Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 50 Issue 5

1 March 2012

Volume 50, Issue 5

Pages i–iv, 831–1041

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    3. Rapid Communications
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      Cover Image, Volume 50, Issue 5 (pages i–ii)

      Article first published online: 25 JAN 2012 | DOI: 10.1002/pola.25917

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      Polyplex nanoparticles for nonviral gene delivery are prepared using plasmid DNA and positively charged poly-D/L aspartate-diethylenetriamine [Poly(D/L Asp-DET)] polymer, as presented by Janni Mirosevich and colleagues on page 836. These polyplexes are capable of transfecting colon and prostate cancer cells in vitro. The confocal fluorescence microscopy image demonstrates in vitro delivery of Cy5-labeled DNA to HCT-116 colon cancer cells using Poly(D/L Asp-DET) Poly(D/L Asp-DET)/Cy5-DNA polyplexes (red), rhodamine phalloidin staining of F-actin (green), and DAPI nuclear stain (blue). In addition, the polyplex nanoparticles could be further modified by covalent attachment of polyethylene glycol (PEG) to produce PEG-polyplexes that are more stable and have more biocompatible characteristics for in vivo delivery applications.

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      Inside Cover, Volume 50, Issue 5 (pages iii–iv)

      Article first published online: 25 JAN 2012 | DOI: 10.1002/pola.25918

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      Polymeric films with porous structures and microsphere patterns are prepared by the method of breath figures, mixing poly(methyl methacrylate) (PMMA) and amphiphilic copolymers containing glucose moieties in their structure, glycopolymers, as presented by Juan Rodríguez-Hernández and colleagues on page 851. Depending on experimental conditions (water content, humidity, and type of copolymer), the observed final film morphology changes significantly. Thus, films with honeycomb-patterned structures, spherical particles, or a mixture of both are obtained. In addition, polar glucose moieties are oriented principally either inside of the pores in the case of films and towards the surface in the case of particles. The specific surface bioactivity of these materials is examined using Con A-FITC, where successful binding of Con A is demonstrated by more intense fluorescence at the surface of the pores and of the particles.

  2. Rapid Communications

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    3. Rapid Communications
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      Synthesis of cyclic polyelectrolyte via direct copper(I)-catalyzed click cyclization (pages 831–835)

      Fenggui Chen, Guangming Liu and Guangzhao Zhang

      Article first published online: 13 DEC 2011 | DOI: 10.1002/pola.25869

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      Well-defined cyclic poly(acrylic acid) (PAA) has been successfully prepared based on the direct click cyclization. The linear poly(tert-butyl acrylate) (PtBA) with azide and TMS-protected alkyne group forms cyclic chain directly by the copper(I)-catalyzed click cyclization without any deprotection steps. Cyclic PAA is synthesized by the hydrolysis of cyclic PtBA. The present synthetic strategy provides a simple and efficient method to synthesize cyclic polyelectrolyte and can be applied to other polymer systems.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. Nonviral gene delivery using poly-D/L aspartate-diethylenetriamine cationic polymers and polyethylene glycol: A two-step approach (pages 836–850)

      Janni Mirosevich, Gregoire Cardoen, Brian Burke, Tara Costich and Kevin Sill

      Article first published online: 19 NOV 2011 | DOI: 10.1002/pola.25079

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      In this work, poly-D/L aspartate-diethylenetriamine [Poly(D/L Asp-DET)] polymers were synthesized and used to complex plasmid DNA to form polyplexes that were capable of transfecting colon and prostate cancer cells in vitro. Subsequently, these polyplexes were further modified by covalent attachment of polyethylene glycol (PEG) to produce PEG-polyplexes that have more biocompatible characteristics for in vivo applications.

    2. Breath figures method to control the topography and the functionality of polymeric surfaces in porous films and microspheres (pages 851–859)

      Alberto S. de León, Alexandra Muñoz-Bonilla, Marta Fernández-García and Juan Rodríguez-Hernández

      Article first published online: 26 NOV 2011 | DOI: 10.1002/pola.25826

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      Polymeric films with either porous structures or microsphere patterns were prepared by the method of breath figures, mixing high molecular weight PMMA and amphiphilic copolymers containing glucose moieties in their structure, glycopolymers. Films with honeycomb pattern structures, spherical particles, or a mixture of both were obtained by evaporation under controlled ambient conditions. In addition, polar glucose moieties were oriented principally either inside of the pores in the case of films and toward the surface in the case of particles.

