Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 20

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 3.543

ISI Journal Citation Reports © Ranking: 2012: 12/83 (Polymer Science)

Online ISSN: 1099-0518

Associated Title(s): Journal of Polymer Science Part B: Polymer Physics


  1. 1 - 56
  1. Highlights

    1. You have free access to this content
      Orthogonal multiple click reactions in synthetic polymer chemistry

      Umit Tunca

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27379

      Thumbnail image of graphical abstract

      This review highlights the concept of multiple click reaction strategy which is utilized for design and synthesis of well-defined complex macromolecular structures as well as multifunctionalization of well-defined polymers. This review examines the click combinations mainly from double to quadruple and additionally from the most frequently used to the least.

  2. Articles

    1. Crosslinking-induced morphology change of latex nanoparticles: A study of RAFT-mediated polymerization in aqueous dispersed media using amphiphilic double-brush copolymers as reactive surfactants

      Yukun Li, Leela Christian-Tabak, Vivien Li Fong Fuan, Jiong Zou and Chong Cheng

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27387

      Thumbnail image of graphical abstract

      Amphiphlic brush copolymers with each graft junction carrying one hydrophilic graft and one hydrophobic graft are synthesized and characterized. They are further used as both surfactants and polyfunctional RAFT agents for radical polymerization of styrene in miniemulsions. Depending on whether crosslinker is present in the polymerization systems, spherical and vesicular latex nanoparticles are obtained, respectively. The mechanism for such unusual crosslinking-induced morphology change of latex nanoparticles is discussed.

    2. Visible light-induced controlled radical polymerization of methacrylates with perfluoroalkyl iodide as the initiator in conjugation with a photoredox catalyst fac-[Ir(ppy)]3

      Qian Liu, Lianying Liu, Yuhong Ma, Changwen Zhao and Wantai Yang

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27390

      Thumbnail image of graphical abstract

      A new visible light-induced controlled radical polymerization of methacrylates, such as MMA, GMA, and TFEMA, with perfluoro-1-iodohexane (CF3(CF2)5I) as the initiator in the presence of a photoredox catalyst (fac-[Ir(ppy)3]) was developed. This method was used to successfully synthesize a clean diblock copolymer PMMA-b-PGMA with PMMA-I as the macroinitiator.

    3. Thermally curable organic/inorganic hybrid polymers as gate dielectrics for organic thin-film transistors

      Jong-Woon Ha, Yuntae Kim, Jeongkyun Roh, Fei Xu, Jong Il Park, Jeonghun Kwak, Changhee Lee and Do-Hoon Hwang

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27388

      Thumbnail image of graphical abstract

      New low-temperature curable organic/inorganic hybrid polymers were designed and synthesized as gate dielectrics for organic thin-film transistors. The synthesized insulators as gate dielectric layers had higher hole mobilities (up to 0.36 cm2/Vs) than a device using thermally cross-linked poly(vinyl phenol) and melamine as the gate dielectric layer (0.18 cm2/Vs).

    4. Synthesis of novel cyclic olefin polymers with excellent transparency and high glass-transition temperature via gradient copolymerization of bulky cyclic olefin and cis-cyclooctene

      Ji-Xing Yang, Jing Cui, Ying-Yun Long, Yan-Guo Li and Yue-Sheng Li

      Article first published online: 13 SEP 2014 | DOI: 10.1002/pola.27386

      Thumbnail image of graphical abstract

      Novel Cyclic Olefin Polymers (COPs) with high Tg (up to 201.2 °C) and excellent transparency (transmittance >88%) have been synthesized for the first time via gradient ring-opening metathesis copolymerization of bulky norbornene derivative (HBMN) with cis-cyclooctene (COE). To get amorphous copolymers with only one Tg, high HBMN/COE mole ratio and short polymerization time are preferred. In sharp contrast, all the films of HBMN/COE block copolymers are opaque and show decreased film forming ability.

