Macromolecular Rapid Communications

Cover image for Vol. 32 Issue 2

Special Issue: Precision Macromolecular Chemistry

January 17, 2011

Volume 32, Issue 2

Pages 107–244

Issue edited by: H. G. Börner, J.-F. Lutz

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Feature Articles
    6. Communications
    7. Back Cover
    1. Macromol. Rapid Commun. 2/2011

      Jean-François Lutz and Hans G. Börner

      Article first published online: 12 JAN 2011 | DOI: 10.1002/marc.201190000

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      Front Cover: Like an old-time watchmaker… modern polymer chemists aim to control defined molecular parameters, such as polydispersity, tacticity or comonomer sequences, using sharp chemical tools. These precision aspects of macromolecular science are highlighted in the present special issue co-edited by Hans G. Börner and Jean-François Lutz.

  2. Contents

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Feature Articles
    6. Communications
    7. Back Cover
    1. Macromol. Rapid Commun. 2/2011 (pages 107–112)

      Article first published online: 12 JAN 2011 | DOI: 10.1002/marc.201190001

  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Feature Articles
    6. Communications
    7. Back Cover
    1. Precision Macromolecular Chemistry (pages 113–114)

      Jean-François Lutz and Hans G. Börner

      Article first published online: 14 DEC 2010 | DOI: 10.1002/marc.201000728

  4. Feature Articles

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Feature Articles
    6. Communications
    7. Back Cover
    1. Precision Polymers—Modern Tools to Understand and Program Macromolecular Interactions (pages 115–126)

      Hans G. Börner

      Article first published online: 27 DEC 2010 | DOI: 10.1002/marc.201000646

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      Peptide-block-polymer copolymers possess a monodisperse peptide segment with a freely programmable monomer sequence. This can be exploited, to tailor interaction capabilities of these polymer systems, defining interactions to small molecule drugs, DNA, crystallization processes or cells. An overview on the possibilities that arise from these precisely adjustable, functional polymers for materials sciences is presented.

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      Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N-substituted Maleimides (pages 127–135)

      Jean-François Lutz, Bernhard V. K .J. Schmidt and Sebastian Pfeifer

      Article first published online: 3 JAN 2011 | DOI: 10.1002/marc.201000664

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      The controlled radical copolymerization of styrene with N-substituted maleimides allows preparation of unique polymer microstructures. Indeed, we reported in recent years that small amounts of N-substituted maleimides can be placed at specific locations in linear polystyrene chains. Herein, we describe in details this research advance. The kinetic concept, the experimental conditions and the scope of this novel strategy are discussed in this feature article.

    3. Synthesis and Function of Double-Stranded Helical Polymers and Oligomers (pages 136–146)

      Yoshio Furusho and Eiji Yashima

      Article first published online: 22 NOV 2010 | DOI: 10.1002/marc.201000533

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      This paper describes recent developments in the synthesis and functions of double helical polymers and oligomers, highlighting our recent results. Although the artificial double helices are still underdeveloped, significant progress in supramolecular chemistry has fortunately established a robust platform for generating a variety of supramolecular synthons. Now the time is ready to explore the chemistry of artificial double helices.

    4. Precise Synthesis of Molecularly Defined Oligomers and Polymers by Orthogonal Iterative Divergent/Convergent Approaches (pages 147–168)

      Sandra Binauld, Denis Damiron, Luke A. Connal, Craig J. Hawker and Eric Drockenmuller

      Article first published online: 3 DEC 2010 | DOI: 10.1002/marc.201000548

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      By combining orthogonal and highly efficient deprotection and coupling reactions, the iterative divergent/convergent approach is particularly suited for the synthesis of molecularly defined oligomers and polymers. Starting from an orthogonally protected elementary building block, this powerful strategy affords a doubling of the chain length at each deprotection/coupling cycle.

    5. Metal-Catalyzed Synthesis of Alternating Copolymers (pages 169–185)

      Emilie Brulé, Jia Guo, Geoffrey W. Coates and Christophe M. Thomas

      Article first published online: 22 NOV 2010 | DOI: 10.1002/marc.201000524

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      In order to obtain alternating polymers, coordination polymerization using well-defined metal complexes has played a leading role in the last two decades. In the following paper, we will describe selected published efforts to achieve these research goals using discrete, structurally well-characterized metal complexes.

