Macromolecular Rapid Communications

Cover image for Vol. 33 Issue 9

Special Issue: Polymer Science: The Next Generation

May 14, 2012

Volume 33, Issue 9

Pages 713–875

Issue edited by: J.-F Lutz, S. Liu, B. Sumerlin

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Feature Articles
    7. Communications
    1. Macromol. Rapid Commun. 9/2012 (page 713)

      Jacob G. Ray, Sandeep S. Naik, Emily A. Hoff, Ashley J Johnson, Jack T. Ly, Charles P. Easterling, Derek L. Patton and Daniel A. Savin

      Article first published online: 8 MAY 2012 | DOI: 10.1002/marc.201290029

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      Front Cover: Peptide-based ABA triblock copolymers exhibit pH-responsive sphere–vesicle and sphere–disk morphology transitions. These changes result from the energy penalty associated with folding the core B block to form a sphere in relation to the interfacial curvature associated with different charged states of the A block. Further details can be found in the article by J. G. Ray, S. S. Naik, E. A. Hoff, A. J Johnson, J. T. Ly, C. P. Easterling, D. L. Patton, and D. A. Savin* on page 819. Artwork: Courtesy of James Goetz.

  2. Masthead

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Feature Articles
    7. Communications
    1. Macromol. Rapid Commun. 9/2012

      Article first published online: 8 MAY 2012 | DOI: 10.1002/marc.201290030

  3. Contents

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Feature Articles
    7. Communications
    1. Macromol. Rapid Commun. 9/2012 (pages 715–720)

      Article first published online: 8 MAY 2012 | DOI: 10.1002/marc.201290028

  4. Editorial

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Feature Articles
    7. Communications
    1. You have free access to this content
      Polymer Science: The Next Generation (page 721)

      Jean-François Lutz, Shiyong Liu and Brent Sumerlin

      Article first published online: 8 MAY 2012 | DOI: 10.1002/marc.201200171

  5. Feature Articles

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Feature Articles
    7. Communications
    1. Development of Star Polymers as Unimolecular Containers for Nanomaterials (pages 722–734)

      Haifeng Gao

      Article first published online: 14 MAR 2012 | DOI: 10.1002/marc.201200005

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      Star polymers enjoying the advantages of facile synthesis, flexible compositions, and tunable sizes are an important material to be used as unimolecular containers and reactors. This Feature Article highlights the recent development on synthesis and application of core-shell structured star polymers for applications in drug delivery, catalysis, and templates for hybrid nanomaterials.

    2. Solidified Liquid Layer Model Expands the Application Fields of Quartz Crystal Microbalance (pages 735–741)

      Long Fu, Yanyan Chen and Hongwei Ma

      Article first published online: 11 APR 2012 | DOI: 10.1002/marc.201100878

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      The swelling behaviour of surface- tethered weak polyelectrolytes in salt solutions is studied by both ellipsometry and quartz crystal microbalance (QCM). Ellipsometry studies support the proposed solidified liquid layer (SLL) model. QCM experiments designed according to the SLL model are highly sensitive: a 0.18 nm thickness change of the SLL will lead to a 1 Hz frequency change.

    3. The Glycopolymer Code: Synthesis of Glycopolymers and Multivalent Carbohydrate–Lectin Interactions (pages 742–752)

      C. Remzi Becer

      Article first published online: 16 APR 2012 | DOI: 10.1002/marc.201200055

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      Glycopolymers have unique recognition properties and can be used in various bioapplications. The well-defined structures of glycopolymers effect their binding to proteins significantly. It is crucial to gain absolute control over their structure to control specific carbohydrate–lectin interactions. These interactions can be best determined by advanced techniques, QCM and SPR.