    5. Columnar nanostructured polymer films containing ionic liquids in supramolecular one-dimensional nanochannels

      Akihiro Yamashita, Masafumi Yoshio, Seiya Shimizu, Takahiro Ichikawa, Hiroyuki Ohno and Takashi Kato

      Article first published online: 12 SEP 2014 | DOI: 10.1002/pola.27380

      Thumbnail image of graphical abstract

      Supramolecular self-assembly of a diol-functionalized wedge-shaped molecule having polymerizable groups and an imidazolium-based ionic liquid leads to the induction of columnar liquid-crystalline phases. In situ photopolymerization of the columnar assemblies aligned by the application of shearing force provides a new type of columnar nanostructured polymer films with one-dimensionally ordered ionic liquids. Anisotropic ion conduction is achieved for the polymer films.

    6. Well-defined PE-b-PDMS diblock copolymers via the combination of thiol-ene click and esterification reactions: Facile synthesis and compatibilization for HDPE/silicone oil blends

      Zhixian Xu, Suyun Jie and Bo-Geng Li

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27381

      Thumbnail image of graphical abstract

      Well-defined PE-b-PDMS diblock copolymers have been synthesized by the combination of radical initiated thiol-ene click and subsequent esterification reactions, which are proved to be an effective compatibilizer with low loading concentration in HDPE/silicone oil blends.

    7. Preparation and characterization of narrow compositional distribution polyampholytes as potential biomaterials: Copolymers of N-(3-Aminopropyl)methacrylamide hydrochloride (APM) and methacrylic acid (MAA)

      Ankita Dubey, Nicholas A. D. Burke and Harald D. H. Stöver

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27377

      Thumbnail image of graphical abstract

      Adjusting the methacrylic acid (MAA) to sodium methacrylate (NaMAA) ratio, in copolymerizations with a cationic monomer N-(3-aminopropyl)methacrylamide hydrochloride (APM), can lead to effective APM/MAA reactivity ratios of unity. This results in copolymerizations without the otherwise common compositional drift, and produces well-defined APM/MAA copolymers with solubilities responsive to composition, pH, temperature, and salt that are of interest as building blocks for biomaterials.

  3. Rapid Communication

    1. A turn-off fluorescent substrate for horseradish peroxidase improves the sensitivity of ELISAs

      Abhinav P. Acharya, Payel Sen, Kiana Aran, Austin B. Gardner, Mohammad Rafi, Deborah Dean and Niren Murthy

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27376

      Thumbnail image of graphical abstract

      A new turn-off fluorescent substrate for horseradish peroxidase is introduced, termed clics, which enhance the sensitivity of commercial enzyme-linked immunosorbant assays (ELISA) by 32-fold and detect chlamydial infections in patients. Clics are cost-effective, stable, and can be easily incorporated in commercial ELISA kits, and therefore should have a great impact in the fields of medicine and biology.

  4. Articles

    1. Synthesis and photovoltaic properties of conjugated D–A copolymers based on thienyl substituted pyrene and diketopyrrolopyrrole for polymer solar cells

      Ning Wang, Xichang Bao, Yan Yan, Dan Ouyang, Mingliang Sun, V. A. L. Roy, Chun Sing Lee and Renqiang Yang

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27378

      Thumbnail image of graphical abstract

      A new donor-acceptor (D-A) conjugated copolymer (PDTPyDPP), comprising thienyl substituted pyrene as D building block and diketopyrrolopyrrole (DPP) as A unit, was synthesized and showed good light-harvesting characteristic.

    2. Poly(oxanorbornenedicarboximide)s dendronized with amphiphilic poly(alkyl ether) dendrons

      Xiaoli Liang, Mani K. Sen, Jo-Ann Jee, Oleg Gelman, Jeannette E. Marine, Kenneth Kan, Maya K. Endoh, Deborah A. Barkley, Tadanori Koga and Jonathan G. Rudick

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27385

      Thumbnail image of graphical abstract

      A new family of dendrons, amphiphilic poly(alkyl ether) dendrons, are readily polymerized in a living manner. Ring-opening metathesis polymerization of the dendritic macromonomers yields single polymer molecules and cylindrical core-shell nanostructures with narrow molecular weight distribution and a controlled degree of polymerization.

