Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 20

15 October 2009

Volume 47, Issue 20

Pages 5195–5563

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      Development of synthetic double helical polymers and oligomers (pages 5195–5207)

      Yoshio Furusho and Eiji Yashima

      Version of Record online: 8 SEP 2009 | DOI: 10.1002/pola.23596

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      This short review highlights the recent advances in the synthesis, structures, and functions of double helical polymers and oligomers based on synthetic chemistry. In particular, we focus on an important role of supramolecular chemistry in the design and synthesis of double helices. Although the artificial double helices are still underdeveloped, the recent advancement of supramolecular chemistry provides plenty of structural motifs for new designs. Now the time is ready to explore the chemistry of artificial double helices. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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    1. Visibly observed photocrosslinking reaction in indolyl based pendant liquid crystalline polymers: Synthesis and optical property (pages 5208–5220)

      Kumarasamy Gayathri, Chinnusamy Saravanan and Palaninathan Kannan

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23570

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      Visibly observed photocrosslinkable pendant liquid crystalline polymers containing indole based chalcones were synthesized by free-radical polymerization and characterized spectroscopically. The differential scanning calorimetry and polarized optical microscopy were used to examine the liquid crystalline property. The photocrosslinking and luminescence properties were monitored by UV-Vis spectrophotometer and spectrofluorimeter, respectively. It demonstrates the chalcone did not manifest cis [LEFT RIGHT ARROW]trans-isomerization reaction along with 2π+2π photodimerization upon irradiation with UV light like other chalcones hitherto reported. The photocrosslinking was visibly monitored in solution through change of fluorescent color to colorless. The fluorescence maximum was blue shifted around 70 nm in chloroform solution upon irradiation with UV light confirms the 2π+2π photodimerization of chalcone. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. A π-stacked and conjugated hybrid based on poly(N-vinylcarbazole) postfunctionalized with terfluorene for stable deep-blue hole-transporting materials (pages 5221–5229)

      Ling-Hai Xie, Xian-Yu Deng, Lin Chen, Shu-Fen Chen, Ran-Ran Liu, Xiao-Ya Hou, King-Young Wong, Qi-Dan Ling and Wei Huang

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23571

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      In this study, a double-channeled π-stacked and conjugated hybrid, poly(vinylcarbazole) (PVK)-terfluorene (TF), has been synthesized via Friedal-Crafts click postmodification (FCCP) of PVK. There are no obvious π-stacks between Cz and TF due to steric hindrance effect, which has been confirmed via conformational analysis basing on UV–vis, PL, EL, and molecular simulations. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Role of dispersion stabilizer with hydroxy groups in preparation of monodisperse polylactide microspheres (pages 5230–5240)

      Makoto Muranaka and Tsutomu Ono

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23572

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      Monodisperse poly(D,L-lactide) (PDLLA) microspheres were prepared by dispersion polymerization of D,L-lactide in xylene/heptane (1/2, v/v) with poly[(dodecyl methacrylate)- co-(2-hydroxyethyl methacrylate)] (P(DMA-co-HEMA)) as a dispersion stabilizer. P(DMA-co-HEMA) contains hydroxy groups, which act as an initiation group for pseudoanionic dispersion polymerization. The best coefficient of variation (CV) values concerning particle diameter distribution and particle diameter of obtained PDLLA microspheres were 3.7% and 5.3 μm, respectively. The particle diameter decreased with increasing concentrations of P(DMA- co-HEMA) and HEMA maintained low CV (<10%) values. As a result, monodisperse PDLLA microspheres ranging from 1.3 to 5.3 μm were obtained.