  6. Communications

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Feature Articles
    7. Communications
    1. Transforming Frozen Self-Assemblies of Amphiphilic Block Copolymers Into Dynamic pH-Sensitive Micelles (pages 753–759)

      Fabien Dutertre, Olivier Boyron, Bernadette Charleux, Christophe Chassenieux and Olivier Colombani

      Article first published online: 24 APR 2012 | DOI: 10.1002/marc.201200078

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      This article presents a chemistry-based method to transform frozen aggregates of amphiphilic block copolymers into dynamic micelles by introducing pH-sensitive hydrophilic units into the hydrophobic block of the block copolymer. The figure represents the reversible aggregation of micelles formed by a P(nBMA50%-stat-DMAEMA50%)-block-PDMAEMA diblock copolymer as a function of the ionization degree of the DMAEMA units.

    2. Synthesis of Functional Core, Star Polymers via RAFT Polymerization for Drug Delivery Applications (pages 760–766)

      Jinna Liu, Hien Duong, Michael R. Whittaker, Thomas P. Davis and Cyrille Boyer

      Article first published online: 12 APR 2012 | DOI: 10.1002/marc.201200029

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      Well-dispersed biodegradable star polymers are described for conjugating drugs via a pH-responsive linker. Doxorubicin was conjugated to the star cores using amine–aldehyde coupling reactions. Subsequently, the star polymer–doxorubicin conjugates were subjected to in vitro analyses to assess toxicity and doxorubicin release.

    3. A POSS-Based Supramolecular Amphiphile and Its Hierarchical Self-Assembly Behaviors (pages 767–772)

      Binbin Jiang, Wei Tao, Xin Lu, Yong Liu, Haibao Jin, Yan Pang, Xiaoyi Sun, Deyue Yan and Yongfeng Zhou

      Article first published online: 14 MAR 2012 | DOI: 10.1002/marc.201100877

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      This work reports a POSS-based supramolecular amphiphile generated through the host–guest inclusion complexation between a mono adamantane-functionalized POSS and a cyclodextrin oligomer, which further self-assembles into hollow nanospheres, sphere layers, and nanoporous films in a hierarchical way. The obtained supramolecular structures have demonstrated great potential in biomedical applications, e.g., as matrix materials for cell adhesion and proliferation.

    4. Regulation of Supramolecular Chirality in Co-Assembled Polydiacetylene LB Films with Removable Azobenzene Derivatives (pages 773–778)

      Hao Jiang, Xin Chen, Xiujuan Pan, Gang Zou and Qijin Zhang

      Article first published online: 21 FEB 2012 | DOI: 10.1002/marc.201100806

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      Chiral regulation has been achieved through the co-assembly of PCDA with different azobenzene derivatives, or by the photo-isomerization of the azobenzene chromophores, combining supramolecular chemistry and the LB technique. The hydrogen bonding interaction between PCDA and PAzo is suggested to be responsible for the regular helical packing of PCDA molecules in the monolayer, resulting in chiral amplification of PDA LB films.

    5. Exploiting Thermoresponsive Polymers to Modulate Lipophilicity: Interactions With Model Membranes (pages 779–784)

      Yussif Saaka, Robert C. Deller, Alison Rodger and Matthew I. Gibson

      Article first published online: 15 MAR 2012 | DOI: 10.1002/marc.201100873

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      The interactions of thermoresponsive poly[oligo(ethyleneglycol)methacrylates] with phospholipid bilayers as the polymers are heated above their lower critical solution temperature (LCST) are studied. Above the LCST, the polymers are lipophilic and can, therefore, insert in lipid bilayers, as probed by a series of complementary assays. This provides insight into the role of “smart” polymers in biotechnological applications.

    6. Mesoporous Polymer Networks–Ultraporous DVB Resins by Hard-Templating of Close-Packed Silica Spheres (pages 785–790)

      Antje Wilke and Jens Weber

      Article first published online: 21 FEB 2012 | DOI: 10.1002/marc.201100862

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      Meso- and microporous poly(DVB) resins can be synthesized by a simple hard-templating method. The resulting resins have high surface areas combined with a high porosity, typically exceeding 60%. The resins can be functionalized without loss of porosity and show good performance for adsorption applications. Because of their spherical pore shape, they can also be used as model systems for the analysis of pore stability in ultraporous systems.