    3. SET-LRP of methyl acrylate to complete conversion with zero termination (pages 860–873)

      Nga H. Nguyen, Martin E. Levere and Virgil Percec

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25838

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      The single electron transfer-living radical polymerization of methyl acrylate has been carried out to complete monomer conversion. Using low levels of active Cu(0) wire catalyst and replace 0 to 5% CuBr2 the reaction reached total conversion with zero termination throughout the polymerization, enabling perfect retention of chain-end functionality.

    4. Preparation of siloxane-based urethane dimethacrylates carrying carboxylic groups and the effect of silver nanoparticles on the properties of composite polymer films (pages 874–883)

      Tinca Buruiana, Violeta Melinte, Florentina Jitaru, Emil C. Buruiana and Lavinia Balan

      Article first published online: 19 NOV 2011 | DOI: 10.1002/pola.25839

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      Siloxane-urethane macromers with carboxylic groups were successfully used to disperse silver nanoparticles (2.5 wt %) prior obtained or one-step in situ generated during UV-light- induced polymerization. Attention is focused on the influence of the monomer structure and composition on the resulting Ag/polymer nanocomposite properties. The formation of hybrid nanocomposites with nanosilver particles (diameter: 2–15 nm) uniformly distributed in the polymer network and stabilized by the acid groups and poly(ethylene oxide) segment from the macrochain was confirmed via UV/vis spectrometry and traditional microscopic techniques such as TEM and ESEM/EDX.

    5. One-pot direct synthesis of fluorescent polyaniline-porphyrin macrospheres from porphyrin (pages 884–889)

      Singh Ajit, Srinivasan Palaniappan, Putcha Uday Kumar and Perikati Madhusudhanachary

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25840

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      One layer combination of fluorescent polyaniline-sulfonated porphyrin spherical material was successfully prepared by chemical route for the first time. Moreover, this material was synthesized directly from porphyrin using simple and cheaper process and no need of using sulfonated porphyrin, which is a difficult process and also a less available costly material. The electrical and optical properties of this polymer suggest that it may be very useful component in PV/LED devices.

    6. A series of poly[N-(2-hydroxypropyl)methacrylamide] copolymers with anthracene-derived fluorophores showing aggregation-induced emission properties for bioimaging (pages 890–899)

      Hongguang Lu, Fengyu Su, Qian Mei, Xianfeng Zhou, Yanqing Tian, Wenjing Tian, Roger H. Johnson and Deirdre R. Meldrum

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25841

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      A monomeric hydrophobic fluorophore possessing aggregation-induced emission (AIE) properties was copolymerized with N-(2-hydroxypropyl)methacrylamide to form a series of new copolymers. The copolymers were soluble in water to enable the bioapplications of the hydrophobic AIE fluorophore. The AIE fluorophores aggregated in the cores of micelles formed from the copolymers to show high quantum efficiencies. The polymers were endocytosed by U87MG and CP-A cells.

    7. A direct route to polythiophenes displaying lateral substituents: Easy one-step synthesis and polymerization of thiophene monomers substituted by a dimethylenecarboxylate (CH2CH2COOR) appendage on the 3-position (pages 900–911)

      Stéphane Sengmany, Claire Ceballos, Romain Belhadj, Christine Cachet-Vivier, Erwan Le Gall, Blandine Brissault, Jacques Penelle and Eric Léonel

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25842

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      Easy access to laterally substituted polythiophenes, a class of functional polymers with vast technological potential, is hampered by the difficulty to obtain polymerizable functional monomers in a simple, economically viable, and versatile way. This contribution describes the direct, one-step synthesis of thiophenes bearing dimethylenecraboxylate pendent groups on the 3-position of the heterocycle and the subsequent polymerization of these monomers, using the corresponding ethyl ester monomer as a model.