  5. Communications

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Feature Articles
    6. Communications
    7. Back Cover
    1. De Novo Design of Supercharged, Unfolded Protein Polymers, and Their Assembly into Supramolecular Aggregates (pages 186–190)

      Anke Kolbe, Loretta L. del Mercato, Azhar Z. Abbasi, Pilar Rivera Gil, Sekineh J. Gorzini, Wim H. C. Huibers, Bert Poolman, Wolfgang J. Parak and Andreas Herrmann

      Article first published online: 15 NOV 2010 | DOI: 10.1002/marc.201000491

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      Supercharged, unfolded protein polymers based on elastin-like peptides (ELPs) are designed and expressed by introducing positively and negatively charged amino acids, respectively, within each of the repetitive pentapeptide units. An example of their potential for the fabrication of supramolecular structures is presented in this work by the assembly of multilayer capsules.

    2. Toroidal Nanostructures from Self-Assembly of Block Copolypeptides Based on Poly(L-Arginine) and β-Sheet Peptide (pages 191–196)

      Yong-beom Lim, Eunji Lee and Myongsoo Lee

      Article first published online: 15 NOV 2010 | DOI: 10.1002/marc.201000512

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      Block copolypeptides based on poly(L-arginine) and β-sheet peptide, can form toroidal nanostructures in aqueous solution by rolling-up of 1D nanoribbon and end-to-end connection of the nanoribbon under charge balanced condition. This finding offer new opportunity not only for fabricating more sophisticated peptide-based nanobiomaterials, but for understanding protein misfolding mechanism also.

    3. Precise Positioning of Chiral Building Blocks in Monodisperse, Sequence-Defined Polyamides (pages 197–202)

      Simone Mosca, Felix Wojcik and Laura Hartmann

      Article first published online: 22 DEC 2010 | DOI: 10.1002/marc.201000593

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      A novel building block for the solid phase synthesis of monodisperse, sequence-defined polyamides is presented introducing chirality to the polymer segment. The synthetic approach uses natural amino acids as a pool of chiral compounds. Here, we present the use of L-alanine for the synthesis of a mono Fmoc-protected diamine building block. Applying automated polymer synthesis, a first monodisperse, sequence-defined polyamide segment comprising chiral centers is synthesized.

    4. A Comparison of Triazole-forming Bioconjugation Techniques for Constructing Comb-Shaped Peptide–Polymer Bioconjugates (pages 203–208)

      Luiz A. Canalle, Matthijs van der Knaap, Mark Overhand and Jan C. M. van Hest

      Article first published online: 15 NOV 2010 | DOI: 10.1002/marc.201000507

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      The SPAAC and CuAAC “click” reactions are compared in the construction of comb-shaped peptide–polymer bioconjugates. It is shown that the CuAAC gives higher grafting densities, while the steric bulk of the conjugation moiety used in SPAAC seems to limit the degree of functionalization.

    5. Designer Template Initiator for Sequence Regulated Polymerization: Systems Design for Substrate-Selective Metal-Catalyzed Radical Addition and Living Radical Polymerization (pages 209–214)

      Shohei Ida, Makoto Ouchi and Mitsuo Sawamoto

      Article first published online: 15 NOV 2010 | DOI: 10.1002/marc.201000503

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      We achieved highly selective radical addition and polymerization of acid monomer utilizing the template initiators carrying single- or multi-amine recognition units. These results indicated the adequate design of the template and the selective recognition contributed the high selectivity. Such highly selective radical reactions would be the key reaction in sequence-regulated polymerization.