    4. Controlled vinyl-type polymerization of norbornene with a Nickel(II) diphosphinoamine/methylaluminoxane catalytic system (pages 5241–5250)

      Georgios C. Vougioukalakis, Ioannis Stamatopoulos, Nikolaos Petzetakis, Catherine P. Raptopoulou, Vassilis Psycharis, Aris Terzis, Panayotis Kyritsis, Marinos Pitsikalis and Nikos Hadjichristidis

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23573

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      The synthesis of a novel nickel diphosphinoamine-coordinated complex along with a detailed study on its norbornene polymerization behavior is described. The obtained polynorbornenes (PNBs) are characterized by high molecular weights and relatively narrow and monomodal molecular weight distributions. The linear dependence of the molecular weight of the PNB on norbornene concentration is in agreement with a controlled polymerization reaction. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. Cationic polymerization of styrene involving ionization of the C[BOND]Cl bond in ionic liquid/SO2 mixture (pages 5251–5257)

      Małgorzata Baśko, Tadeusz Biedroń and Przemysław Kubisa

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23574

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      Controlled cationic polymerization of styrene initiated with alkyl (aryl) halides involves equilibrium between active (ionic) and dormant (halide terminated) species. This process has been studied in ionic liquid/sulfur dioxide mixtures (IL/SO2) containing up to 70 mol % of SO2. Due to the high ionizing power of SO2 ionization of the C[BOND]Cl bond in dormant species should be facilitated. It has been shown that in the absence of coinitiator (Lewis acid) alkyl chloride alone can initiate polymerization leading to complete conversion. The rate of exchange between dormant and active species, however, is not sufficient to fulfill the requirements of controlled polymerizaton.

    6. Synthesis, photopolymerization, and adhesive properties of new bisphosphonic acid monomers for dental application (pages 5258–5271)

      Yohann Catel, Michel Degrange, Loïc Le Pluart, Pierre-Jean Madec, Thi-Nhàn Pham, Fei Chen and Wayne D. Cook

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23575

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      In this study, new hydrolytically stable 3-(N-alkylacrylamido)propylidenebisphosphonic acid (6a–6d) have been prepared in good yields. Photopolymerization behaviors with N,N′-diethyl-1,3-bis(acrylamido)propane and adhesive properties of these monomers have been studied. Primers based on bisphosphonic acid monomers (6a–6d), when coupled with an appropriate hydrophobic resin, are able to generate a strong bond between the tooth substance and a composite.

    7. PVA networks grafted with PDMS branches (pages 5272–5277)

      Ummadisetty Subramanyam and Joseph P. Kennedy

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23576

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      Hydrophilic poly(vinyl alcohol) networks grafted with hydrophobic PDMS branches (PVAnetw-g-PDMS) were obtained by photocrosslinking PVA fitted with a few photoactive acryl amide groups and grafted with PDMS branches (PVAAA-g-PDMS) (see sketch). The use of the binary solvent mixture NMP/THF (67/33) enabled the thermodynamically unfavorable mixing of PDMS-NCO (polydimethylsiloxane fitted with NCO termini) with PVAAA and thus the urethane linking of these moieties. In the presence of a sufficient volume of PDMS branches, PVA networks with cocontinuous hydrophilic/hydrophobic domains were obtained. These amphiphilic constructs may be of use as extended wear soft contact lenses. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Polyisobutylene-based polyurethanes. III. Polyurethanes containing PIB/PTMO soft co-segments (pages 5278–5290)

      Gabor Erdodi, Jungmee Kang, Joseph P. Kennedy, Emel Yilgor and Iskender Yilgor

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23577

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      We are presenting the synthesis, characterization, and structure-property relationship of polyurethanes containing PIB and PTMO soft co-segments and HMDI/ HDO hard segments. PIB-based polyurethanes with HMDI/HDO hard segments show significantly better mechanical properties than earlier polyurethanes containing highly crystalline hard segments. The addition of moderate amounts (20% by weight) of PTMO significantly increased both tensile strengths and elongations and maintained good hysteresis behavior. In the presence of larger amounts of PIB, these polyurethanes are expected to possess oxidative/hydrolytic/enzymatic stabilities superior to commercially available polyurethanes, such as, Bionate®, Elast-Eon®, and so forth. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Synthesis and white electroluminescent properties of multicomponent copolymers containing polyfluorene, oligo(phenylenevinylene), and porphyrin derivatives (pages 5291–5303)

      Hui Li, Na Xiang, Lei Wang, Bin Zhao, Ping Shen, Junjian Lu and Songting Tan

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23578

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      Two novel multicomponent copolymers containing polyfluorene (PF), oligo(phenylenevinylene) (OPV), and porphyrin (Por) derivatives have been designed and synthesized. Both of the copolymers exhibit thermotropic liquid crystalline properties and represent the characteristic Schlieren textures in a wide temperature range. A single layer device based on the copolymerP2 emits white electroluminescence with CIE coordinates of (0.29, 0.30) at 9 V.