    8. Nonaqueous synthesis of uniform polyaniline nanospheres Via cellulose acetate template (pages 912–917)

      Li Zhang, Huiyan Ma, Fei Cao, Jian Gong and Zhongmin Su

      Article first published online: 29 NOV 2011 | DOI: 10.1002/pola.25843

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      Uniform polyaniline (PANI) nanospheres have been synthesized in bulk quantities by using cellulose acetate as template in a nonaqueous system for the first time. The diameter of PANI is at the nanoscale, which endows their superior performance as chemical sensors. The PANI nanospheres show super performance in sensitivity, time response, and reversibility to NH3 even at 1 ppm of NH3 gas.

    9. Synthesis and properties of comb polymers with semirigid mesogen-jacketed polymers as side chains (pages 918–926)

      Ziyue Ma, Cui Zheng, Zhihao Shen, Dehai Liang and Xinghe Fan

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25844

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      A series of new comb polymers containing rod-like side chains, polystyrene-g- poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PS-g-PMPCS), with different lengths of the backbone and side chains were successfully synthesized by the “grafting onto” method. The PMPCS combs showed different aggregation morphologies when depositing on silicon wafers with/without chemical modification. By using Langmuir-Blodgett technique it was found that the PMPCS comb polymer showed a worm-like chain conformation on polymer-modified silicon wafer.

    10. Electromagnetic properties of Fe3O4-functionalized graphene and its composites with a conducting polymer (pages 927–935)

      Tran Thanh Tung, Jean-Francois Feller, TaeYoung Kim, Hyeongkeun Kim, Woo Seok Yang and Kwang S. Suh

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25847

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      A hybrid materials with interconnected 3D network of Fe3O4-decorated reduced graphene oxide (RGO) and poly(3,4-ethylenedioxythiophene) (PEDOT) was prepared by poly(ionic liquids) (PILs)-mediated hybridization. PILs were found to function as multiple roles for: stabilizing Fe3O4-RGO against aggregation, transferring Fe3O4-RGO nanomaterials from aqueous into organic phase, and associating Fe3O4-RGO nanomaterials with PEDOT. These hybrid materials consisting of graphene, magnetic nanocrystals, and conducting polymers exhibit multifunctional properties such as superparamagnetic behavior, good electrical conductivity, and mechanical properties.

      Corrected by:

      Corrigendum: Electromagnetic properties of Fe3O4-functionalized graphene and its composites with a conducting polymer

      Vol. 51, Issue 17, 3767, Article first published online: 5 JUN 2013

    11. Zero-valent bimetallic iron/copper catalyzed SET-LRP: A dual activation by zero-valent iron (pages 936–943)

      Lili Zhou, Zhengbiao Zhang, Wenxiang Wang, Zhenping Cheng, Nianchen Zhou, Jian Zhu, Wei Zhang and Xiulin Zhu

      Article first published online: 28 NOV 2011 | DOI: 10.1002/pola.25849

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      In this work, bimetallic zero-valent metal (Fe(0) and Cu(0)) was used to mediate the SET-LRP of MMA at 25 °C in DMSO. With the increase of the molar ratio of Fe(0) to Cu(0), the polymerization rate was slightly depressed with a prolonged induction period. Interestingly, the control over the molecular weights was improved upon the increase of Fe(0) in a certain range. A best control (initiation efficiency = 91%) was achieved at [Fe(0)]0/[Cu(0)]0 = 1/0.5. Explorations of available solvents and ligands confirmed that the Fe(0)/Cu(0)-catalyzed polymerization complied with the SET-LRP mechanism. Fe(0) was suggested to play a dual role in the process: one was the activation agent for Cu(0), which favored a better control over the molecular weights; the other was the alternative catalyst for the activation of R-X or Pn-X to generate radicals, which assured a comparable polymerization rate as that of Cu(0). The Fe(0)/Cu(0) can also be used for the SET-LRP of MA with comparable results of those catalyzed by equivalent Cu(0). This work provided a more economical and environment-friendly catalyst for SET-LRP, and would eventually reinforce the SET-LRP technique.

