Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 24

15 December 2013

Volume 51, Issue 24

Pages i–iv, 5163–5306

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
    1. You have free access to this content
      Cover Image, Volume 51, Issue 24 (pages i–ii)

      Article first published online: 6 NOV 2013 | DOI: 10.1002/pola.26993

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      Biodegradable copolyester hydrogels based on triblock polylactide and poly(ethylene glycol) macromonomer crosslinked with modified hyperbranched polyester Boltorn H20 were synthesized by David K. Wang, Srinivas Varanasi, Peter M. Fredericks, David J. T. Hill, Anne L. Symons, Andrew K. Whittaker, and Firas Rasoul on page 5163. The hydrogels exhibit well-tuned degradability due to hydrolysis in phosphate buffered saline at 37 °C, and the partially degraded hydrogels were comprehensively characterized by ATR-FTIR. The release of the by-products and the degrading hydrogels demonstrated good cytocompatibility for osteoblast differentiation and proliferation in vitro over a 28-day degradation period between days 23 and 28.

    2. You have free access to this content
      Cover Image, Volume 51, Issue 24 (pages iii–iv)

      Article first published online: 6 NOV 2013 | DOI: 10.1002/pola.26994

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      It is now clear that many recognition events are mediated by carbohydrate–protein binding processes. Polymer vesicles (polymersomes) with carbohydrate moieties presented on their external surface by self-assembly of suitably functionalized amphiphilic block copolymers are currently attracting ever-increasing interest in materials science and biomedicine. Giant vesicles of larger than 5 μm in diameter are of special interest due to their potential as a simple model of biological cells. The cover image shows a representative micrograph of glycosylated polymer giant unilamellar vesicles (GUVs) by confocal fluorescence microscopy. On page 5184, Neil R. Cameron et al. demonstrate a simple approach to synthesize and characterize amphiphilic glycosylated polymers that are capable of forming giant polymersomes using the electro-formation method.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    1. FT-IR characterization and hydrolysis of PLA-PEG-PLA based copolyester hydrogels with short PLA segments and a cytocompatibility study (pages 5163–5176)

      David K. Wang, Srinivas Varanasi, Peter M. Fredericks, David J.T. Hill, Anne L. Symons, Andrew K. Whittaker and Firas Rasoul

      Article first published online: 24 SEP 2013 | DOI: 10.1002/pola.26930

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      Functionalized pegylated hyperbranched polyester Boltorn H20 was crosslinked with poly(lactide-b-ethylene glycol-b-lactide) (PLA-PEG-PLA) diacrylate to form a series of in situ crosslinkable degradable hydrogels for the delivery of drug and bioactive molecules. The process of polymerc degradation is influenced by the presence of the Boltorn, the PEG and lactide block lengths, all of which played vital roles in determining the structure–property relationships in these materials. Over a 28-day hydrolysis period, cultured osteoblasts were viable and proliferating, much on par with the control tissue culture plates.

    2. Contracted helix to stretched helix Rearrangement of an aromatic polyacetylene prepared in n-hexane with [Rh(norbornadiene)Cl]2-triethylamine catalyst (pages 5177–5183)

      Asahi Motoshige, Yasuteru Mawatari, Ranko Motoshige, Yoshiaki Yoshida and Masayoshi Tabata

      Article first published online: 11 OCT 2013 | DOI: 10.1002/pola.26961

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      Polymerization at 25 °C of p-n-heptylphenylacetylene using [Rh(norbornadiene)Cl]2-triethylamine as catalyst and n-hexane as solvent afforded the red poly(p-n-heptylphenylacetylene) Poly(R)CC having helical cis-cisoid structures in 97% yield. On heating at 80 °C in N2 for 1 h, the purple-red Poly(R)CC changed to the black tetragonal crystals TetraPoly(B)CC and TetraPoly(B)CT. The color changes occurred because of the transformation from pristine contracted cis-cisoid helices to contracted cis-cisoid helices TetraPoly(B)CC and stretched cis-transoid helices TetraPoly(B)CT.

    3. Spotlight Article

      Polymersome-forming amphiphilic glycosylated polymers: Synthesis and characterization (pages 5184–5193)

      Ahmed M. Eissa, Michael J.P. Smith, Artur Kubilis, Jackie A. Mosely and Neil R. Cameron

      Article first published online: 16 OCT 2013 | DOI: 10.1002/pola.26959

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      Glycosylated amphiphilic polymers are prepared in a simple two-step process involving end-functionalization of poly(ethylene-block-ethylene glycol) with an alkyne moiety then click reaction with azidoethyl glycosides. The resulting polymers can be assembled into giant polymersomes by electroformation, and the glucosyl derivative is shown to be able to bind to the lectin Concanavalin A.