    10. High performance polymer field-effect transistors based on polythiophene derivative with conjugated side chain (pages 5304–5312)

      Youjun He, Weiping Wu, Yunqi Liu and Yongfang Li

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23579

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      Poly(3-[2-(5-hexyl-2-thienyl) ethenyl]-2,2′-bithiophene) (P2) with conjugated side chain was synthesized by Pd-catalyzed Stille coupling method. The organic field-effect transistor (OFET) based on P2 after thermal annealing at 180 °C exhibited high hole mobility up to 0.061 cm2/Vs with the threshold voltage VT of −1.15 V and the on-off ratio of 104. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. A comprehensive investigation into “controlled/living” chain growth crosslinking copolymerization including a back to basics modeling (pages 5313–5327)

      Julien Poly, D.James Wilson, Mathias Destarac and Daniel Taton

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23580

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      Controlled/living (C/L) crosslinking copolymerization (CC) has recently emerged as a promising methodology for the synthesis of well-defined branched polymeric architectures, such as nano/microgels or star-like polymers. A theoretical approach to this new synthetic route is developed in this contribution. In particular, a simple kinetic scheme consistent with an “ideal” C/L behavior is enriched with the distinction between intramolecular (cyclization) and intermolecular crosslinking. A key differential equation governing C/L CC is derived, enabling an easy forecast of the characteristic magnitudes of the products. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Poly(cyclohexene oxide)/clay nanocomposites by photoinitiated cationic polymerization via activated monomer mechanism (pages 5328–5335)

      Ayhan Oral, Mehmet Atilla Tasdelen, Adem Levent Demirel and Yusuf Yagci

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23581

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      Poly(cyclohexene oxide) (PCHO)/clay nanocomposites were prepared by in situ photoinitiated activated monomer cationic polymerization. The polymerization of cyclohexene oxide through the interlayer galleries of the clay can provide distribution of the clay layers in the polymer matrix homogenously and results in the formation of PCHO/clay nanocomposites. The exfoliated structures were characterized by X-ray diffraction (XRD) spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and atomic force microscopy (AFM). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    13. Synthesis and characterization of new low bandgap polyfluorene copolymers for bulk heterojunction solar cells (pages 5336–5343)

      Steve Lien-Chung Hsu, Yu-Chen Lin, Rong-Fong Lee, Chinnaiah Sivakumar, Jen-Sue Chen and Wei-Yang Chou

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23582

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      Two new low bandgap alternating polyfluorene copolymers based on dioctylfluorene and donor-acceptor-donor monomers have been synthesized. The resulting copolymers have low optical bandgaps at 1.99–1.98 eV. The power conversion efficiencies of solar cells based on copolymers 1 and 2 are 0.37 and 0.42%, respectively, under the illumination of AM 1.5, 100 mW/cm2.

    14. An efficient approach to synthesize polysaccharides-graft-poly(p-dioxanone) copolymers as potential drug carriers (pages 5344–5353)

      Fang Lu, Xiu-Li Wang, Si-Chong Chen, Ke-Ke Yang and Yu-Zhong Wang

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23584

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      The method described in this article allowed highly-efficiently obtaining a family of acetylated starch-g-PPDO copolymers via the ring-opening polymerization of p-dioxanone (PDO) with an acetylated starch (SA) initiator and a Sn(Oct)2 catalyst in bulk. These copolymers exhibited excellent solubility in common organic solvents and improved biodegradability. These characteristics were used to elaborate microspheres with an average volume diameter of 20 μm, which have a big potential in controlled release of drugs.