    7. Oligoaniline-Containing Supramolecular Block Copolymer Nanodielectric Materials (pages 791–797)

      Christopher G. Hardy, Md. Sayful Islam, Dioni Gonzalez-Delozier, Harry J. Ploehn and Chuanbing Tang

      Article first published online: 14 FEB 2012 | DOI: 10.1002/marc.201100849

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      Supramolecular block copolymers are prepared by reversible addition fragmentation transfer (RAFT) polymerization followed by oxidative doping with oligomer aniline. These microphase-separated supramolecular block copolymers exhibit much higher permittivity and lower dielectric loss than undoped neat block copolymers.

    8. Fully-Branched Hyperbranched Polymers with a Diselenide Core as Glutathione Peroxidase Mimics (pages 798–804)

      Yu Fu, Junyi Chen, Huaping Xu, Chantal Van Oosterwijck, Xi Zhang, Wim Dehaen and Mario Smet

      Article first published online: 21 MAR 2012 | DOI: 10.1002/marc.201100860

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      A novel fully-branched hyperbranched polymer with a diselenide catalytic core is successfully synthesized by post modification of the focal point. The cored polymer demonstrates prominent glutathione peroxidase (GPx) activity, due to the interaction between the densely branched and core-shell structured hyperbranched polymer and the substrates.

    9. Use of Solvent Effects to Improve Control Over Nitroxide-Mediated Polymerization of Isoprene (pages 805–810)

      Simon Harrisson, Patrick Couvreur and Julien Nicolas

      Article first published online: 21 FEB 2012 | DOI: 10.1002/marc.201100866

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      Control over the nitroxide-mediated polymerization of isoprene initiated by acid-functional alkoxyamines is significantly improved by carrying out the polymerization in the hydrogen-bond-accepting solvents 1,4-dioxane or pyridine. Both solvents increase the rate of initiator consumption, while the overall rate of polymerization of isoprene is increased in pyridine solution.

    10. Biocompatible Zwitterionic Sulfobetaine Copolymer-Coated Mesoporous Silica Nanoparticles for Temperature-Responsive Drug Release (pages 811–818)

      Jiao-Tong Sun, Zhi-Qiang Yu, Chun-Yan Hong and Cai-Yuan Pan

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201100876

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      The biocompatible ampholytic copolymer has been grafted onto the mesoporous silica nanoparticles via surface RAFT polymerization. The dual thermo-sensitive copolymer shell behaves specially with the increasing temperature. Thermoresponsive release of payload from the novel nanocarrier has been studied in this paper.

    11. Stimuli-Responsive Peptide-Based ABA-Triblock Copolymers: Unique Morphology Transitions With pH (pages 819–826)

      Jacob G. Ray, Sandeep S. Naik, Emily A. Hoff, Ashley J Johnson, Jack T. Ly, Charles P. Easterling, Derek L. Patton and Daniel A. Savin

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201100881

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      Poly(L-lysine)-b-poly(propylene oxide)-b-poly(L-lysine) triblock copolymers exhibit sphere-vesicle and sphere-disk micelle transitions as a function of pH. The unique responsive behavior for these triblock systems can be utilized in areas such as drug delivery, whereby a delivered drug could be spontaneously released upon pH-driven morphology transitions.

    12. Enhanced Selectivity for the Hydrolysis of Block Copoly(2-oxazoline)s in Ethanol–Water Resulting in Linear Poly(ethylene imine) Copolymers (pages 827–832)

      Huub P. C. van Kuringen, Victor R. de la Rosa, Martin W. M. Fijten, Johan P. A. Heuts and Richard Hoogenboom

      Article first published online: 4 APR 2012 | DOI: 10.1002/marc.201200046

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      A methodology for controlled and selective hydrolysis of (co)poly(2-oxazoline)s is developed. The influence of the ethanol–water solvent mixture on the hydrolysis is highlighted, even yielding enhanced selectivity for block copolymers of poly(2-methyl-2-oxazoline) and poly(2-ethyl-2-oxazoline).