    3. Different synthetic pathways of nanoparticle-cored dendrimers (NCDs): Effects on the properties and their application as redox active centers

      Julieta I. Paez, Pablo Froimowicz, Katharina Landfester, Verónica Brunetti and Miriam Strumia

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27375

      Thumbnail image of graphical abstract

      Nanoparticle-cored dendrimers (NCDs) with diverse chemical and structural features are synthesized via surface functionalization of iron oxide nanoparticles and by combining a silane coupling agent and dendritic moieties. The nanostructure of the material is controlled not only by the information programmed into the dendritic branches, but also by the presence of other organic molecules within the modifying layer, by the molecular ordering, and by the interaction between the different modifiers and with the dispersing media, affecting macroscopic and physicochemical properties.

    4. Norbornene/n-Butyl methacrylate copolymerization over α-Diimine nickel and palladium catalysts supported on multiwalled carbon nanotubes

      Ping Huo, Wanyun Liu, Xiaohui He and Yiwang Chen

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27384

      Thumbnail image of graphical abstract

      The covalently immobilized multiwalled carbon nanotubes (MWNTs) supported three-dimensional geometry α-diimine nickel, palladium catalysts exhibit high activities and productivities in norbornene homopolymerization or copolymerization with polar monomer. MWNTs are dispersed uniformly in polymers and wrapped by polymers to squeeze out of spherical particles, leading to the enhanced processability and mechanical properties.

    5. Photoresponsive polymers and block copolymers by molecular recognition based on multiple hydrogen bonds

      Alberto Concellón, Eva Blasco, Milagros Piñol, Luis Oriol, Isabel Díez, Cristina Berges, Carlos Sánchez-Somolinos and Rafael Alcalá

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27373

      Thumbnail image of graphical abstract

      The preparation of a series of photoaddressable supramolecular materials is demonstrated by mixing different polymers, which contain 2,6-diacylaminopyridine derivative units, and azobenzene chromophores having thymine (tAZO) or carboxylic groups with a dendritic structure (dAZO), which can form either three or two hydrogen bonds with the 2,6-diacylaminopyridine groups, respectively. Homogeneous materials are obtained with full complexation degrees without showing macrophase separation. We have also studied thermal, optical and assembly properties of these supramolecular materials.

    6. Stabilization and functionalization of single-walled carbon nanotubes with polyvinylpyrrolidone copolymers for applications in aqueous media

      Brian V. Popp, Dillon H. Miles, Jake A. Smith, Irene M. Fong, Matteo Pasquali and Zachary T. Ball

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27365

      Thumbnail image of graphical abstract

      Polyvinylpyrrolidone copolymers permit the synthesis of carbon nanotubes that are stable to significant pH gradients, allowing noncovalent functionalization with dye molecules and control over surface charge.

  5. Rapid Communications

    1. Polarity reversal of nanoparticle surfaces by the use of light-sensitive polymeric emulsifiers

      Robert Dorresteijn, Nils Billecke, Sapun H. Parekh, Markus Klapper and Klaus Müllen

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27363

      Thumbnail image of graphical abstract

      A polarity reversal of a nanoparticle surface with a light-sensitive PEG-block-poly((1-pyrenyl methyl)glutamate) (PEG-b-PGlu(Pyr)) copolymer is presented. The copolymer is successfully applied as emulsifier in a nonaqueous emulsion polymerization of lactide. The hydrophobic pyrenyl methylene units are readily cleaved from the outer hydrophilic PGlu-block by UV irradiation. The initially hydrophobic particles can now be dispersed in aqueous medium without the need of additional surfactants.

  6. Articles

    1. Design of high-χ block copolymers for lithography

      William J. Durand, Gregory Blachut, Michael J. Maher, Stephen Sirard, Summer Tein, Matthew C. Carlson, Yusuke Asano, Sunshine X. Zhou, Austin P. Lane, Christopher M. Bates, Christopher J. Ellison and C. Grant Willson

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27370

      Thumbnail image of graphical abstract

      Several silicon-containing block copolymers composed of styrene and its derivatives were investigated for lithographic applications. The interaction parameter (χ) of each material was estimated via two well-known techniques, demonstrating increases two to three times that of poly(styrene-block-4-trimethylsilylstyrene) upon appending various functional groups. Perpendicular-oriented thin films of BCPs were developed by reactive ion etching to demonstrate high aspect ratio patterns. Higher silicon-content components demonstrated greater etch resistance, and more strongly segregated BCPs improve pattern fidelity.

