Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 41 Issue 22

Special Issue: Japan-US Seminar on Advanced Polymer Chemistry for the 21st Century

15 November 2003

Volume 41, Issue 22

Pages 3469–3712

Issue edited by: Y. Okamoto, T. M. Swager

  1. Foreword

    1. Top of page
    2. Foreword
    3. Articles
    1. You have free access to this content
      Foreword (page 3469)

      Timothy Swager and Yoshio Okamoto

      Version of Record online: 2 OCT 2003 | DOI: 10.1002/pola.10827

  2. Articles

    1. Top of page
    2. Foreword
    3. Articles
    1. Transition-metal-templated synthesis of rotaxanes and catenanes: From small molecules to polymers (pages 3470–3477)

      Jean-Marc Kern, Jean-Pierre Sauvage, Gerard Bidan and Bernadette Divisia-Blohorn

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10842

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      This article provides an overview of the fundamental principles of the synthesis of metallocatenanes and metallorotaxanes. It also describes the synthesis and properties of electronic conducting polymers—polypyrrole and polythiophene—built around metallocatenanes and metallorotaxanes. The particular properties of this new class of polymers, including the possibility of transmetallation reactions being performed with them and the observation of electronic coupling between the metal centers and the conducting matrix, are discussed.

    2. Reversible catenation of coordination rings with Pd(II) and/or Pt(II) metal centers: Chirality induction through catenation (pages 3478–3485)

      Akiko Hori, Hisashi Kataoka, Akihiko Akasaka, Takashi Okano and Makoto Fujita

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10844

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      Chirality induction/deduction through the reversible catenation of Pd(II)- and/or Pt(II)-linked coordination rings is discussed. The chirality induction is most probably ascribed to the planer [RIGHTWARDS ARROW] double helical conformational change of a pentakis(m-phenylene) unit in the component rings, which is induced by the efficient aromatic stacking of two rings.

    3. Nanostructured ion-conductive films: Layered assembly of a side-chain liquid-crystalline polymer with an imidazolium ionic moiety (pages 3486–3492)

      Koji Hoshino, Masafumi Yoshio, Tomohiro Mukai, Kenji Kishimoto, Hiroyuki Ohno and Takashi Kato

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10832

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      Free-standing films with layered nanostructures were prepared by in situ photopolymerization of a uniformly oriented smectic A liquid-crystalline monomer with an imidazolium tetrafluoroborate moiety. The resultant film shows two-dimensional ionic conductivity.

    4. Electric properties of self-assembled monolayers of helical peptides by scanning tunneling spectroscopy (pages 3493–3500)

      Kazuya Kitagawa, Tomoyuki Morita, Megumi Kawasaki and Shunsaku Kimura

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10833

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      Electric properties of self-assembled monolayers (SAMs) of helical peptides were examined by scanning tunneling spectroscopy. Scanning tunneling microscopy images of the helical peptide SAMs exhibited bright spots at high-bias voltage. The current/voltage (I-V) curves at the bright domains showed a rectification behavior where current response was asymmetric and increased at high-bias voltage. However, I-V curves with the tip being inserted in the peptide SAM at low-bias voltage showed a zero-conductance region in the I-V curves. Helical peptides may function as molecular wire or molecular capacitors depending on the electric configuration.

    5. Synthesis and self-organization of rod–dendron and dendron–rod–dendron molecules (pages 3501–3518)

      Sébastien Lecommandoux, Harm-Anton Klok, Mehmet Sayar and Samuel I. Stupp

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10855

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      Molecules containing one or two dendritic segments and a rigid-rod-like segment were synthesized, and their structures in the solid state were investigated. The variables investigated included rod segment length as well as dendron generation, and all materials obtained were characterized by optical microscopy, differential scanning calorimetry, and X-ray scattering. Depending on the size of the rod segment and generation number of the dendritic segment, molecules organized into smectic, columnar, or cubic phases, and the symmetries observed were dominated by the anisotropic rod–rod interactions.