    13. Efficient and Robust Star Polymer Catalysts for Living Radical Polymerization: Cooperative Activation in Microgel-Core Reactors (pages 833–841)

      Takaya Terashima, Akihisa Nomura, Makoto Ouchi and Mitsuo Sawamoto

      Article first published online: 23 APR 2012 | DOI: 10.1002/marc.201200045

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      Multifunctional star polymer ruthenium catalysts are designed to enhance activity, controllability, and functionality tolerance in living radical polymerization. Typically, the formation of pseudo hetero P,N-chelating ruthenium complexes in a star core is quite effective for methyl methacrylate and unprotected methacrylic acid.

    14. Chain-Growth Polymerization of Aryl Grignards Initiated by a Stabilized NHC-Pd Precatalyst (pages 842–847)

      Zachary J. Bryan, Mitchell L. Smith and Anne J. McNeil

      Article first published online: 5 APR 2012 | DOI: 10.1002/marc.201200096

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      A Pd catalyst that can mediate a living, chain-growth polymerization of π-conjugated monomers is reported. Using (IPr)Pd(3-chloropyridine)Cl2 as a precatalyst, both homopolymers and block copolymers of phenylene- and thiophene-based monomers were prepared. Although a living, chain-growth mechanism is observed during polymerization, the catalyst resting state is somewhat unstable after the monomer is consumed.

    15. Highly Efficient Ring-Opening Reaction of Azlactone-Based Copolymer Platforms for the Design of Functionalized Materials (pages 848–855)

      Aurélie Laquièvre, Naomi S. Allaway, Joël Lyskawa, Patrice Woisel, Jean-Marc Lefebvre and David Fournier

      Article first published online: 17 APR 2012 | DOI: 10.1002/marc.201200063

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      A platform of well-defined azlactone-functionalized copolymers was elaborated via the RAFT process using 2-styryl-4,4-dimethylazlactone (SDA) and styrene as comonomer. Highly effective ring-opening reactions are executed in mild conditions with a wide range of functionalized amines in order to provide materials with interesting properties via the anchorage of NMR-, fluorinated-, fluroescent- and electroactive- probes as well as sugars and biological peptides.

    16. Design and Synthesis of Novel “Orthogonally” Functionalizable Maleimide-Based Styrenic Copolymers (pages 856–862)

      Idil Ipek Yilmaz, Mehmet Arslan and Amitav Sanyal

      Article first published online: 20 APR 2012 | DOI: 10.1002/marc.201200036

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      Novel maleimide-containing styrenic copolymers that are “orthogonally” reactive toward thiol- and amine-containing molecules, as well as two different thiol-containing molecules via the nucleophilic thiol-ene and the radical thiol-ene “click” reactions are reported.

    17. Rapid Synthesis of Polymer Brush Surfaces via Microwave-Assisted Surface-Initiated Radical Polymerization (pages 863–868)

      Wei Guo, Ryan M. Hensarling, Arthur L. LeBlanc, Emily A. Hoff, Austin D. Baranek and Derek L. Patton

      Article first published online: 18 APR 2012 | DOI: 10.1002/marc.201100829

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      Microwave-assisted surface-initiated radical polymerization (μW-SIP) enables the rapid synthesis of polymer brush surfaces with significant enhancement in film growth over conventional heating.

    18. Multibrominated Hyperbranched Polymers: Synthesis and Further Functionalizations by ARGET ATRP or Click Chemistry (pages 869–875)

      Delia-Laura Popescu and Nicolay V. Tsarevsky

      Article first published online: 18 APR 2012 | DOI: 10.1002/marc.201200065

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      Hyperbranched polymers with peripheral alkyl bromide groups were prepared by the copolymerization of styrene and a crosslinker in the presence of CBr4 (chain transfer agent which delayed gelation and served as the source of terminal Br atoms). The alkyl bromide groups were used in further chemical reactions (ATRP or azidation followed by click coupling) that yielded star copolymers.

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