Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 24

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

Impact Factor: 3.245

ISI Journal Citation Reports © Ranking: 2013: 14/82 (Polymer Science)

Online ISSN: 1099-0518

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

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  1. 1 - 58
  1. Articles

    1. Novel heterocyclic poly(pyridine-imide)s with unsymmetric carbazole substituent and noncoplanar structure: High thermal, mechanical and optical transparency, electrochemical, and electrochromic properties

      Ying-Chi Huang, Kun-Li Wang, Wei-Yi Lee, Yi-An Liao, Der-Jang Liaw, Kueir-Rarn Lee and Juin-Yih Lai

      Article first published online: 21 NOV 2014 | DOI: 10.1002/pola.27438

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      Diamine-containing pyridine and unsymmetrical carbazole groups were synthesized via a Chichibabin reaction and subsequent reduction, and used in the preparation of poly(pyridine-imide)s PI-1–8. When the HCl concentration was increased, a new absorption band appeared at approximately 350 nm, and the intensity of the fluorescent peak at 380 nm observed in the neutral polymer solution decreased, along with the appearance of the new fluorescent peak at 540 nm.

  2. Erratum

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    2. You have free access to this content
      Erratum: Synthesis of unsaturation containing P(VDF-co-TrFE-co-CTFE) from P(VDF-co-CTFE) in one-pot catalyzed with Cu(0)-based single electron transfer living radical polymerization system

      Xin Hu, Shaobo Tan, Guoxin Gao, Yunchuan Xie, Qinzhuo Wang, Na Li and Zhicheng Zhang

      Article first published online: 18 NOV 2014 | DOI: 10.1002/pola.27464

      This article corrects:

      Cover Image, Volume 52, Issue 23

      Vol. 52, Issue 23, i–ii, Article first published online: 27 OCT 2014

  3. Rapid Communications

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      Stabilization of factor VIII by poly(2-oxazoline) hydrogels

      Matthias Hartlieb, Stephanie Schubert, Kristian Kempe, Norbert Windhab and Ulrich S. Schubert

      Article first published online: 18 NOV 2014 | DOI: 10.1002/pola.27457

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      Using a bis-functional monomer, poly(2-oxazoline) hydrogels were synthesized via cationic ring-opening polymerization and used to stabilize FVIII in aqueous solution.

  4. Articles

    1. pH-responsive near-infrared emitting conjugated polymer nanoparticles for cellular imaging and controlled-drug delivery

      Jousheed Pennakalathil, Alp Özgün, Irem Durmaz, Rengül Cetin-Atalay and Dönüs Tuncel

      Article first published online: 17 NOV 2014 | DOI: 10.1002/pola.27458

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      pH-responsive near-infrared emitting conjugated polymer nanoparticles (CPNs) were prepared, characterized, and their stabilities were investigated under various conditions. It was shown that CPNs can be effectively utilized as vehicles for pH-triggered release of anticancer drugs and for cellular imaging.

    2. Isobutylene-rich macromonomers: Dynamics and yields of peroxide-initiated crosslinking

      Jackson M. Dakin, Karthik Vikram Siva Shanmugam, Christopher Twigg, Ralph A. Whitney and J. Scott Parent

      Article first published online: 17 NOV 2014 | DOI: 10.1002/pola.27462

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      Peroxide-initiated crosslinking dynamics and yields of a range of isobutylene-rich macromonomers are examined and discussed.

    3. Design, polymerization, and properties of polyurethane elastomers from miscible, immiscible, and hybridized seed-oil derived soft segment blends

      Mark F. Sonnenschein, Valeriy V. Ginzburg, Adam L. Grzesiak, Klaus Schiller and Benjamin L. Wendt

      Article first published online: 10 NOV 2014 | DOI: 10.1002/pola.27450

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      Polyol soft segments can be blended, but phase separated if mixing thermodynamics are unfavorable. This is particularly evident in attempts to blend seed-oil polyols with some conventional petrochemical polyols. Polyurethane elastomers from phase separated polyols have broad glass transitions and poor tensile properties. Seed-oil soft segment blends that are chosen for miscibility, or are chemically polymerized forming a single soft segment can result in high-performing elastomers with narrow glass transitions and good tensile properties.

