Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 21

1 November 2014

Volume 52, Issue 21

Pages i–iv, 3005–3145

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
    4. Notes
    1. You have free access to this content
      Cover Image, Volume 52, Issue 21 (pages i–ii)

      Article first published online: 23 SEP 2014 | DOI: 10.1002/pola.27404

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      Two innovative methods using amphiphilic block copolymers for gold nanoparticle synthesis are reported on page 3069 (DOI: 10.1002/pola.27354) by Angel Leiva, Irma Fuentes, Esteban Bossel, Marcela Urzúa, Maximiliano Méndez, Maximiliano Pino, Deodato Radić, Valeria Márquez, and Fernando D. González-Nilo. In one method, copolymer aggregates act as reducing agents and stabilizers, and nanoparticles surrounded by aggregates are obtained. In the other method, nanoparticle formation occurs simultaneously with the aggregation of the copolymers, resulting in copolymer aggregates with embedded gold nanoparticles. Both methods provide nanocomposites of gold nanoparticles associated with copolymer aggregates that have a high number of potential applications.

    2. You have free access to this content
      Cover Image, Volume 52, Issue 21 (pages iii–iv)

      Article first published online: 23 SEP 2014 | DOI: 10.1002/pola.27405

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      On page 3107 (DOI: 10.1002/pola.27360), Po-Chih Yang, Hsin-Cheng Chen, Hua-Wen Wen, and Po-I Wu report the synthesis of two azobenzene-containing diblock copolymers to investigate the effect of azobenzene on the photoisomerization kinetics and self-assembly behaviors of copolymers using sequential RAFT polymerization. The diblock copolymer, poly(StO54-b-Cazo9), shows lower photoisomerization rate constants (kt = 0.039 s−1) compared with Cazo monomer (kt = 0.097 s−1). Poly(StO54-b-Cazo9) takes advantage of the moderate self-assembly behavior of diblock copolymer to yield spherical micelles with a mean diameter of approximately 238.3 nm in THF/H2O media.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    4. Notes
    1. Spotlight Article

      Synthesis and characterization of a biodegradable ABC triblock terpolymer as co-delivery carrier of doxorubicin and DNA (pages 3005–3016)

      Jiao Bian, Ying Hao, Jinlin He, Wenling Zhang, Mingzu Zhang and Peihong Ni

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27361

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      A new kind of cationic ABC triblock terpolymer PEEP-b-PCL-b-PDMAEMA has been successfully prepared via a combination of two-step ring-opening polymerization and atom-transfer radical polymerization reactions. The chemical structures, self-assembly behavior, in vitro enzymatic degradation, cytotoxicity, and pH-dependent controlled release of encapsulated DOX were investigated in detail. In addition, the study by a live cell imaging system further demonstrated that the polymer/DOX/DNA polyplexes could efficiently co-deliver DOX and GFP–DNA into HeLa cells, indicating that they may find potential applications for combinatorial cancer therapy.

    2. An efficient nonisocyanate route to polyurethanes via thiol-ene self-addition (pages 3017–3025)

      Mariola Calle, Gerard Lligadas, Juan C. Ronda, Marina Galià and Virginia Cádiz

      Article first published online: 7 AUG 2014 | DOI: 10.1002/pola.27347

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      The synthesis of a nonisocyanate polyurethane was carried out via thiol–ene self-photopolymerization using a carbamate monomer (AMC) including a thiol and double-bond end-functionalities. The thiol–ene carbamate monomer was synthesized from cysteamine and allyl chloroformate and therefore the urethane group is directly into the precursor monomer. The highly reactive AMC is successfully stabilized with pyrogallol (1% wt) as a radical inhibitor. The obtained polyurethane possesses a semi-crystalline nature and very high thermal stability (T5% = ∼325 °C).

    3. The pH induced vesicle to micelle morphology transition of a THP-protected polymer (pages 3026–3031)

      Kay E. B. Doncom, Helen Willcock and Rachel K. O'Reilly

      Article first published online: 16 AUG 2014 | DOI: 10.1002/pola.27348

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      A diblock copolymer containing a protected acid block, a permanently hydrophobic block, and a charged hydrophilic end group was synthesized by RAFT polymerization. The polymer self-assembled into vesicles in aqueous solution, directed by the hydrophilic end group, and the removal of the protecting groups yielded an amphiphilic diblock copolymer, which exists as micelles in aqueous solution. The vesicle to micelle morphology was demonstrated by dynamic light scattering and TEM.

    4. Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates (pages 3032–3036)

      Hiroharu Ajiro, Tatsuaki Ueyama and Mitsuru Akashi

      Article first published online: 21 AUG 2014 | DOI: 10.1002/pola.27350

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      Radical polymerizations of methacrylic acid in the porous isotactic-poly(methyl methacrylate) film, prepared by alternative layer-by-layer technique, were achieved at various temperatures. The results suggested that the thermal mobility of polymer chains is necessary to form stereocomplexes during the polymerization process, as evidenced by FT-IR spectral analyses.