    12. The effect of cosurfactants and the initiator concentration on the polymer to surfactant concentration in nanolatexes (pages 944–956)

      Raul P. Moraes, Izabelle Zavecs, Philippe Lauvernier, Niels M. B. Smeets, Robin A. Hutchinson and Timothy F. L. McKenna

      Article first published online: 29 NOV 2011 | DOI: 10.1002/pola.25850

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      The Pol/Surf ratio can be significantly increased by increasing the initiator concentration of emulsion polymerization recipes. Particle sizes are comparable to microemulsion latexes, however, less surfactant is required. The reduction in the particle size with higher initiator concentration is attributed to a higher efficiency of particle nucleation and to a higher nucleation rate relative to the rate of monomer transfer. Nanolatexes (particle size < 30 nm) were obtained with 19 wt % soilds content and Pol/Surf of 3.6 in ab initio.

    13. Stereoselective ring-opening polymerization of D,L-lactide, initiated by aluminum isopropoxides bearing tridentate nonchiral schiff-base ligands (pages 957–966)

      Kouki Matsubara, Chihiro Terata, Hiromichi Sekine, Kenji Yamatani, Tatsuo Harada, Kiyoka Eda, Misato Dan, Yuji Koga and Munehisa Yasuniwa

      Article first published online: 29 NOV 2011 | DOI: 10.1002/pola.25851

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      Ring-opening polymerization of D,L-lactide was stereoselectively achieved using newly designed aluminum alkoxide complexes as initiators. These half-SALEN aluminum compounds bearing tridentate nonchiral Schiff-base ligands are racemates, which provide chirality in the aluminum centers, efficiently afforded a stereoblock copolymer of D,L-lactide.

    14. Synthesis and applications of a novel supramolecular polymer network with multiple H-bonded melamine pendants and uracil crosslinkers (pages 967–975)

      Dhananjaya Patra, Mohan Ramesh, Duryodhan Sahu, Harihara Padhy, Chih-Wei Chu, Kung-Hwa Wei and Hong-Cheu Lin

      Article first published online: 1 DEC 2011 | DOI: 10.1002/pola.25853

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      A novel supramolecular cross-linking polymer PBT/F is developed by self-assembly of pendent melamine units in main-chain polymer PBT with uracil motifs in H-bonded cross-linker F. Compared with polymer PBT, a higher power conversion efficiency (PCE) value of 0.86% is obtained in H-bonded cross-linking polymer PBT/F due to its higher crystallinity induced by H-bonded cross-linker F.

    15. Engineering a sharp physiological transition state for poly(n-isopropylacrylamide) through structural control (pages 976–985)

      Kai Chang, Zachary T. Dicke and Lakeshia J. Taite

      Article first published online: 29 NOV 2011 | DOI: 10.1002/pola.25854

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      Poly(N-isopropylacrylamide) has been a subject of widespread interest for biological applications; however, some applications have been hindered due to the difficulty of maintaining a sharp transition when the polymer is modified for a physiological transition temperature, especially in isotonic solutions. As shown, the combined use of RAFT polymerization, appropriate end groups, molecular weight control, and tacticity control to synthesize well-defined pNIPAAm demonstrate a sharp transition at 37.6 °C under isotonic conditions.

    16. Salicylaldiminato nickel(II) catalysts with 5-halo-3-methoxy groups for ethylene polymerization (pages 986–995)

      Nikhil A. Kolhatkar, Amber M. Monfette, Shuo Lin and Massoud J. Miri

      Article first published online: 13 DEC 2011 | DOI: 10.1002/pola.25855

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      A 5-chloro-3-methoxy salicylaldiminato methylpyridine nickel(II) (left) and its bromo analog were synthesized and applied as single-component catalysts for the polymerization of ethylene in toluene. Catalyst activities were relatively high, and branched polyethylene was obtained as also indicated by the melting points of the polymers (right).