    15. Deep-red emissive conjugated poly(2,6-BODIPY-ethynylene)s bearing alkyl side chains (pages 5354–5366)

      Venkat R. Donuru, Giri K. Vegesna, Singaravelu Velayudham, Ge Meng and Haiying Liu

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23585

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      Three new deep-red emissive BODIPY-based conjugated polymers have been prepared by palladium-catalyzed Sonogashira coupling reaction. Significant delocalization was observed in the rigid BODIPY-type polymers, where bridging alkynyl functionalities allow for a high degree of π-conjugation between BODIPY monomer units. The thin films of the polymers are fluorescent in near-infrared region and significantly red-shifted compared with those in methylene chloride solution. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Preparation of nanocomposites by reversible addition-fragmentation chain transfer polymerization from the surface of quantum dots in miniemulsion (pages 5367–5377)

      Ana Catarina C. Esteves, Philip Hodge, Tito Trindade and Ana M. M. V. Barros-Timmons

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23586

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      Grafting from synthetic strategy to prepare QDs/polymer (PS) nanocomposites by in situ RAFT polymerization in miniemulsion. The polymer chains were grafted from the surface of QDs previously modified with the RAFT chain transfer agent: 4-cyano-4-(thiobenzoylsulfanyl)pentanoic acid. The QDs/polymer nanocomposites are organized in spherical clusters (TEM image shown in the graph, bar = 250 nm). Quantum confinement effects were assigned to the nanocomposite. An indication of the living character of the polymer shell was given by the polymerization of a second monomer n-BA in the presence of the QDs polymer composites bearing the macroRAFT transfer agent. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. Near-infrared electrochromic poly(aryl ether)s based on isolated electroactive tetraphenyl-p-phenylenediamine moieties (pages 5378–5385)

      Guey-Sheng Liou, Hung-Ju Yen and Ming-Che Chiang

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23587

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      A series of NIR electrochromic aromatic polyethers with TPPA units in the backbone were prepared by the high temperature solution polycondensation. These polymers were readily soluble in many organic solvents and showed useful thermal stability associated with high glass-transition temperatures. The electroactive polyether films showed high contrast ratio and coloration efficiency both in the visible range and NIR region with good electrochromic stability. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Incorporation of poly(2-acrylamido-2-methyl-N-propanesulfonic acid) segments into block and brush copolymers by ATRP (pages 5386–5396)

      Lynne A. McCullough, Bruno Dufour and Krzysztof Matyjaszewski

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23588

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      2-Acrylamido-2-methyl-N-propanesulfonic acid (AMPSA) was successfully polymerized via ATRP using a CuCl/bpy catalyst complex after in situ neutralization of the acidic proton in AMPSA with tri(n-butylamine) (TBA). Improved conversion resulted from the use of AGET ATRP with CuCl2/bpy as the catalyst and ascorbic acid as the reducing agent. Block copolymers and brush copolymers were also prepared.

    19. Microwave-assisted graft polymerization of ε-caprolactone onto magnetite (pages 5397–5404)

      Alexandrina Nan, Rodica Turcu, Izabell Craciunescu, Ovidiu Pana, Holger Scharf and Jürgen Liebscher

      Version of Record online: 11 SEP 2009 | DOI: 10.1002/pola.23589

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      Sn(oct)2 catalyzed surface-initiated ROP of ε-caprolactone in the presence of surface stabilized magnetite nanoparticles was successfully conducted by microwave irradiation for the first time. The rate accelerating effect of microwave irradiation allowed reducing the time of polymerization. Resulting core-shell nanoparticles were characterized by FTIR, TEM, XRD, XPS, and magnetic measurements. They exhibit good superparamagnetic properties making them attractive for further applications. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    20. Aqueous RAFT polymerization of 2-aminoethyl methacrylate to produce well-defined, primary amine functional homo- and copolymers (pages 5405–5415)