    6. Supramolecular polymers formed by cinnamoyl cyclodextrins (pages 3519–3523)

      Akira Harada, Masahiko Miyauchi and Taiki Hoshino

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10831

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      6-Cinnamoyl α-cyclodextrin (6-CiO-α-CD) and 6-cinnamoyl β-cyclodextrin (6-CiO-β-CD) were prepared. 6-CiO-α-CD formed intermolecular complexes to give supramolecular oligomers. 6-CiO-β-CD formed insoluble supramolecular complexes in the solid state. The structures of these complexes are discussed.

    7. Morphology-dependent luminescence properties of poly(benzyl ether) dendrimers (pages 3524–3530)

      Shu-Ichi Kimata, Dong-Lin Jiang and Takuzo Aida

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10830

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      Poly(benzyl ether) dendrimers [o-(Gn)2Ar, m-(Gn)2Ar, and p-(Gn)2Ar] consisting of two dendron subunits (Gn) linked by ortho-, meta-, and para-dialkoxybenzene focal cores (Ar) showed morphology-dependent conformational change activities, emission properties, and fluorescence depolarization activities.

    8. Amphiphilic and hydrophobic surface patterns generated from hyperbranched fluoropolymer/linear polymer networks: Minimally adhesive coatings via the crosslinking of hyperbranched fluoropolymers (pages 3531–3540)

      Daoji Gan, Anja Mueller and Karen L. Wooley

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10968

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      Covalent crosslinking reactions provide for the kinetic trapping of phase-segregating mixtures of hyperbranched fluoropolymers and linear polymer chains to yield coatings that exhibit morphological and topographical complexity.

    9. Synthesis of glycosaminoglycans via enzymatic polymerization (pages 3541–3548)

      Shiro Kobayashi, Ryosuke Itoh, Hidekazu Morii, Shun-Ichi Fujikawa, Shunsaku Kimura and Masashi Ohmae

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10839

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      Hyaluronic acid and chondroitin were successfully synthesized via enzymatic polymerization catalyzed by testicular hyaluronidases. A newly designed N-acetylhyalobiuronate oxazoline derivative (1) served as a transition-state analogue substrate monomer for the enzyme, giving rise to artificial hyaluronic acid in 52% yields with a number-average molecular weight of 1.35 × 104 through ring-opening polyaddition in a perfect regioselective and stereoselective manner. A novel N-acetylchondrosine oxazoline derivative (2) also acted as a transition-state analogue substrate monomer for the enzyme, yielding artificial chondroitin in 35% yields with a number-average molecular weight of 2.5 × 103.

    10. Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin: The first example of polycarbonate synthesis from 1-atm carbon dioxide (pages 3549–3555)

      Hiroshi Sugimoto, Hiromitsu Ohshima and Shohei Inoue

      Version of Record online: 7 OCT 2003 | DOI: 10.1002/pola.10835

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      The first successful example of the formation of polycarbonate from 1-atm carbon dioxide and epoxide was achieved by the alternating copolymerization of carbon dioxide and cyclohexene oxide with (porphinato)manganese acetate under the 1-atm pressure of carbon dioxide, giving a copolymer with an alternating sequence.

    11. Liquid-crystalline stereoregular polyketone prepared from a mesogenic vinylarene and carbon monoxide (pages 3556–3563)

      Yasutoyo Kawashima, Kyoko Nozaki, Tamejiro Hiyama, Masafumi Yoshio, Kiyoshi Kanie and Takashi Kato

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10843

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      Isotactic and syndiotactic polyketones were synthesized by the alternating copolymerizations of a mesogenic vinylarene, 4-cyano-4′-[8-(4-vinylphenyl)octyl-1-oxy]biphenyl, with carbon monoxide, and this revealed the influence of backbone tacticity on their thermal properties. The isotactic polyketone was an amorphous polymer that did not show any mesophase, whereas the syndiotactic polyketone exhibited liquid crystallinity.