    17. Controlled radical polymerization of tert-butyl acrylate at ambient temperature: Effect of initiator structure and synthesis of amphiphilic block copolymers (pages 996–1007)

      Harihara Subramanian Sundaram and Dhamodharan Raghavachari

      Article first published online: 15 DEC 2011 | DOI: 10.1002/pola.25856

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      Controlled and very rapid temperature polymerization of tert-butyl acrylate (tBA) was performed using controlled living radical polymerization methods (ATRP and SET-LRP), at ambient temperature. A very active catalyst, secondary initiator and SET-LRP conditions are observed to facilitate very rapid polymerization with good control. SET-LRP enables very fast polymerization with good control even with a primary initiator. Styrene was polymerized from PtBA macroinitiators and vice versa to obtain block copolymers. The amphiphilic block copolymers obtained by the hydrolysis of the tBA block enable the formation of stable dispersion of CdS nanoparticles.

    18. Deprotection-free preparation of propargyl ether-containing phosphinated benzoxazine and the structure–property relationship of the resulting thermosets (pages 1008–1017)

      Hou Chien Chang, Ching Hsuan Lin, Hung Tse Lin and Shenghong A. Dai

      Article first published online: 8 DEC 2011 | DOI: 10.1002/pola.25857

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      Generally, protection and deprotection procedures of amino groups are required in preparing propargyl ether-containing benzoxazine. In this study, a deprotection-free preparation of a propargyl ether-containing phosphinated benzoxazine is reported.

    19. Skewered reactions in free-radical crosslinking (co)polymerizations of liquid polybutadiene as internal olefinic multivinyl crosslinker (pages 1018–1025)

      Akira Matsumoto, Taisuke Tani, Hiroyuki Aota, Kazuhisa Fushihara and Mikio Yamada

      Article first published online: 7 DEC 2011 | DOI: 10.1002/pola.25858

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      Liquid polybutadiene rubber (LBR) is regarded as an internal olefinic multivinyl crosslinker. First, gelation in the polymerization of LBR was explored, especially at elevated temperatures. The occurrence of intermolecular crosslinking was easier in the order (A) LBR > (B) LBR containing 20 mol % of 1,2-structural units > (C) liquid polyisoprene rubber. Then, the dicumyl peroxide-initiated LBR polymerization was pursued: the ratio of allylic hydrogen abstraction to β-scission reaction of cumyloxy radical was estimated; thus, only 39% of cumyloxy radical was used for the allylic hydrogen abstraction reaction. Finally, the intermolecular and intramolecular skewered reactions were pursued in crosslinking LBR/vinyl pivalate copolymerizations.

    20. A series of furan-aromatic polyesters synthesized via direct esterification method based on renewable resources (pages 1026–1036)

      Min Jiang, Qian Liu, Qiang Zhang, Chong Ye and Guangyuan Zhou

      Article first published online: 7 DEC 2011 | DOI: 10.1002/pola.25859

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      A series of furan-aromatic polyesters are readily prepared via direct esterification method starting from 2,5-furandicarboxylic acid, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol. The preliminary evidence shows that direct esterification method is rewarding and worthy to prepare furan-aromatic polyesters. The research results shows that furan-aromatic polyesters (ρ = 1.19–1.38 kg/m3) are crystalline and hydrophilic, they have satisfactory thermal and mechanical properties, and their thermal stabilities are quite similar to that of corresponding benzene-aromatic polyesters, which would endow them to be a viable alternative to their successful petrochemical benzene-aromatic counterpart and to be used as biopolymer materials in the future.

    21. Influence of the processing solvent on the photoactive layer nanomorphology of P3HT/PC60BM solar cells (pages 1037–1041)

      Raoul Mens, Fatma Demir, Guy Van Assche, Bruno Van Mele, Dirk Vanderzande and Peter Adriaensens

      Article first published online: 7 DEC 2011 | DOI: 10.1002/pola.25865

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      The casting of bulk-hetero junction P3HT/PC60BM 1/1 active layers by doctor blading from solutions in toluene leads to an improved nanocrystallinity when compared with their unannealed, chlorobenzene-casted counterparts. Despite that this is not noticed in the TEM images, solid-state NMR and rapid heating cooling calorimetry experiments, on the other hand, reveal these subtle differences, making them powerful and complementary techniques to investigate the active layer morphology of plastic solar cells.

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