      Alp H. Alidedeoglu, Adam W. York, Charles L. McCormick and Sarah E. Morgan

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23590

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      The direct controlled polymerization of primary amine containing monomers in aqueous solvent without the use of a protecting group is challenging, due to the potential for unwanted side reactions. Aqueous RAFT polymerization, under suitable reaction conditions, affords an opportunity to successfully polymerize such monomers, producing functional polymers of controlled molecular weight and architecture. Reaction parameters including choice of RAFT initiator, solution conditions, and temperature were identified to successfully produce 2-aminoethyl methacrylate (AEMA) polymers and copolymers with PDI lower than 1.2. This study also showed that the controlled polymerization of AEMA depends on both the solution pH and the polymerization temperature. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    21. Photoluminescence behaviors of organic soluble DNA bearing carbazole and pyrene derivatives as side-chain substituents and effect of the copolymer structure on the Förster energy transfer process (pages 5416–5425)

      U Ra Lee, Jung Eun Lee, Min Ju Cho, Kyung Hwan Kim, Young Wan Kwon, Jung-Il Jin and Dong Hoon Choi

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23591

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      Organic soluble DNA bearing two different fluorophores in the side chain was prepared by reacting purified DNA with the cationic molecules 9-(12-bromododecyl)-9H-carbazole and (E)-1-(4-(12-bromododecyloxy)styryl)pyrene in water. The DNA copolymer system showed much better energy transfer efficiency than the other DNA systems. The copolymers were mixed with 2-{2-[2-(4-diethylamino-phenyl)-vinyl]-6-methyl-pyran-4-ylidene}-malononitrile (DCM) at an optimum concentration. At low DCM concentration (0.3 wt %), undesired emissions were observed due to an incomplete energy transfer process from excited pyrene moieties. At high DCM concentration (5.0 wt %), red emissions were predominant; this is attributed to an efficient Förster energy transfer process. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    22. Synthesis, characterization, and photoresponsive behavior of new azobenzene-containing polyethers (pages 5426–5436)

      Sergio Peris, Bartosz Tylkowski, Joan Carles Ronda, Ricard Garcia-Valls, José Antonio Reina and Marta Giamberini

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23592

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      Variation in the aromatic region of 1H NMR spectra in deuterated 1,1,2,2-tetrachloroethane of 4-cyano-4′-glycidyloxyazobenzene after irradiation with UV light, as a consequence of E–Z isomerization.

    23. Michael addition for crosslinking of poly(caprolactone)s (pages 5437–5447)

      Gozde Ozturk and Timothy E. Long

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23593

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      Poly(caprolactone)-based networks were synthesized using Michael addition reaction of acetoacetate-functionalized poly(caprolactone) oligomers with neopentyl glycol diacrylate in the presence of an organic base at room temperature. The influence of precursor molecular weight on thermal and mechanical properties was investigated using DSC and DMA, respectively. Moreover, oligomeric trisacetoacetate PCL precursors were used for network formation to investigate influence of the branching on thermomechanical properties. The modulus of the resulting networks was dependent on the molecular weight and the topology of the PCL precursor, which also influenced the crystallinity and crosslink density.

    24. Synthesis of gradient copolymers with complexing groups by RAFT polymerization and their solubility in supercritical CO2 (pages 5448–5460)

      Tiphaine Ribaut, Patrick Lacroix-Desmazes, Bruno Fournel and Stéphane Sarrade

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23594

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      Fluorinated gradient copolymers with ligand groups have been successfully synthesized by RAFT polymerization in α,α,α-trifluorotoluene. They have shown remarkable solubilities in compressed CO2 that prove their interest as complexing surfactants for various processes in this solvent, such as metal extraction or synthesis of metal nanocomposites. Furthermore, thanks to their very good solubility, the synthesis of these gradient copolymers was demonstrated to be achievable directly in supercritical CO2 in accordance with the green chemistry strategy. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    25. Ionomers for proton exchange membrane fuel cells by sulfonation of novel dendritic multiblock copoly(ether-sulfone)s (pages 5461–5473)