    2. Preparation and evaluation of a polymeric gel containing ionic liquid-functionalized MWCNTs as a novel class of organic solvent absorbent

      Ali Pourjavadi and Malihe Doulabi

      Article first published online: 28 AUG 2014 | DOI: 10.1002/pola.27372

      Thumbnail image of graphical abstract

      Ionic liquid-functionalized MWCNTs consisting of vinyl immidazolium cations and lipophilic tetrafluoroborate counteranions were synthesized and used as a novel crosslinking agent for the preparation of a new absorbent gel. The prepared MWCNT-based polymeric gel (ILMPG) exhibits high organic solvent absorbency, fast organic solvent absorption rate, and good reusability. ILMPG does not swell in water and can potentially be used for cleaning oil and organic solvent spills on water.

  7. Notes

    1. You have free access to this content
      Solubility switching of fluorescent polymer films via lewis acid–base vapor treatments

      Shotaro Hayashi and Toshio Koizumi

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

      Thumbnail image of graphical abstract

      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 a pattern development.

  8. Articles

    1. Rapid metal-free macromolecular coupling via In Situ nitrile oxide-activated alkene cycloaddition

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

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

      Thumbnail image of graphical abstract

      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.

    2. Tuning the energy gap of conjugated polymer zwitterions for efficient interlayers and solar cells

      Zachariah A. Page, Feng Liu, Thomas P. Russell and Todd Emrick

      Article first published online: 25 AUG 2014 | DOI: 10.1002/pola.27349

      Thumbnail image of graphical abstract

      Six narrow energy gap conjugated polymer zwitterions (CPZs) comprised of diketopyrrolopyrrole (DPP) and iso-indigo (iIn) backbones with pendant sulfobetaine (SB) solubilizing chains were synthesized. Probing the electronic properties and surface-metal interactions of the CPZs revealed energy gaps from 1.7 to 1.2 eV, and a 0.9 eV reduction in the work function of Ag. As buffer layers in BHJ solar cells, these CPZs improve device power conversion efficiency from 1.6% without the CPZ to 6.7-7.7% with the CPZ interlayer.

    3. Mechanical and shape-memory properties of poly(mannitol sebacate)/cellulose nanocrystal nanocomposites

      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

      Thumbnail image of graphical abstract

      The synthesis of nanocomposites of poly(mannitol-sebacate) (PMS) and cellulose nanocrystals (CNCs) 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 CNC contents were subsequently prepared by solution casting and curing under vacuum. The new materials display a shape-memory effect.

    4. Tuning the LCST of poly(2-cyclopropyl-2-oxazoline) via gradient copolymerization with 2-ethyl-2-oxazoline

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

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

      Thumbnail image of graphical abstract

      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 mol fraction of c-PropOx, allowing accurate tuning of TCP over a wide temperature range. Surprisingly, the glass transition temperature of all copolymers were lower than those of the homopolymers indicating poor interchain miscibility.

    5. Synthesis and characterization of a biodegradable ABC triblock terpolymer as co-delivery carrier of doxorubicin and DNA

      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

      Thumbnail image of graphical abstract

      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.

    6. Modified soybean oil as a reactive diluent: Synthesis and characterization

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

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

      Thumbnail image of graphical abstract

      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. Smart photoluminescent nanohybrids based on CdSe quantum dots capped with multidentate thiolated pH-responsive and thermoresponsive polymers for nanosensing

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

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

      Thumbnail image of graphical abstract

      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, the most important, an abrupt increase of the fluorescence emission when the polymer collapses at acid media.

    8. Photo-induced thiol-ene polysulfide-crosslinked materials with tunable thermal and mechanical properties

      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

      Thumbnail image of graphical abstract

      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.