    12. Solvent-free polycondensation of 1,3-bis(hydroxyphenylmethyl)benzene. II. The dramatic difference in the polymerization behavior between meso and racemic isomers (pages 3564–3571)

      Masato Suzuki, Takeshi Sasaki, Go Matsuura and Mika Kimura

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10834

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      The meso and racemic forms of 1,3-bis(hydroxyphenylmethyl)benzene underwent solvent-free polycondensation with the aid of an acid catalyst giving polyether. Very interestingly, the diastereoisomerism caused a considerable difference in the polymerization behavior. The meso isomer was polymerized even at 65 °C, whereas the racemic one required heating at 100 °C to undergo polymerization. However, the latter produced a much higher molecular weight than the former (30,000 vs 4000). The contamination of the meso isomer with the racemic one very sensitively reduced the polymerization temperature: the 98.5% meso monomer underwent polymerization at 50 °C. In contrast to solvent-free polymerization, two diastereomeric monomers showed almost identical behavior in solution polymerization.

    13. Biodegradations of block copolymers composed of L- or D,L-lactide and six-membered cyclic carbonates prepared with organolanthanide initiators (pages 3572–3588)

      Chikara Tsutsumi, Katsuhiro Yamamoto, Akiko Ichimaru, Mitsufumi Nodono, Katsuhiko Nakagawa and Hajime Yasuda

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10828

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      Diblock copolymerizations of L- or D,L-lactide (LA) with trimethylene carbonate (TMC) or 2,2-dimethyltrimethylene carbonate (2,2-DTMC) were carried out with SmMe(C5Me5)2(tetrahydrofuran) as an initiator in toluene. The degradabilities of the resulting polymers a were analyzed with phosphate buffer, a compost, and an enzyme, proteinase K, and compared with that of the corresponding random copolymers. Triblock copolymerizations of L- or D-LA with cyclic carbonates were also examined with (C5Me5)2]2(PhC[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]CPh) as an initiator to give poly(LA)-block-poly(cyclic carbonate)-block-poly(LA) b. Their biodegradabilities and mechanical properties were compared with those of diblock and random copolymers. Morphological change during biodegradation was measured by scanning electron microscopic observation.

    14. Nucleobase-induced supramolecular polymerization in the solid state (pages 3589–3596)

      Stuart J. Rowan, Phiriyatorn Suwanmala and Sona Sivakova

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10967

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      Supramolecular polymeric materials were obtained by the addition of adenine and thymine derivatives to the ends of low-molecular-weight poly(tetrahydrofuran). The adenine-derived supramolecular telechelic polymer self-assembled in the solid state to yield materials with film- and fiber-forming capabilities. This material was thermally reversible and exhibited a ceiling temperature, above which a drop in viscosity was observed and fibers could no longer be obtained.

    15. Amino alcohol additives for the fast living radical polymerization of methyl methacrylate with RuCl2(PPh3)3 (pages 3597–3605)

      Tsuyoshi Ando, Chie Sawauchi, Makoto Ouchi, Masami Kamigaito and Mitsuo Sawamoto

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10837

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      Amino alcohols were proven to be effective additives (cocatalysts) for the Ru-catalyzed living radical polymerization of methyl methacrylate. HO[BOND](CH2)2[BOND]NEt2 and related amino alcohols accelerated the polymerization at 60 °C, whereas the additive-free system was not active at all. The polymerization rate was enhanced by an order of magnitude, whereas the polymer molecular weight was finely controlled. The fast polymerization also led to polymers of high molecular weights beyond 105. The additives were thought to interact with the Ru center in a bidentate and cooperative fashion via their dual functionalities to form a more active catalyst in situ.