      Sumiko Matsumura, Antisar R. Hlil, Mohammed A. K. Al-Souz, Julie Gaudet, Daniel Guay and Allan S. Hay

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23598

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      Dendritic multiblock copoly(ether-sulfone)s (PESs) bearing dendritic clusters of sulfonic acid groups on the dendritic block were synthesized by a three-step reaction: (1) one-pot synthesis of dendritic blocks consisting of difunctional dendritic block and monofunctional dendritic end-group by aromatic nucleophilic substitution reaction using controlled ratio of hexakis(4-(4-fluorophenylsulfonyl)phenyl)benzene and 1-(4-hydroxyphenyl)-2,3,4,5,6-pentaphenylbenzene; (2) polycondensation of 4,4′-dihydroxybenzophenone and bis(4-fluorophenyl)sulfone in the presence of the dendritic blocks; (3) post-sulfonation of the hexaphenylbenzene moieties of the dendritic block. The PESs with relatively long main chain formed strong membranes. At a similar level of IEC as Nafion, these PES membranes showed proton conductivities comparable to that of Nafion.

    26. Photopolymerization of vinyl ether networks using an iodonium initiator—The role of photosensitizers (pages 5474–5487)

      Wayne D. Cook, Shaohua Chen, Fei Chen, Muhammet U. Kahveci and Yusuf Yagci

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23599

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      Generalized schemes of electron and hydrogen transfer between the photosensitizer (PS) and the iodonium salt (Ph2IPF6) in the presence of abstractable hydrogens. These mechanisms suggest that photosensitized onium cationic polymerization does not necessarily follow a single mechanism and will depend on the photosensitizer.

    27. Synthesis and optoelectronic properties of alternating benzofuran/terfluorene copolymer with stable blue emission (pages 5488–5497)

      Haichang Zhang, Erqian Guo, Yujie Fang, Peihua Ren and Wenjun Yang

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23600

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      Synthesis and optoelectronic properties of a novel blue-emitting alternating benzofuran/terfluorene copolymer with pendent oxadiazole groups (PBF-OXD) are investigated. PBF-OXD shows excellent thermal and optical stability, high glass transition temperature and fluorescence quantum yield. A simple device ITO/PEDOT:PSS/PBF-OXD/Ba/Al displays a stable blue emission (λmax = 435 nm), a good colour purity (full width half-maximum) = 59 nm, a maximum brightness of 1400 cd m−2, and a maximum luminance efficiency of 0.95 cd A−1.

    28. You have free access to this content
      Low bandgap π-conjugated copolymers based on fused thiophenes and benzothiadiazole: Synthesis and structure-property relationship study (pages 5498–5508)

      Shiming Zhang, Yunlong Guo, Haijun Fan, Yao Liu, Hsiang-Yu Chen, Guanwen Yang, Xiaowei Zhan, Yunqi Liu, Yongfang Li and Yang Yang

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23601

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      A series of low bandgap conjugated polymers consisting of benzothiadiazole alternating with dithienothiophene (DTT) or dithienopyrrole (DTP) unit with or without 3-alkylthiophene bridge have been synthesized. Effect of the fused rings and 3-alkylthiophene bridge on the thermal, optical, electrochemical, charge transport, and photovoltaic properties of these polymers have been investigated. These polymers show broad absorption extending from 300 to 1000 nm with optical bandgaps as low as 1.2 eV. The field-effect transistors and polymer solar cells based on the DTP polymer with 3-alkylthiophene bridge exhibited hole mobility of 0.03 cm2 V−1 s−1 and power conversion efficiency of 0.43%, respectively. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    29. Y-shaped diblock copolymer with epoxy-based block of poly(glycidyl methacrylate): Synthesis, characterization, and its morphology study (pages 5509–5526)

      Bao Zhang, Yapeng Li, Peng Ai, Zhongpeng Sa, Yili Zhao, Meng Li, Di Wang and Ke Sha

      Version of Record online: 11 SEP 2009 | DOI: 10.1002/pola.23602

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      Amphiphilic Y-shaped diblock copolymers were successfully synthesized by the combination of enzymatic ring-opening polymerization and atom transfer radical polymerization (ATRP). The kinetic analysis indicated a “living”/controlled radical polymerization. The structures of all the polymer products have been well characterized by means of NMR, GPC, and IR measurements. The thermal properties were investigated by DSC. Polymers with a number-average molecular weight of 13,900–70,700 g/mol and low polydispersity index (Mw/Mn = 1.26–1.50) were obtained. The morphologies of solution-cast films of the Y-shaped block copolymers were studied by tapping-mode AFM. Various patterns formed in different solvents and at different concentrations.