    4. Methyl branching in PE from homopolymerization of ethylene with N-arylcyano-β-diketiminate methallyl nickel-B(C6F5)3

      Oleksandra S. Trofymchuk, Griselda Barrera Galland, Marcéo A. Milani and Rene S. Rojas

      Article first published online: 10 NOV 2014 | DOI: 10.1002/pola.27456

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      The N-arylcyano-β-diketiminate methallyl nickel complexes activated with B(C6F5)3 catalyze polymerization of ethylene leading to linear low density polyethylenes with mainly isolated methyl branches. The unique nature of these materials could be an alternative to replace copolymerization of ethylene with propene.

    5. Comparison of monomethoxy-, dimethoxy-, and trimethoxysilane anchor groups for surface-initiated RAFT polymerization from silica surfaces

      Dennis Huebner, Vanessa Koch, Bastian Ebeling, Jannik Mechau, Judith Elisabeth Steinhoff and Philipp Vana

      Article first published online: 7 NOV 2014 | DOI: 10.1002/pola.27454

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      The immobilization of RAFT agents on silica for surface-initiated RAFT polymerizations was studied systematically in dependence of the functionality of the RAFT-agent anchor group. Monoalkoxy-, dialkoxy-, and trialkoxy silyl ether groups were incorporated in trithiocarbonate-type RAFT agents and bound to planar silica surfaces as well as to silica nanoparticles. The immobilization efficiency and the structure of the bound RAFT-agent film varied strongly in dependence of the used solvent and the anchor group functionality.

    6. Synthesis and asymmetric anionic polymerization of substituted 7-aryl-2,6-dimethyl-1,4-benzoquinone methides

      Takahiro Uno, Hiroshi Ohta, Atsushi Yamane, Masataka Kubo and Takahito Itoh

      Article first published online: 7 NOV 2014 | DOI: 10.1002/pola.27449

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      Asymmetric anionic polymerizations of 7-substituted aryl-2,6-dimethyl-1,4-benzoquinone methides (R = p-OMe (2a), p-Cl (2b), m-Cl (2c), and o-Cl (2d)) using the complex of lithium 4-isopropylphenoxide with (−)-sparteine gave corresponding polymers with negative specific rotation. The largest specific rotation value was obtained in the polymerization of 2d with an electron-withdrawing ortho-chloro substituent.

    7. A benzophenone-naphthalimide derivative as versatile photoinitiator of polymerization under near UV and visible lights

      Jing Zhang, Nicolas Zivic, Frédéric Dumur, Pu Xiao, Bernadette Graff, Didier Gigmes, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 7 NOV 2014 | DOI: 10.1002/pola.27451

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      A naphthalimide-benzophenone derivative (N-(4-benzophenone)-4-[2-(dimethylamino)ethyl]-1,8-naphthalimide) bearing a tertiary amine group was designed and synthesized. It can be used as a one-component photoinitiator or be incorporated into two-component photoinitiating systems for the free radical polymerization of acrylates as well as the cationic polymerization of epoxides under exposure to various LEDs. This newly developed benzophenone derivative exhibited excellent polymerization efficiency and it was even more efficient than the well-known camphorquinone based systems and the commercial photoinitiator bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (BAPO) upon certain irradiation.

  5. Rapid Communications

    1. Synthesis of amino-containing syndiotactic polystyrene as efficient polymer support for palladium nanoparticles

      Zhenghai Shi, Fang Guo, Yang Li and Zhaomin Hou

      Article first published online: 7 NOV 2014 | DOI: 10.1002/pola.27455

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      Amino-containing functionalized syndiotactic polystyrenes with high melting temperatures and temperature stability are synthesized by the direct polymerization of amino-containing styrenic monomers in the presence of a half-sandwich scandium catalyst system [(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2]/[Ph3C][B(C6F5)4]. The high syndiotactic poly(N,N-dimethylamino)styrene (rrrr > 99%), then used as novel polymer supports, effectively anchored Pd nanoparticles (3 wt % of Pd) with a diameter of 4 or 5 nm that were uniformly dispersed on polymer matrix.