    9. 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

      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

      Thumbnail image of graphical abstract

      Two interesting 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. Rapid Communication

    1. Advanced photoresist technologies by intricate molecular brush architectures: Diblock brush terpolymer-based positive-tone photoresist materials

      Guorong Sun, Sangho Cho, Fan Yang, Xun He, Adriana Pavía-Sanders, Corrie Clark, Jeffery E. Raymond, Stanislav V. Verkhoturov, Emile A. Schweikert, James W. Thackeray, Peter Trefonas and Karen L. Wooley

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27362

      Thumbnail image of graphical abstract

      The reported diblock brush terpolymer displays the fundamental advantages of high macromolecular and regiochemical control in simultaneous top-down/bottom-up construction of advanced positive-tone photoresist materials. By selective partition the substrate adhesion, surface-active migration, and chemically-reactive deblocking functional compositions into the cylindrical polymer brush architectures, large-areas of vertical alignment of the polymers within thin films are realized. The bottom-up premeditated system enables effective top-down lithography to produce near-molecular pixel resolution (2–3 molecules) at low operation dosage.

  10. Articles

    1. Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates

      Hiroharu Ajiro, Tatsuaki Ueyama and Mitsuru Akashi

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

      Thumbnail image of graphical abstract

      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.

    2. Preparation and self-assembly of stimuli-responsive azobenzene-containing diblock copolymers through microwave-assisted RAFT polymerization

      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, by using sequential reverse addition-fragmentation transfer (RAFT) polymerization. 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 diblock copolymer to yield spherical micelles with a mean diameter of ∼238.3 nm in THF/H2O media.

    3. Chiral sensing of Eu(III)-containing achiral polymer complex from chiral amino acids coordination induction

      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

      Thumbnail image of graphical abstract

      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 Cotton effect of CD spectra.

    4. Revisiting thiol-yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

      Johannes K. Sprafke, Jason M. Spruell, Kaila M. Mattson, Damien Montarnal, Alaina J. McGrath, Robert Pötzsch, Daigo Miyajima, Jerry Hu, Allegra A. Latimer, Brigitte I. Voit, Takuzo Aida and Craig J. Hawker

      Article first published online: 18 AUG 2014 | DOI: 10.1002/pola.27345

      Thumbnail image of graphical abstract

      Polymer coupling reactions are some of the most challenging chemical transformations due to low end-group concentration, steric hindrance, and decreased reactivity. Thiol-yne chemistry is shown to be a near-quantitative and selective strategy for the coupling of pre-formed polymers to give block and graft copolymers. With aromatic alkynes under a wide range of conditions, specific mono-addition is achieved with efficiencies surpassing those of traditional thiol-ene chemistry.

    5. The pH induced vesicle to micelle morphology transition of a THP-protected polymer

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

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

      Thumbnail image of graphical abstract

      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 DLS and TEM.

    6. Influence of linkage chemistry on folding, self-assembly, and photoresponse of amphiphilic azobenzene main chain polymers

      Zhilin Yu and Stefan Hecht

      Article first published online: 14 AUG 2014 | DOI: 10.1002/pola.27344

      Thumbnail image of graphical abstract

      Two types of amphiphilic polymers, composed of azobenzene repeat units in the main chain connected either via ethynylene or butadiynylene linkages and carrying (chiral) oligo(ethylene glycol) side chains, have been synthesized via Sonogashira–Hagihara or Glaser polycondensation. Solvent titration experiments reveal that both polymers fold into stable helices in a polar environment. While the ethynylene-bridged polymer (PAzoE) resembles the behavior of its oligomeric counterparts, introduction of the extended diacetylene unit strengthens π,π-stacking interactions in case of the butadiynylene-bridged polymer (PAzoB), leading to a pronounced aggregation tendency and suppressing photoisomerization in the folded state.

    7. Synthesis of chiral iridium complexes immobilized on amphiphilic polymers and their application to asymmetric catalysis

      Shinichi Itsuno, Yosuke Hashimoto and Naoki Haraguchi

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

      Thumbnail image of graphical abstract

      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.