    4. Facile synthesis of amphoteric ion exchange membrane by radiation grafting of sodium styrene sulfonate and N,N-dimethylaminoethyl methacrylate for vanadium redox flow battery (pages 5194–5202)

      Jie Yuan, Chuhong Yu, Jing Peng, Yu Wang, Jun Ma, Jingyi Qiu, Jiuqiang Li and Maolin Zhai

      Article first published online: 5 OCT 2013 | DOI: 10.1002/pola.26949

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      Sodium styrene sulfonate and N,N-dimethylaminoethyl methacrylate are grafted into poly(vinylidene difluoride) film using γ-radiation techniques. The CH3+ cations generated by the radiolysis of DMSO make the quaternization occur at the same time with grafting. Therefore, it is a unique way to synthesize a quaternized amphoteric ion exchange membrane in one step.

    5. Synthesis and characteristics of poly(methacrylic acid-co-N-isopropylacrylamide) thermosensitive composite hollow latex particles and their application as drug carriers (pages 5203–5214)

      Tzu-Yu Pan, Chia-Fen Lee and Chun-Hsun Chu

      Article first published online: 8 OCT 2013 | DOI: 10.1002/pola.26950

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      Poly(MAA-NIPAAm) hollow latex particles were synthesized by a three-step reaction. Transmission electron microscopy was used to observe the appearance morphology and cross-sectional morphology of magnetic composite latex particles shown as (a) and (b), respectively. The results show that the latex particles possessed a hollow structure. Both poly(MAA-NIPAAm) hollow latex particles and poly(MMA-MAA)/poly(MAA-NIPAAm) core–shell solid latex particles were used as carriers to load with caffeine. The results showed that the hollow latex particles were loaded with a larger amount of caffeine than the solid latex particles.

    6. Synthesis and polymerization of styrene monomer carrying isothiocyanate moiety and its copolymerization with HEMA based on chemo-selectivity to nucleophiles (pages 5215–5220)

      Ryu Yamasaki and Takeshi Endo

      Article first published online: 8 OCT 2013 | DOI: 10.1002/pola.26951

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      A styrene monomer bearing an isothiocyanate group was prepared without using any harmful reagents. The characteristic chemo-selectivity of the isothiocyanate group enabled synthesis of a copolymer with HEMA, which has alcohol. The reaction of alcohol and isothiocyanate was promoted by the addition of DBU to afford a networked polymer.

    7. Copolymerization of 2-isothiocyanatoethyl methacrylate and 2-hydroxyethyl methacrylate or methacrylic acid based on a nucleophile-tolerant property of the isothiocyanato group (pages 5221–5229)

      Ryota Seto, Kozo Matsumoto and Takeshi Endo

      Article first published online: 8 OCT 2013 | DOI: 10.1002/pola.26952

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      Radical copolymerizations of 2-isothiocyanatoethyl methacrylate (ITEMA) and 2-hydroxyethyl methacrylate (HEMA) or methacrylic acid (MAA) were examined, and fundamental properties of the obtained copolymers were investigated. The copolymerizations of various ITEMA/HEMA or ITEMA/MAA compositions proceeded effectively in THF or DMF by using 2,2'-azobisbutyronitorile (AIBN) as an initiator, keeping the isothiocyanato groups and hydroxyl or carboxyl groups unchanged.

    8. Synthesis of a polyurea from a glucose- or mannose-containing N-alkyl urea peptoid oligomer (pages 5230–5238)

      Yongshun Huang, Leeanne Taylor, Xiaoping Chen and Neil Ayres

      Article first published online: 8 OCT 2013 | DOI: 10.1002/pola.26953

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      The synthesis of two heparin mimetic polymers is reported. The polymers were prepared through a step-growth polymerization of a sugar-functionalized N-alkyl urea peptoid monomer and a diisocyanate to yield the final polyurea. The N-alkyl urea peptoids have been functionalized with either glucose or mannose groups using carbohydrate synthesis techniques. The final sulfated polymers are demonstrated to be highly hydrophilic with an average of 3.5 sulfate groups per saccharide.

    9. Precise synthesis of pH-responsive copolymers with naphthoic acid side groups via living cationic polymerization (pages 5239–5247)

      Yu Shinke, Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 5 OCT 2013 | DOI: 10.1002/pola.26954

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      Living cationic polymerization of ethyl 6-[2-(vinyloxy)ethoxy]-2-naphthoate (EVEN) was achieved using Et1.5AlCl1.5 as a Lewis acid catalyst in the presence of an added base in CH2Cl2 at 0 °C. Subsequent alkaline hydrolysis of the side-chain esters yielded a carboxy-containing polymer quantitatively. Aqueous solutions of the obtained polymer showed a pH-driven phase separation at pH 7.0. Stimuli-responsive behaviors of well-defined random and block copolymers were also investigated in terms of solution transmittance and size of aggregate.