    5. Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis (pages 3037–3044)

      Shinichi Itsuno, Yosuke Hashimoto and Naoki Haraguchi

      Article first published online: 14 AUG 2014 | DOI: 10.1002/pola.27351

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      Polymerization of the achiral amphiphilic monomer, divinylbenzene, and polymerizable chiral 1,2-diamine monosulfonamide ligand results in a polymer-immobilized chiral ligand. Complexation of the polymeric chiral ligand with [IrCl2Cp*]2 affords the polymeric chiral complex, which has been successfully applied to asymmetric transfer hydrogenation of cyclic imines in both organic solvents and water to give chiral cyclic amines with a high level of enantioselectivity. The polymeric catalyst can be recycled many times without loss of the catalytic activity.

    6. Spotlight Article

      Modified soybean oil as a reactive diluent: Synthesis and characterization (pages 3045–3059)

      Priyanka P. Nalawade, Brinda Mehta, Coleen Pugh and Mark D. Soucek

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27352

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      Soybean oil was modified in two steps: (1) conjugation of soybean oil, (2) Diels-Alder addition with 3-(trimethoxysilyl)propyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and triallyl ether acrylate. 13C-1H gHSQC NMR spectra helped confirm the formation of a cyclohexene ring in all reactions, indicating a Diels-Alder addition. The diluent efficiency of modified soybean oil was evaluated in long oil alkyd formulation. Triallyl ether functionalized soybean oil resulted in the highest reduction in the viscosity of the alkyd formulations.

    7. Photo-induced thiol-ene polysulfide-crosslinked materials with tunable thermal and mechanical properties (pages 3060–3068)

      So Young An, Dong Geun Lee, Ji Won Hwang, Kyung Nam Kim, Joon Hyun Nam, Hyun Wook Jung, Seung Man Noh and Jung Kwon Oh

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27353

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      A versatile and effective approach is reported utilizing high-molecular-weight methacrylate copolymers, with pendant thiol and vinyl groups (MCPsh and MCPenes), to modulate the thermal and mechanical properties of photo-induced thiol-ene crosslinked materials.

    8. Block copolymers in the synthesis of gold nanoparticles. Two new approaches: Copolymer aggregates as reductants and stabilizers and simultaneous formation of copolymer aggregates and gold nanoparticles (pages 3069–3079)

      Angel Leiva, Irma Fuentes, Esteban Bossel, Marcela Urzúa, Maximiliano Méndez, Maximiliano Pino, Deodato Radić, Valeria Márquez and Fernando. D. González-Nilo

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27354

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      Two methods for the synthesis of gold nanoparticles are reported. In the first, copolymer aggregates react with AuCl4, and nanoparticles surrounded by aggregates are obtained. In the second, nanoparticle formation takes place simultaneously with the aggregation of copolymers, resulting in copolymer aggregates with embedded gold nanoparticles.

    9. Chiral sensing of Eu(III)-containing achiral polymer complex from chiral amino acids coordination induction (pages 3080–3086)

      Chunhui Dai, Yuxiang Wang, Yiwu Quan, Qingmin Chen, Yixiang Cheng and Chengjian Zhu

      Article first published online: 18 AUG 2014 | DOI: 10.1002/pola.27356

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      A novel β-diketonate-based Eu(III)-containing polymer complex was designed as a CD probe for direct enantioselective recognition of N-Boc-proline enantiomers. The linear regression analysis of in situ CD sensing shows a good agreement between the magnitude of molar ellipticity and concentration of chiral N-Boc-l or d-proline, indicating that this kind Eu(III)-containing achiral polymer complex can be used as a chiral-sensing probe for enantioselective recognition of N-Boc-l or d-proline enantiomers based on the Cotton effect of CD spectra.

    10. Smart photoluminescent nanohybrids based on CdSe quantum dots capped with multidentate thiolated pH-responsive and thermoresponsive polymers for nanosensing (pages 3087–3095)

      Marta Liras, Elena Peinado, Pedro Cañamero, Isabel Quijada-Garrido and Olga García

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27358

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      Well-defined thermoresponsive polymers obtained by the atom transfer radical polymerization (ATRP) of MEOnMA (n = 2, 3, or 8) with small ratios of a thiolated comonomer (AcSEMA) can replace the hydrophobic trioctylphosphine oxide capping of CdSe quantum dots (QDs). After ligand exchange, the mild hydrolysis of the acetylthiol group into thiol is the key to enhance the QD luminescence. These copolymers endowed the final materials with their thermoresponsive and amphiphilic properties. The hybrids showed good water dispersability, lower critical solubility temperature around body temperature and, most importantly, an abrupt increase of the fluorescence emission when the polymer collapses in acidic media.