    30. Cylindrical molecular brushes with a loose grafting density (pages 5527–5533)

      Guohua Deng and Yongming Chen

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23603

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      A loose molecular brush with tailored graft interval was prepared by a combination of radical copolymerization of styrene/maleimide and ATRP graft polymerization. Characterization by AFM and static light scattering gave the length of molecular brush per monomer unit of backbone to be 0.066 nm, indicating the brush is rather flexible. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    31. Selective 17-β-estradiol molecular imprinting (pages 5534–5542)

      Shimon Farber, Bernard S. Green and Abraham J. Domb

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23604

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      Combination of covalent and noncovalent techniques for synthesis of molecular imprinting polymer (MIP) for quantitative determination of β-estradiol resulted in highly selective and specific imprinted polymer. MIPs were prepared by radical polymerization of 17-β-estradiol 4-vinyl-benzene carboxyl or sulfonyl esters used as covalent functional monomers and methacrylic acid used as noncovalent monomer. Bounded 17-β-estradiol was removed from the polymer network by basic hydrolysis. Obtained MIP demonstrated excellent affinity toward 17-β-estradiol as evidenced by selective and specific binding of estradiol in the presence of competitive estrogens having similar chemical structure. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  3. Rapid Communications

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    4. Rapid Communications
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      Biocompatible and degradable nanogels via oxidation reactions of synthetic thiomers in inverse miniemulsion (pages 5543–5549)

      Juergen Groll, Smriti Singh, Krystyna Albrecht and Martin Moeller

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23595

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      We present the preparation of degradable and biocompatible nanohydrogels from thiol-functional macromers. Linear poly(glycidol) and star-shaped poly(ethylene oxide-stat-propylene oxide) with molecular weights below 15 kDa were functionalized with thiol groups by polymer-analogous reaction and crosslinked in inverse miniemulsion. Particle size was determined by dynamic light scattering, cryo-field emission scanning electron microscopy and scanning force microscopy. The disulfide crosslinked particles readily degrade on addition of 10 mM aqueous glutathione solution what resembles cytosolic conditions. Biocompatibility has been proven by incubation of L929 fibroblasts with nanogels for 24 and 72 h followed by life-dead staining. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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      Synthesis of glyco-microspheres via a thiol-ene coupling reaction (pages 5550–5556)

      Wenfang Gu, Gaojian Chen and Martina H. Stenzel

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23615

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      Thiol-ene click chemistry was employed to form microspheres with sugar groups with high bioactivity and efficient binding of Concanavalin A. Two systems were investigated – a microsphere prepared from ethyleneglycol dimethacrylate, which contained excess vinyl functionalities as a natural result of the preparation process, and the commercially available Wang microsphere, which had to be modified with acryloylchloride to generate pendant vinyl groups. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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      Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting-through” methodology (pages 5557–5563)

      Zhou Li, Ke Zhang, Jun Ma, Chong Cheng and Karen L. Wooley

      Version of Record online: 10 SEP 2009 | DOI: 10.1002/pola.23626

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      The orthogonality of RAFT and ROMP chemistries are exploited for a highly efficient “grafting through” strategy to afford cylindrical molecular brushes. The ROMP of α-norbornenyl-functionalized poly(t-butyl acrylate) macroRAFT chain transfer agents, catalyzed by a modified 2nd generation Grubbs' catalyst, achieved completion in minutes under air. Following hydrolysis, functionalizable water-soluble poly(acrylic acid) molecular brushes were afforded. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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