    16. Further progress in atom transfer radical polymerizations conducted in a waterborne system (pages 3606–3614)

      Mei Li and Krzysztof Matyjaszewski

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10936

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      An improved atom transfer radical polymerization (ATRP) process was developed for use in a waterborne miniemulsion system. To conduct a successful ATRP in a heterogeneous waterborne system, it is of great importance to ensure control over the polymerization process while preserving colloidal stability. Efforts devoted to optimization of reaction conditions and improvement in the overall productivity of the process allowed the development of a novel, practical initiation system for ATRP suitable for use in a miniemulsion procedure that can provide copolymers of well-defined composition (e.g., block copolymers) and topologies (e.g., multiarm polymer).

    17. Synthesis and absorption/emission properties of novel poly(silylenearylenevinylene)s (pages 3615–3624)

      Giseop Kwak, Ken-Ichi Sumiya, Fumio Sanda and Toshio Masuda

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10829

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      Polymerization of p-(dimethylsilyl)phenylacetylene with RhI(PPh3)3 afforded stereoregular cis- and trans-poly(1a)s with 98% cis- and 99% trans-vinylene moieties. Photoirradiation of cis- and trans-poly(1a)s gave cis-rich mixtures at equilibrium states. These polymers exhibited relatively weak emission, for example, trans polymer, quantum yield: 3.4 × 10−3. Poly(dimethylsilylenearylenevinylene)s containing biphenylene and phenylenesilylenephenylene units [poly(3)s] were prepared. The quantum yield of the trans-rich polymer with biphenylene moiety was fairly large and 0.15. Polyaddition of 1,4-bis(dimethylsilyl)benzene and three types of diethynylarenes (4,4′-diethynylbiphenyl, 2,7-diethynylfluorene, and 2,6-diethynylnaphthalene) provided poly(6)s, which displayed strong blue light emission with high quantum yields (0.04–0.81).

    18. Solvent-induced switching of the macromolecular helicity of poly[(4-carboxyphenyl)acetylene] induced by a single chiral amino alcohol (pages 3625–3631)

      Katsuhiro Maeda, Kazuhide Morino and Eiji Yashima

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10841

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      Cis–transoidal poly[(4-carboxyphenyl)acetylene] (poly-1) complexed with optically active amines and amino alcohols showed an induced circular dichroism (ICD) in the ultraviolet–visible region because of a predominantly one-handed helix formation in water and in dimethyl sulfoxide (DMSO). The Cotton effect signs of the poly-1/chiral amino alcohol complexes were inverted in the presence of water, whereas the ICD pattern of the poly-1/chiral amine complexes showed no change, regardless of the water content. These results demonstrated that the helix sense of poly-1 induced by optically active amino alcohols through noncovalent acid–base interactions could be switched by changes in the solvent ratio in the DMSO–water mixtures.

    19. Dielectric assembly of a collagen-model polypeptide in a triple helix (pages 3632–3639)

      Yukio Imanishi, Naoki Kawazoe and Kensuke Ichizawa

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10840

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      An oriented monolayer assembly of a collagen-model triple-helix polypeptide, (Pro-Pro-Gly)10[BOND]NH2, was immobilized on a thin gold film at a 46° tilt angle of the helix axis against the film surface. The strongly dipolar assembly of the triple-helix polypeptide was stable at temperatures as high as 90 or 150 °C and produced a surface electric potential as well as a pyroelectric effect.

    20. Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures (pages 3640–3656)

      Padma Gopalan, Xuefa Li, Mingqi Li, Christopher K. Ober, Chad P. Gonzales and Craig J. Hawker

      Version of Record online: 8 OCT 2003 | DOI: 10.1002/pola.10930

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      A modular approach has been developed for the synthesis of rod–coil block copolymers that undergo self-assembly to give lamellar microstructures with rigid domains in which the rod units lie in an interdigitated smectic C arrangement.