    11. Well-controlled ring-opening polymerization of cyclic esters catalyzed by aluminum amido complexes: Kinetics and mechanism (pages 3096–3106)

      Junpeng Liu and Haiyan Ma

      Article first published online: 13 AUG 2014 | DOI: 10.1002/pola.27359

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      A series of aluminum dimethyl complexes bearing bidentate amido ligands were synthesized and characterized. These complexes can initiate the ring-opening polymerizations of ε−caprolactone and rac-lactide in a well-controlled manner as single component catalysts and afford narrowly distributed polycaprolactones or polylactides end-capped with the bidentate amido ligands. This proves that the polymerizations of ε−caprolactone and rac-lactide are initiated via the insertion of monomer into the Al[BOND]N (amido) bond of the complexes.

    12. Preparation and self-assembly of stimuli-responsive azobenzene-containing diblock copolymers through microwave-assisted RAFT polymerization (pages 3107–3117)

      Po-Chih Yang, Hsin-Cheng Chen, Hua-Wen Wen and Po-I Wu

      Article first published online: 21 AUG 2014 | DOI: 10.1002/pola.27360

      Thumbnail image of graphical abstract

      Two azobenzene-containing diblock copolymers were synthesized to investigate the effect of azobenzene on the photoisomerization kinetics and self-assembly behaviors of copolymers using sequential reverse addition-fragmentation transfer (RAFT) polymerization. The diblock copolymer, poly(StO54-b-Cazo9), showed lower photoisomerization rate constants (kt = 0.039 s−1) compared with Cazo monomer (kt = 0.097 s−1). Poly(StO54-b-Cazo9) takes advantage of the moderate self-assembly behavior of the diblock copolymer to yield spherical micelles with a mean diameter of ∼238.3 nm in THF/H2O media.

    13. Spotlight Article

      Tuning the LCST of poly(2-cyclopropyl-2-oxazoline) via gradient copolymerization with 2-ethyl-2-oxazoline (pages 3118–3122)

      Mathias Glassner, Kathleen Lava, Victor R. de la Rosa and Richard Hoogenboom

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27364

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      A series of P(c-PropOx-grad-EtOx) gradient copolymers were prepared by living cationic ring opening polymerization of 2-cyclopropyl-2-oxazoline and 2-ethyl-2-oxazoline. All copolymers showed a reversible LCST transition in aqueous solution. The cloud point temperature (TCP) decreased linearly with increasing mole fraction of c-PropOx, allowing accurate tuning of TCP over a wide temperature range. Surprisingly, the glass transition temperatures of all copolymers were lower than those of the homopolymers, indicating poor interchain miscibility.

    14. Mechanical and shape-memory properties of poly(mannitol sebacate)/cellulose nanocrystal nanocomposites (pages 3123–3133)

      Águeda Sonseca, Sandra Camarero-Espinosa, Laura Peponi, Christoph Weder, E. Johan Foster, José M. Kenny and Enrique Giménez

      Article first published online: 25 AUG 2014 | DOI: 10.1002/pola.27367

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      The synthesis of nanocomposites of poly(mannitol-sebacate) and cellulose nanocrystals was achieved in two steps. A low-molecular-weight pre-polymer that was soluble in common solvents was first formed via the polycondensation reaction between sebacic acid and D-mannitol. Nanocomposites with different cellulose nanocrystal contents were subsequently prepared by solution casting and curing under vacuum. The new materials display a shape-memory effect.

    15. Rapid metal-free macromolecular coupling via In Situ nitrile oxide-activated alkene cycloaddition (pages 3134–3141)

      Michael J. Isaacman, Weibin Cui and Luke S. Theogarajan

      Article first published online: 25 AUG 2014 | DOI: 10.1002/pola.27371

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      Metal-free polymer-polymer conjugation is crucial to the development of smart materials, especially for drug delivery and biosensing. A scalable, versatile, and modular procedure is presented for the synthesis of ABA triblock copolymers based on 1,3 dipolar cycloaddition. The versatility of the approach is demonstrated by coupling both hydrophilic and hydrophobic A blocks with a polysiloxane B block. Hydrophilic A blocks imparting stealth, thermoresponsive, and self-assembled nanopatterning behavior were successfully coupled, thus illustrating the modularity of the approach.

  3. Notes

    1. Top of page
    2. Cover Image
    3. Articles
    4. Notes
    1. You have free access to this content
      Solubility switching of fluorescent polymer films via lewis acid–base vapor treatments (pages 3142–3145)

      Shotaro Hayashi and Toshio Koizumi

      Article first published online: 25 AUG 2014 | DOI: 10.1002/pola.27366

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      Fluorescence and solubility switching of a pyridine-fluorene alternating copolymer film via Lewis acid (BF3-OEt2)-base (Et3N) vapor treatments is reported. The solubility switching of the polymer film via the Lewis acid-base vapor treatment method could be applied to pattern development.

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