    6. Supported Neodymium Catalysts for Isoprene and rac-β-Butyrolactone Polymerization: Modulation of Reactivity by Controlled Grafting (pages 215–219)

      Michael Terrier, Emilie Brulé, Marta J. Vitorino, Noureddine Ajellal, Carine Robert, Régis M. Gauvin and Christophe M. Thomas

      Article first published online: 22 NOV 2010 | DOI: 10.1002/marc.201000653

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      A series of supported catalytic systems based on Nd(III) precursors have been shown to mediate isoprene polymerization when combined with alkyl aluminum activators. The surface species nature was correlated with isoprene polymerization activity and selectivity. This approach has been extended to rac-β-butyrolactone isoselective ring opening polymerization.

    7. Periodic Incorporation of Pendant Hydroxyl Groups in Repeating Sequence PLGA Copolymers (pages 220–225)

      Ryan M. Stayshich, Ryan M. Weiss, Jian Li and Tara Y. Meyer

      Article first published online: 15 NOV 2010 | DOI: 10.1002/marc.201000608

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      Repeating sequence PLGA copolymers bearing regularly spaced pendant alcohols are prepared by condensation of benzyl protected preformed segmers and subsequent hydrogenolysis. Molecular weights comparable to analogous random copolymers prepared by ring-opening are obtained. Microstructure analysis using NMR spectroscopy verifies the retention of sequence and stereochemistry in the copolymers.

    8. Nucleobase-Mediated Stereospecific Radical Polymerization and Combination with RAFT Polymerization for Simultaneous Control of Molecular Weight and Tacticity (pages 226–232)

      Youhua Tao, Kotaro Satoh and Masami Kamigaito

      Article first published online: 3 DEC 2010 | DOI: 10.1002/marc.201000614

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      A highly soluble thymine-based compound mediates the syndiospecific radical polymerization of an acrylamide monomer via the selective and strong triple hydrogen-bonding interaction. A combination with the RAFT polymerization enables the simultaneous control of molecular weight and tacticity as well as the synthesis of the stereoblock polymers.

    9. Kinetic Control of Monomer Sequence Distribution in Living Anionic Copolymerisation (pages 233–237)

      Adrian Natalello, John N. Hall, E. Alex L. Eccles, Solomon M. Kimani and Lian R. Hutchings

      Article first published online: 15 NOV 2010 | DOI: 10.1002/marc.201000482

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      Diphenylethylene and its derivatives offer the possibility of producing controlled yet complex monomer sequences when used as a comonomer in living anionic copolymerisation. Kinetic control and the inability of DPE monomers to undergo homopolymerisation enables simultaneous terpolymerisations in which the monomers react in a predefined and highly ordered sequence.

    10. Solubility and Aggregation Behavior of Dendronized Poly(p-Benzamide)s (pages 238–244)

      Christof Storz, Maren Schulze and Andreas F. M. Kilbinger

      Article first published online: 27 DEC 2010 | DOI: 10.1002/marc.201000617

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      In this paper, the solution and aggregation behavior of dendronized poly-(p-benzamide)s is studied. Copper catalyzed azide-alkyne cycloaddition was used to attach a first generation (G1) and a second generation (G2) Fréchet dendron. Depending on the size of the dendron, a poor organo-soluble (G1) and a non-aggregating, good organo-soluble (G2) polymer could be obtained. Furthermore, a strictly alternating G1-TEG-dendronized polymer has been synthesized showing good solubility and no aggregation compared to the parent homopolymer.

  6. Back Cover

    1. Top of page
    2. Cover Picture
    3. Contents
    4. Editorial
    5. Feature Articles
    6. Communications
    7. Back Cover
    1. Macromol. Rapid Commun. 2/2011

      Sandra Binauld, Denis Damiron, Luke A. Connal, Craig J. Hawker and Eric Drockenmuller

      Article first published online: 12 JAN 2011 | DOI: 10.1002/marc.201190002

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      Back Cover: The iterative divergent/convergent geometrical growth is a powerful approach for the synthesis of discrete mass oligomers. It relies on orthogonal deprotection and coupling strategies and allows chain length doubling at each iteration. It has been broadly applied to the synthesis of conjugated, amorphous or crystalline oligomers and polymers. Further information can be found in the article by S. Binauld, D. Damiron, L. A. Connal, C. J. Hawker,* and E. Drockenmuller*on page 147.

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