    10. Helical poly(phenylacetylene)s containing schiff-base and amino groups: Synthesis, secondary structures, and responsiveness to benzoic acid (pages 5248–5256)

      Yu Zhang, Keke Gao, Zhongfu Zhao, Dongmei Yue, Yanming Hu and Toshio Masuda

      Article first published online: 5 OCT 2013 | DOI: 10.1002/pola.26955

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      Novel poly(phenylacetylene)s containing Schiff-base and amino groups were synthesized. Large optical rotations and strong CD signals demonstrated that the polymers take helical structures with a predominantly one-handed screw sense. The CD patterns of the polymer containing free amino moieties were completely inverted by the addition of benzoic acid. Upon further addition of NaOH, the CD pattern returned to the original one, indicating the reversible conformational change of these polymers according to pH.

    11. Spotlight Article

      In situ synthesis of A3-type star polymer/clay nanocomposites by atom transfer radical polymerization (pages 5257–5262)

      Muhammed Aydin, Mehmet Atilla Tasdelen, Tamer Uyar and Yusuf Yagci

      Article first published online: 11 OCT 2013 | DOI: 10.1002/pola.26957

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      Intercalated clay containing a quaternary trifunctional atom transfer radical polymerization (ATRP) initiator is prepared directly by ion exchange reaction. In situ ATRP of methyl methacrylate with 1% of organic clay loading leads to A3-type star polymer/MMT nanocomposites possessing exfoliated nanolayers in the polymer matrix.

    12. Synthesis of well-defined copolymer of acrylonitrile and maleic anhydride via RAFT polymerization (pages 5263–5269)

      Shaogan Niu, Mingqiang Ding, Mengting Chen, Ting Feng, Lifen Zhang, Liang Wei, Zhenping Cheng and Xiulin Zhu

      Article first published online: 5 OCT 2013 | DOI: 10.1002/pola.26956

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      A well-defined copolymer of acrylonitrile and maleic anhydride was successfully synthesized via RAFT polymerization, which can be used as a precursor for electrospinning.

    13. Spotlight Article

      Arborescent polypeptides from γ-benzyl l-glutamic acid (pages 5270–5279)

      Greg Whitton and Mario Gauthier

      Article first published online: 8 OCT 2013 | DOI: 10.1002/pola.26958

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      Branched polymers with characteristics mimicking globular proteins have been obtained through successive grafting reactions of polypeptide chains. These molecules display size variations in solution that are typical for proteins experiencing randomly coiled (disorganized) to α-helical (organized) conformation transitions.

    14. Naphthodithiophene-Diketopyrrolopyrrole-Based donor–Acceptor alternating π-Conjugated polymers for Organic thin-Film transistors (pages 5280–5290)

      Tae Wan Lee, Dae Hee Lee, Jicheol Shin, Min Ju Cho and Dong Hoon Choi

      Article first published online: 10 OCT 2013 | DOI: 10.1002/pola.26960

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      Novel donor–acceptor-conjugated polymers with different branched side chains are synthesized via Pd(0)-catalyzed Stille coupling reaction. PNDTDPP-DH polymer bearing relatively longer dodecylhexadecyl side chains exhibits much better charge-transport behavior than PNDTDPP-OD polymer with shorter octyldodecyl side chains. The thermally annealed PNDTDPP-DH polymer thin films exhibit an outstanding charge carrier mobility of ∼1.32 cm2 V−1 s−1 (Ion/Ioff ∼ 108) measured under ambient conditions.

    15. Preparation of a Yb(III)-Incorporated porous polymer by post-Coordination: Enhancement of gas adsorption and catalytic activity (pages 5291–5297)

      Hyungwoo Kim, Min Chul Cha, Hyun Woo Park and Ji Young Chang

      Article first published online: 10 OCT 2013 | DOI: 10.1002/pola.26962

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      Yb(III) ions were incorporated into an adamantane-based microporous polymer by post-coordination. The Yb(III)-incorporated microporous polymer showed enhanced CO2 and H2 adsorption properties and high catalytic activity in the acetalization of an aldehyde.

    16. Ethylene polymerization and ethylene/hexene copolymerization by vanadium(III) complexes bearing bidentate phenoxy-phosphine oxide ligands (pages 5298–5306)

      Sen-Wang Zhang, Ling-Pan Lu, Ying-Yun Long and Yue-Sheng Li

      Article first published online: 10 OCT 2013 | DOI: 10.1002/pola.26963

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      A series of new vanadium complexes bearing bidentate phenoxy-phosphine oxide ligands have been synthesized, characterized, and investigated as the catalyst precursors for ethylene polymerization and ethylene/hexene copolymerization.

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