    8. Well-controlled ring-opening polymerization of cyclic esters catalyzed by aluminum amido complexes: Kinetics and mechanism

      Junpeng Liu and Haiyan Ma

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

      Thumbnail image of graphical abstract

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

    9. Importance of unpaired electrons in organic electronics

      Jonathan D. Yuen, Mingfeng Wang, Jian Fan, Dennis Sheberla, Moureen Kemei, Natalie Banerji, Mariateresa Scarongella, Sebastian Valouch, Toan Pho, Rajeev Kumar, Eneida C. Chesnut, Michael Bendikov and Fred Wudl

      Article first published online: 11 AUG 2014 | DOI: 10.1002/pola.27321

      Thumbnail image of graphical abstract

      PBBTPD, a low bandgap, ambipolar conjugated donor-acceptor polymer based on benzobisthiadiazole (BBT), is shown to possess an open-shell singlet ground state as well as a thermally accessible triplet state. Theoretical predictions have suggested that such behavior is due to the biradicaloid character of BBT. This biradicaloid structure is in each BBT moiety and therefore PBBTPD is in fact a polyradicaloid. These observations will aid in development of better n-type polymeric acceptors for organic semiconductor applications.

  11. Foreword

  12. Articles

    1. An efficient nonisocyanate route to polyurethanes via thiol-ene self-addition

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

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

      Thumbnail image of graphical abstract

      The synthesis of a nonisocyanate polyurethane was carried out via thiol–ene self-photopolymerization by 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 urethane group is directly into the precursor monomer. The high reactive AMC is successfully stabilized with pyrogallol (1% wt) as radical inhibitor. The obtained polyurethane presents semi-crystalline nature and very high thermal stability (T5% = ∼325 °C).

    2. Synthesis of amphiphilic homopolymers with high chain end functionality by SET–LRP

      Shampa R. Samanta, Ruilong Cai and Virgil Percec

      Article first published online: 7 AUG 2014 | DOI: 10.1002/pola.27331

      Thumbnail image of graphical abstract

      For the first time SET–LRP of two amphiphilic acrylates, 2-methoxyethyl acrylate up to [M]0/[I]0 = 1000 and di(ethylene glycol) 2-ethylhexyl ether acrylate up to [M]0/[I]0 = 200 with very good control of molecular weight and molecular weight distribution is demonstrated in a common organic solvent, trifluoroethanol at 25 °C. Analysis of the chain end functionality of the resulting polymers demonstrates the synthesis of near-perfect chain-end functional homopolymers. This facile method opens up attractive possibilities for the fast synthesis of polymers with complex architecture under mild reaction conditions from amphiphilic monomers.

    3. One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a “catalyst switch” strategy

      Junpeng Zhao, David Pahovnik, Yves Gnanou and Nikos Hadjichristidis

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27332

      Thumbnail image of graphical abstract

      Two epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator using a strong phosphazene base promoter. An excess of diphenyl phosphate was introduced, followed by successive addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). Linear- and star-tetrablock quarterpolymers were prepared in one pot using this “catalyst switch” strategy.

  13. Rapid Communication

    1. Aspect ratio effect of nanorod surfactants on the shape and internal morphology of block copolymer particles

      Kang Hee Ku, Hyunseung Yang, Jae Man Shin and Bumjoon J. Kim

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27333

      Thumbnail image of graphical abstract

      The effect of aspect ratio (AR) of nanorod (NR) surfactants on the shape and internal morphology of block copolymer (BCP) particles was systemically investigated using CuPt NRs with different AR values ranging from 1 to 15. The positioning of the NRs in the BCP particles was dependent strongly on their AR values, and it enabled the modulation of the interfacial properties at selective locations on the BCP particles, thus producing interesting morphological transition of the BCP particles.

  14. Articles

    1. Controlled cyclopolymerization of 4,5-disubstituted 1,7-octadiynes and its application to the synthesis of a dendronized polymer using Grubbs catalyst

      Hyeon Park, Ho-Keun Lee, Eun-Hye Kang and Tae-Lim Choi

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27317

      Thumbnail image of graphical abstract

      Cyclopolymerization of 4,5-disubstituted 1,7-octadiyne using a third generation Grubbs catalyst is reported. With this highly reactive polymerization method, monomers with substituents varying from small ester to large dendron were successfully polymerized with rapid propagation rate.