  6. Articles

    1. Synthesis and characterization of high nitrile content polyimides as dielectric films for electrical energy storage

      David H. Wang, Brian A. Kurish, Imre Treufeld, Lei Zhu and Loon-Seng Tan

      Article first published online: 30 OCT 2014 | DOI: 10.1002/pola.27445

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      In the polyimide films, an increase in dipole moment density by the presence of three neighboring CN per repeat unit can increase relative permittivity. Polarization response results implicate that (i) an increase in the number of CN dipoles is insufficient in elevating permittivity proportionally without cooperative alignment of the multiple dipoles; (ii) paraphenylene is more effective than meta-phenylene in enhancing relative permittivity probably because of its greater facility in sub-Tg mobility (“ring flipping”) that aids such cooperative dipole alignment with applied electric field.

    2. Organic nanoparticles as fragmentable support for Ziegler–Natta catalysts

      Sven Nietzel, Daejune Joe, Joseph W. Krumpfer, Frank Schellenberger, Abdulhamid A. Alsaygh, Gerhard Fink, Markus Klapper and Klaus Müllen

      Article first published online: 29 OCT 2014 | DOI: 10.1002/pola.27442

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      Micrometer-sized aggregates of polystyrene nanoparticles are presented as organic support materials for Ziegler–Natta catalysts. The catalytic activity in ethylene slurry polymerizations is found to be directly correlated to the hydroxyl group content of the supports. The ability to produce medium molecular weight distributions of high-density polyethylene in a one-pot, one-catalyst process in conjunction with good support fragmentability is demonstrated.

    3. Preparation, properties, and antibacterial behavior of a novel cellulose derivative containing lactam groups

      Fanny Joubert, Gary J. Sharples, Osama M. Musa, David R. W. Hodgson and Neil R. Cameron

      Article first published online: 29 OCT 2014 | DOI: 10.1002/pola.27441

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      A novel cellulose derivative is prepared by the chemical modification of hydroxyethyl cellulose with pyrrolidone groups. The new material has improved solubility, lower solution viscosity, and enhanced thermal stability compared with HEC, as well as some antibacterial properties.

    4. Toward model-driven engineering of supramolecular copolymers

      Peter A. Korevaar, Christophe Grenier and E. W. Meijer

      Article first published online: 29 OCT 2014 | DOI: 10.1002/pola.27446

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      The coassembly of two different π-conjugated oligo(p-phenylene vinylene) derivatives is studied. ROPV3 and SOPV4 have opposite chirality; where SOPV4 can easily coassemble into helices formed by ROPV3, the opposite is not true. As a result, the assemblies comprise mixed or phase-separated building blocks. The consequences of this phenomenon are demonstrated for one molecular system and the co-assembly pathways involved are analysed via a kinetic model and disclose general lessons for the development of supramolecular copolymers.

    5. Synthesis and characterization of copoly(amide triazole)s derived from d-Glucose

      Manuel Bueno-Martínez, Inmaculada Molina-Pinilla, Khalid Hakkou and Juan A. Galbis

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27444

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      Several degradable linear copoly(amide triazole)s have been prepared by thermal cycloaddition reaction, starting from monomers coming from natural regrowing resources. The copolymers present different characteristics like hydrophilicity, solubility, or thermal properties depending on the ratio of the monomers in the polymer chain or on the procedure used to their preparation. The copolymers present free secondary alcohol functions that were used for preparing polymeric networks.

    6. Influence of branching on the chiral self-assembly of poly(phenylene ethynylene)

      Joost Steverlynck, Pieter Leysen and Guy Koeckelberghs

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27443

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      A series of all-conjugated poly(phenylene ethynylenes) with a controllable degree of branching was prepared. The influence of branching on the self-assembly was studied by using UV–vis, CD, fluorescence spectroscopy and DSC, as were the effects of that branching, and the resulting change in self-assembly, on the chiral expression.

