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991.
For weak polyelectrolytes, the interplay between pH, solvent properties, and polymer structure affects the amount of charges, their distribution, and hence their conformations via Coloumb repulsion. Attractive interactions can also develop between charged and neutral sites counteracting the expected Coulomb‐induced expansion. To gauge how such competition affects polyelectrolyte structure and ionization, the titration of a single polyelectrolyte chain, isolated or close to a charged sphere, mimicked with a novel many‐body potential model is simulated with Monte Carlo. Apart from showing a 10‐fold higher ionization than isolated monomers at low pH, interacting species contracted forming short‐range clusters of charged and neutral ionizable groups. The presence of a charged sphere synergically boosted both effects due to monomer interactions, forcing the chains to condense onto its surface at much lower pH. Structural properties, however, seem to be controlled only by the ionization degree despite the presence of the topological restraint represented by the spherical surface. Using Monte Carlo titration results, the equilibrium ionization of isolated chains is also estimated; the results evidence that even weak interactions can easily lead to a doubling of the total charge. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 650–663  相似文献   
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The results of the annihilation cross sections measurement of 5.3 MeV antiprotons on nickel, tin, platinum and Mylar targets performed by the ASACUSA Collaboration at CERN are presented and compared with the existing data and models. From the experimental point of view the presented data are the first measurement of antinucleon annihilation cross sections at low energies obtained with a pulsed beam. This results open the road for the next measurements at the very low energies of the order of 100 keV that are in progress by the ASACUSA Collaboration. The experimental method foreseen for the 100 keV measurement is illustrated.  相似文献   
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Direct experimental access to the monomeric friction coefficient (ζ0) relies on the availability of a suitable polymer dynamics model. Thus far, no method has been suggested that is applicable to filled systems, such as filled rubbers or microphase‐segregated A–B–A thermoplastic elastomers (TPEs) at Tg,B < T < Tg,A. Building upon the procedure proposed by Ferry for entangled and unfilled polymer melts, the Rouse–Bueche theory is applied to an undiluted triblock copolymer to extract ζ0 from the linear behavior in the rubber‐glass transition region, and to estimate the size of Gaussian submolecules. When compared at constant TTg, the matrix monomeric friction factor is consistent with the corresponding value for the homopolymer melt. In addition, the characteristic Rouse dimensions are in good agreement with independent estimates based on the Kratky–Porod worm‐like chain model. These results seem to validate the proposed approach for estimating ζ0 in filled systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1437–1442  相似文献   
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Neutral and cationic cyclopentadienone (CpO) N‐heterocyclic carbene (NHC) bis‐carbonyl iron(0) complexes bearing, appended to the NHC ligand, either a terminal amino group on the lateral chain, [Fe(η4‐CpO)(CO)2C‐NHC(CH2)nNH2)] with n = 2 ( 2a ) and 3 ( 2b ), or a cationic NMe3+ fragment, [Fe(η4‐CpO)(CO)2C‐NHC(CH2)2NMe3)](I) ( 3 ), were prepared and characterized in terms of their structure, stability and reactivity. The photochemical properties of 2a and 2b were examined both in organic solvents and in water, revealing the photoactivated release of one CO ligand followed by the formation of the chelated complex [Fe(η4‐CpO)(CO)(κ2C,N‐NHC(CH2)2NH2)] ( 4 ), whose molecular structure was confirmed by single crystal X‐ray diffraction studies. This metallacyclization occurs only in the case of 2a , with the ethylene spacer between NHC ring and NH2 group in the lateral chain, allowing the formation of a stable 6‐membered ring. On the other hand, 2b undergoes decomposition upon irradiation. The reactivity in aqueous solutions revealed the chemical speciation of the complexes at different pH and especially under physiological conditions (phosphate buffer solution at pH 7.4 and 37 °C). The lack of data on the biological properties of iron(0) complexes prompted us to preliminarily investigate their cytotoxicity against model cancer cells (AsPC‐1 and HPAF‐II), along with a determination of their lipophilicity.  相似文献   
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