    21. Functionalization of polyethylene based on metallocene catalysis and its application to syntheses of new graft copolymers possessing polar polymer segments (pages 3657–3666)

      Norio Kashiwa, Tomoaki Matsugi, Shin-Ichi Kojoh, Hideyuki Kaneko, Nobuo Kawahara, Shingo Matsuo, Tadahito Nobori and Jun-Ichi Imuta

      Version of Record online: 9 OCT 2003 | DOI: 10.1002/pola.10838

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      The structures of hydroxylated polyethylenes were controlled through changes in the experimental conditions in the copolymerization of ethylene with allyl alcohol or 10-undecen-1-ol. The obtained copolymers were useful as macroinitiators that allowed polar polymer segments to grow on the polyethylene backbones, leading to the creation of unique graft copolymers. In this way, polyethylene-g-poly(propylene glycol) (PE-g-PPG) and polyethylene-g-poly(ϵ-caprolactone) (PE-g-PCL) were synthesized. The 13C NMR analysis of PE-g-PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization, and transmission electron microscopy demonstrated nanoorder phase separation and indistinct phase boundaries. The formation of PE-g-PCL was indicated by 13C NMR and gel permeation chromatography analyses.

    22. Aminosalicylate-based biodegradable polymers: Syntheses and in vitro characterization of poly(anhydride-ester)s and poly(anhydride-amide)s (pages 3667–3679)

      Theodore J. Anastasiou and Kathryn E. Uhrich

      Version of Record online: 9 OCT 2003 | DOI: 10.1002/pola.10973

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      Poly(anhydride-esters) and poly(anhydride-amides) derived from both 4- and 5- aminosalicylates (4- and 5-A5 A) were synthesized, then evaluated as drug delivery systems. All polymers fully degraded at physiological pH (7.4) but degradation was insignificant in acidic media (pH 1.2) in the gastrointestinal time scale (30–40 h) for the polymers.

    23. Control of polymer topology through late-transition-metal catalysis (pages 3680–3692)

      Zhibin Guan

      Version of Record online: 9 OCT 2003 | DOI: 10.1002/pola.10969

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      Late-transition-metal polymerization catalysts are shown to be powerful for controlling polymer topologies. By the judicious selection or design of late-transition-metal catalysts, polymers with a broad range of topologies, including linear, short-chain-branched, hyperbranched, dendritic, and cyclic topologies, have been successfully synthesized. For example, a chain-walking catalyst has been demonstrated to control the polyethylene topology from a linear form to a hyperbranched form to a dendritic form.

    24. Cofacially constrained organic semiconductors (pages 3693–3702)

      John D. Tovar and Timothy M. Swager

      Version of Record online: 10 OCT 2003 | DOI: 10.1002/pola.10970

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      This article describes an efficient strategy for the synthesis of bridged, cofacially oriented oligo(thiophene) groups. The bis(terthiophene) monomer shown displayed extended electronic delocalization relative to the analogous mono(terthiophene) as evidenced by spectroscopic and electrochemical studies. These monomers underwent anodic polymerization to provide highly crosslinked yet electrochromic polymer films.

    25. Preparation and chiral recognition ability of cellulose 3,5-dimethylphenylcarbamate immobilized on silica gel through radical polymerization (pages 3703–3712)

      Takateru Kubota, Chiyo Yamamoto and Yoshio Okamoto

      Version of Record online: 9 OCT 2003 | DOI: 10.1002/pola.10836

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      Polysaccharide-immobilized chiral stationary phases (CSPs) were prepared by the copolymerization of cellulose 3,5-dimethylphenylcarbamate derivatives having a polymerizable vinyl group with a vinyl monomer such as styrene on silica gel under various conditions, and their chiral recognition abilities were evaluated by high-performance liquid chromatography. These immobilized CSPs were stable when used with an eluent containing 10% chloroform, which cannot be used with conventional polysaccharide-coated CSPs. The chiral recognition abilities of the immobilized CSPs were similar to those of the coated CSPs when the vinyl monomer content was low.

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