Macromolecular Chemistry and Physics

Cover image for Vol. 214 Issue 12

June 25, 2013

Volume 214, Issue 12

Pages 1289–1404

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      Macromol. Chem. Phys. 12/2013 (page 1289)

      Nobuhiko Hosono, Naoki Yoshihara, Yoshihiko Murakami and Toshiyuki Watanabe

      Version of Record online: 14 JUN 2013 | DOI: 10.1002/macp.201370041

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      Front Cover: A hinge-linked network is created featuring rotatable molecular machinery at a crosslink point. The crosslinker synthesized here has four reactive amine groups connected to a ferrocenyl center that provides a pivotal motion, and forms a hinge-linked polymer framework with poly(amide acid) backbones Further details can be found in the article by N. Hosono,* N. Yoshihara, Y. Murakami, and T. Watanabe* on page 1356.

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    1. Macromol. Chem. Phys. 12/2013

      Version of Record online: 14 JUN 2013 | DOI: 10.1002/macp.201370042

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    1. Non-Natural Amino Acids for Protein Engineering and New Protein Chemistries (pages 1295–1301)

      Inchan Kwon and Sung In Lim

      Version of Record online: 18 MAR 2013 | DOI: 10.1002/macp.201200710

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      Two distinct strategies, residue-specific and site-specific incorporation, allow biosynthesis of a protein containing non-natural amino acids. Non-natural amino acids introduced into a protein can be used to manipulate spectral and catalytic properties of a protein and provide new protein chemistries for bioconjugation with versatile molecules.

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    1. New Thiols for Photoinitiator-Free Thiol-Acrylate Polymerization (pages 1302–1308)

      Mohamad-Ali Tehfe, Shovan Mondal, Malek Nechab, Frédéric Dumur, Michèle P. Bertrand, Bernadette Graff, Didier Gigmes, Jean-Pierre Fouassier and Jacques Lalevée

      Version of Record online: 26 APR 2013 | DOI: 10.1002/macp.201300077

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      New thiols for efficient thiol-ene photopolymerization reactions are presented. They are characterized by quite good light-absorption properties and generate thiyl radicals upon UV-light exposure (i.e., the polymerizations can be carried out without the presence of any additional photoinitiator). These systems are also very efficient in overcoming oxygen inhibition.

    2. Polysaccharide-Based Polyanion–Polycation–Polyanion Ternary Systems in the Concentrated Regime and Hydrogel Form (pages 1309–1320)

      Eleonora Marsich, Andrea Travan, Massimo Feresini, Romano Lapasin, Sergio Paoletti and Ivan Donati

      Version of Record online: 15 MAY 2013 | DOI: 10.1002/macp.201300057

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      Alginate–hyaluronan-modified chitosan ternary mixtures in concentrated solution and hydrogel state show the presence of supramolecular complexes with inhomogeneity in elastic response and stimulate primary chondrocyte proliferation.

    3. Novel Atom Transfer Radical Polymerization Method to Yield Copper-Free Block Copolymeric Biomaterials (pages 1321–1325)

      Justin R. Adams and Surya K. Mallapragada

      Version of Record online: 3 MAY 2013 | DOI: 10.1002/macp.201300034

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      A new catalyst for atom transfer radical polymerization (ATRP) for the synthesis of copper-free block copolymers is reported. Biocompatibility is an increasing concern with growing applications for polymers synthesized by ATRP in the fields of biology and medicine. The use of cuprous oxide nanoparticles as catalysts allows for the controlled synthesis of polymers with low toxicity with no residual copper.

    4. Synthesis and Characterization of End-Functionalized Poly(3-butylthiophene) with Semifluoroalkyl Chains (pages 1326–1331)

      Jusha Ma, Yanfang Geng, Kazuhito Hashimoto and Keisuke Tajima

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/macp.201300081

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      End-fluoroalkylated poly(3-buthylthiophene) with a well-defined structure and narrow molecular-weight distribution is successfully synthesized by quasi-living polymerization and fluoroalkylation on one end only. This polymer may be useful for controlling the surface and interfacial properties of semiconducting thin films, as demonstrated by the decrease of the contact angle of the solutions.

    5. Control of Molecular Weight and Tacticity in Stereospecific Living Cationic Polymerization of α-Methylstyrene at 0 °C Using FeCl3-Based Initiators: Effect of Tacticity on Thermal Properties (pages 1332–1344)

      Sanjib Banerjee, Tapas K. Paira and Tarun K. Mandal

      Version of Record online: 17 MAY 2013 | DOI: 10.1002/macp.201300092

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      Poly(α-methylstyrene)s of varying syndiotacticity (59.1% to 79.2%) and controllable molecular weight (Mn = 4300–32 100 g mol−1) with moderately narrow polydispersity indices (PDI ≈ 1.3) are synthesized via stereospecific living cationic polymerization of α-methylstyrene using an FeCl3-based initiating system at 0 °C. The glass-transition temperature and the thermal stability are found to depend on the syndiotacticity of the as-synthesized poly(α-methylstyrene).

