to December 2002. We test the spectral properties of C against random matrix predictions and find some agreement between the distributions of eigenvalues, nearest neighbour spacings, distributions of eigenvector components and the inverse participation ratios for eigenvectors. We show that interpolating both missing data and illiquid trading days with a zero-order hold increases agreement with RMT predictions. For the more realistic estimation of correlations in an emerging market, we suggest a pairwise measured-data correlation matrix. For the data set used, this approach suggests greater temporal stability for the leading eigenvectors. An interpretation of eigenvectors in terms of trading strategies is given, as opposed to classification by economic sectors. 相似文献
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A. Ertoprak B. Cederwall C. Qi M. Doncel U. Jakobsson B. M. Nyakó G. Jaworski P. Davies G. de France I. Kuti D. R. Napoli R. Wadsworth S. S. Ghugre R. Raut B. Akkus H. Al Azri A. Algora G. de Angelis A. Atac T. Bäck A. Boso E. Clément D. M. Debenham Zs. Dombrádi S. Ertürk A. Gadea F. Ghazi Moradi A. Gottardo T. Hüyük E. Ideguchi H. Li C. Michelagnoli V. Modamio J. Nyberg M. Palacz C. M. Petrache F. Recchia M. Sandzelius M. Siciliano J. Timár J. J. Valiente-Dobón Z. G. Xiao 《The European Physical Journal A - Hadrons and Nuclei》2018,54(9):145
20.
Hyun Jong Park Olga Kryliouk Tim Anderson Dmitry Khokhlov Timur Burbaev 《Physica E: Low-dimensional Systems and Nanostructures》2007,37(1-2):142
InN films and nanorods were grown by hydride metalorganic vapor phase epitaxy (H-MOVPE) and the effects of growth temperature, and NH3/TMIn and HCl/TMIn ratios on morphological dependences were studied. The growth habit of InN varied from thin film to microrod to nanorod to no deposition as the growth conditions were changed about transition from growth to etching conditions. The growth and etch regimes were also predicted by chemical equilibrium calculations of In–C–H–Cl–N-inert system. The optical properties of InN nanorods and columnar structured films were measured by room temperature PL and a maximum intensity was observed at 1.08 eV for both structures. 相似文献