  15. Rapid Communications

    1. Synthesis and characterization of novel amphiphilic super-H copolymers with linear–dendritic architecture

      Ivan Gitsov, Iliana V. Berlinova and Nikolay G. Vladimirov

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27318

      Thumbnail image of graphical abstract

      Novel linear–dendritic super-H block copolymers are prepared by multistage synthetic process involving “living” polymerizations.

    2. Self-assembly and reassembly of fiber-forming dipeptides for pH-triggered DNA delivery

      Glenn R. Hafenstine, Dylan W. Domaille, Jennifer N. Cha and Andrew P. Goodwin

      Article first published online: 31 JUL 2014 | DOI: 10.1002/pola.27319

      Thumbnail image of graphical abstract

      Hydrazone-based conjugates of PEG-dipeptide and DNA-dipeptide were designed to form stable vesicles at neutral pH, break apart at mildly acidic pH, and form large peptide fibers on release. Light scattering measurements showed that DNA-loaded vesicles of ∼80 nm were stable at pH 7.4 for 6 h and fell apart within 1 h at pH 5, with the DNA fully released from the formed fibers.

  16. Articles

    1. Bulk dispersion of single-walled carbon nanotubes in silicones using diblock copolymers

      Ryan C. Chadwick, Darryl Fong, Nicole A. Rice, Michael A. Brook and Alex Adronov

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27313

      Thumbnail image of graphical abstract

      Supramolecular complexes of poly(3-decylthiophene)-block-polydimethylsiloxanes (P3DT-b-PDMS) with single-walled carbon nanotubes (SWNTs) enable homogeneous incorporation of SWNTs within a bulk silicone elastomer, resulting in a low percolation threshold. The block copolymer anchors SWNTs within the silicone elastomer, allowing repeated stretching and relaxation without degradation of conductivity.

  17. Highlight

    1. You have free access to this content
      Functional aqueous assemblies of linear-dendron hybrids

      Greg Whitton and Elizabeth R. Gillies

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27316

      Thumbnail image of graphical abstract

      Recent progress on the development of aqueous assemblies of linear-dendron hybrids capable of performing functions is described. By engineering chemical functionalities in the linear or dendritic component, as well as their architectures, a wide variety of functions—including drug encapsulation, cell targeting, lectin binding, hydrogel formation, and catalysis—can be introduced. In addition, the assemblies can be designed to respond to a variety of stimuli including pH, temperature, light, and enzymes.

  18. Articles

    1. Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

      Jun'ichi Nagasawa, Sonoko Wakahara, Hajime Matsumoto, Hideyuki Kihara and Masaru Yoshida

      Article first published online: 28 JUL 2014 | DOI: 10.1002/pola.27310

      Thumbnail image of graphical abstract

      Positively charged polyelectrolytes with N,N′ -(trans-cyclohexane-1,4-diyl)dibenzamide linkages and varying spacer lengths have been synthesized and their ability to effect gelation for six ionic liquids and the properties of the resulting ionogels have been examined. The polymers gelatinize most of the tested ionic liquids at low concentrations (0.9-50 g/L). Gel-sol transition temperatures are dependent on the spacer length, while ionic conductivities of the various ionogels are near those of the neat ionic liquids and are not affected by spacer length.

  19. Rapid Communication

    1. You have free access to this content
      Kilogram scale inverse vulcanization of elemental sulfur to prepare high capacity polymer electrodes for Li-S batteries

      Jared J. Griebel, Guoxing Li, Richard S. Glass, Kookheon Char and Jeffrey Pyun

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27314

      Thumbnail image of graphical abstract

      Synthetic conditions to prepare high sulfur content copolymers via inverse vulcanization on a kilogram scale is reported. By investigation of polymerization comonomer feed ratios, reaction temperature, and scale, the development of conditions to enabled the large scale synthesis of poly(sulfur-random-(1,3-diisopropenylbenzene) was conducted. We further demonstrated enhanced device performance of these sulfur copolymers as active cathode materials in Li-S batteries.