    6. Morphological Heterogeneity by Diffusional Kurtosis NMR Spectroscopy in Perfluorosulfonic Acid/SiO2 Composite Proton-Exchange Membranes (pages 1345–1355)

      Dan E. Demco, Carmen Filipoi, Xiaomin Zhu, Radu Fechete and Martin Möller

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/macp.201300039

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      Diffusional kurtosis is introduced to characterize the anisotropy and heterogeneity of the channel architecture for ionic transport in proton-exchange membranes (PEMs) and is applied to perfluorinated sulfonic acid (PFSA)/SiO2 nanocomposites. Water diffusion coefficients and diffusional kurtosis are measured as a function of temperature and relative humidity for different silica contents and membrane orientations relative to the field-gradient direction.

    7. Hinge-Linked Polymer Gels: A Rigid Network Cross-Linked with a Rotatable Tetrasubstituted Ferrocene (pages 1356–1362)

      Nobuhiko Hosono, Naoki Yoshihara, Yoshihiko Murakami and Toshiyuki Watanabe

      Version of Record online: 13 MAR 2013 | DOI: 10.1002/macp.201200705

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      A new type of polymer network is designed and synthesized, based on rotatable ferrocene-type cross-links. The resulting polymeric gel exhibits good mechanical strength and elastic properties, even though cross-linking originates only from metal–organic coordination at the ferrocenyl centers.

    8. A New Method for the Analysis of the Substitution Pattern of Hydroxyethyl(methyl)-Celluloses Along the Polysaccharide Chain (pages 1363–1374)

      Petra Mischnick, Inga Unterieser, Kristin Voiges, Julia Cuers, Marian Rinken and Roland Adden

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/macp.201300070

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      Substituent distribution of hydroxyethyl groups in cellulose ethers in the polymer chain is important to understand the properties. A new sample preparation allows the analysis of hydroxyethyl(methyl)-celluloses (HEMCs) and HECs in a wide molar degree of substitution (MS) range by electrospray ionization-ion trap-mass spectrometry (ESI-IT-MS).

    9. Chiral pH-Responsive Amphiphilic Polymer Co-networks: Preparation, Chiral Recognition, and Release Abilities (pages 1375–1383)

      Lu Shi, Peng Xie, Zhimin Li, Youping Wu and Jianping Deng

      Version of Record online: 28 MAY 2013 | DOI: 10.1002/macp.201200729

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      Chiral amphiphilic polymer co-networks (APCNs) are prepared by free-radical copolymerization starting from N-acryloyl-L-alanine (NAA) (a chiral monomer) and methacrylate-terminated polydimethylsiloxane (M-PDMS). The APCNs swell considerably in both water and n-hexane. They demonstrate the desired chirality and pH-responsiveness swelling in water. More interestingly, they demonstrate enantioselective adsorption and chirally controlled release abilities towards enantiomers.

    10. Investigations into the Mass Spectrometric Method for the Determination of the Mode of Termination in Radical Polymerization (pages 1384–1395)

      Majed M. Alghamdi and Gregory T. Russell

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/macp.201200734

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      A recently piloted method for the determination, by a mass spectrometric analysis, of the fraction of termination by disproportionation in radical polymerization is investigated. It is shown that the method performs as it should over a variety of different circumstances, giving confidence that it has broad fitness for use. At the same time, optimum mass spectrometry conditions are established and the occurrence of chain transfer to solvent is uncovered.

    11. Grafting of Chitosan with Styrene and Maleic Anhydride via Nitroxide-Mediated Radical Polymerization in Supercritical Carbon Dioxide (pages 1396–1404)

      Omar García-Valdez, Diana Guadalupe Ramírez-Wong, Enrique Saldívar-Guerra and Gabriel Luna-Bárcenas

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/macp.201300014

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      A synthesis route to produce chitosan-graft-poly(styrene-maleic anhydride)-OH-TEMPO (CTS-g-PSMA-T) is reported, using acetic acid solution and supercritical CO2 as reaction media. By 13C CP-MAS NMR and FTIR spectroscopy, and TGA, the production of CTS-g-PSMA-T is evidenced. A modified CTS with a graft content of 68% in weight is obtained.

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