  20. Articles

    1. Synthesis of degradable molecular brushes via a combination of ring-opening polymerization and click chemistry

      Yi Shi, Xiaofeng Wang, Robert W. Graff, William A. Phillip and Haifeng Gao

      Article first published online: 23 JUL 2014 | DOI: 10.1002/pola.27307

      Thumbnail image of graphical abstract

      Molecular brushes with an acid-degradable backbone and densely-grafted side chains (2 side chains per backbone repeating unit) are synthesized using an efficient grafting-onto method. The incorporated side chains vary from homopolymers to block copolymers and grafted polymers, and the produced molecular brushes can be degraded completely into linear polymers. When a mixture of side chains are used, the amphiphilic hetero-grafted molecular brushes can assemble in water and form either spherical micelles or hollow vesicles depending on sample compositions.

    2. Facile synthesis of high-molecular-weight acid-labile polypeptides using urethane derivatives

      Shirley Wong and Young Jik Kwon

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27320

      Thumbnail image of graphical abstract

      Preparation of acid-labile polypeptides by conventional methods, which polymerize unstable, moisture-sensitive amino acid monomers under highly restrictive conditions, has been challenging. A new method is reported that allows convenient synthesis of stable monomers and fast polymerization under easily applicable conditions, yielding high-molecular-weight acid-labile polypeptides with narrow polydispersity. The highly facile strategy demonstrated in this study could contribute to synthesizing stimuli-responsive peptide-based biomaterials for various biomedical applications.

    3. Synthetic control over the dynamics of mesoscaled cargo release from colloidal polymer vectors inside live cells

      Harvind S. Chahal, Dev S. Chahal, Patrick M. McBride and Brett A. Helms

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27312

      Thumbnail image of graphical abstract

      Dynamic complementarity between colloidal polymer vectors and their electrostatically adsorbed cargo is a critical parameter that influences the rate of cargo release once inside cells. Where endogenous macromolecules within the cytosol favorably compete for adsorption sites at the vector surface, cargo can be efficiently released and trafficked to intracytosolic targets.

    4. Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

      Alice M. Savage, Elizabeth Ullrich, Stacey M. Chin, Zachary Kiernan, Caitlyn Kost and S. Richard Turner

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27296

      Thumbnail image of graphical abstract

      Two sterically crowded stilbene comonomers, 3-methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene, are polymerized separately with maleic anhydride using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. RAFT agent compatibilities and reaction kinetics for each comonomer system are compared. Double hydrophilic block copolymers are synthesized from these copolymers and converted to polyelectrolytes. The isoelectric point and dissociation behavior of the polyelectrolytes are determined using ζ-potential and acid-base titrations, respectively.

    5. ABA triblock copolymers from two mechanistic techniques: Polycondensation and atom transfer radical polymerization

      Natalia A. Agudelo, Andrea M. Elsen, Hongkun He, Betty L. López and Krzysztof Matyjaszewski

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27300

      Thumbnail image of graphical abstract

      A series of ABA triblock copolymers were synthesized utilizing two polymerization techniques, polycondensation and atom transfer radical polymerization (ATRP). The choice of polymerization mechanisms results in block copolymers with unique molecular weight distributions the center of these triblock copolymers are disperse, resulting from polycondensation while the outside blocks have narrow molecular weight distribution due to the control afforded from ATRP.

  21. Highlight

    1. Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

      Andrey E. Rudenko and Barry C. Thompson

      Article first published online: 20 JUN 2014 | DOI: 10.1002/pola.27279

      Thumbnail image of graphical abstract

      Just like any other method of polymerization, direct arylation polymerization (DArP) produces defects in polymer structure, which have a strong impact on polymer properties. Therefore, it is important for polymer scientists to understand what causes the defect formation and how to control them. DArP produces four major classes of defects, and here we discuss in detail the origin of defects, their influence on polymer properties and the available methods to control them.


  1. 1 - 56