    7. Ordered nanostructures from self-assembly of H-shaped coil–rod–coil molecules

      Zhuoshi Wang, Keli Zhong, Yongri Liang, Tie Chen, Bingzhu Yin, Myongsoo Lee and Long Yi Jin

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27448

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      H-shaped coil–rod–coil oligomers, consisting of biphenyl, phenylene vinylene, and phenylene ethynylene units, as the rigid segment have been synthesized. The experimental results reveal that the lateral methyl groups attached to the surface of the rod and coil segments dramatically influence the formation of various supramolecular nanostructures in the crystalline phase.

  7. Rapid Communications

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      Hydrolytically stable polyurethanes

      Jungmee Kang and Joseph P. Kennedy

      Article first published online: 27 OCT 2014 | DOI: 10.1002/pola.27447

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      Polyisobutylene-based polyurethanes exhibit outstanding hydrolytic stability. PU samples were immersed in PBS at pH 7.4 and aqueous buffers at pH 1 and 11, and heated at 85 °C for 10 weeks. According to SEC analysis, Mn, Mw, Mw/Mn did not change (within experimental variation) in the course of the test. In contrast, a PDMS-based PU severely degraded after one week under the same conditions.

  8. Articles

    1. Comparing linear and cyclic synthetic homopolypeptides: Synthesis and molecular characterization

      Nikolaos Politakos, George Liontos, Galder Kortaberria, Jamie M. Messman, Javier Calvo, Sergio E. Moya, Jimmy W. Mays and Apostolos Avgeropoulos

      Article first published online: 24 OCT 2014 | DOI: 10.1002/pola.27434

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      The successful synthesis and characterization of linear and cyclic poly(o-Bn-l-Tyr) are described. The verification of the cyclic architecture was accomplished by various molecular characterization techniques. Special attention is given in the behavior and specific shifts in NMR spectroscopy experiments given by characteristic groups/bonds on the cyclic versus the linear corresponding homopolypeptide.

    2. Iron complexes as photoinitiators for radical and cationic polymerization through photoredox catalysis processes

      Jing Zhang, Damien Campolo, Frederic Dumur, Pu Xiao, Jean Pierre Fouassier, Didier Gigmes and Jacques Lalevée

      Article first published online: 23 OCT 2014 | DOI: 10.1002/pola.27435

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      A series of iron complexes (FeCs) were developed and applied as photocatalysts in photoinitiating systems for radical and cationic polymerization. These FeC-based systems exhibit photocatalytic properties, undergo the formation of radicals, radical cations, and cations and can operate through oxidation or/and reduction cycles. These reported systems are characterized by an unprecedented reactivity on LED irradiation. Contrary to the most famous reference system (BAPO), the newly developed systems with very low FeC content (0.02 wt %) is still highly efficient in photopolymerization, illustrating the performance of the proposed catalytic approach.

    3. ROMP synthesis of novel thermo-, pH-, and salt-responsive (co)polymers containing the morpholino functional group

      Johannes A. van Hensbergen, Sylvia Ganda, Peter J. Roth, Robert P. Burford and Andrew B. Lowe

      Article first published online: 21 OCT 2014 | DOI: 10.1002/pola.27436

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      A series of new (co)polymers containing the multiresponsive morpholino functional group have been prepared by ring-opening metathesis polymerization (ROMP) with RuCl2(PCy3)2CHPh.

    4. Using controlled radical polymerization to confirm the lower critical solution temperature of an N-(alkoxyalkyl) acrylamide polymer in aqueous solution

      Xeniya Savelyeva, Lucia Li and Milan Marić

      Article first published online: 21 OCT 2014 | DOI: 10.1002/pola.27437

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      Poly(N-(3-methoxypropyl) acrylamide (MPAM) homopolymers and block copolymers with N,N-diethylacrylamide (DEAAM) as a second block were synthesized and well controlled by CRP methods, particularly RAFT. The solution properties were assessed by UV–Vis and dynamic light scattering. Dual lower critical solution temperature type behavior was found for the block copolymers and the cloud point temperature of poly(MPAM) was determined to be about 73–92 °C, depending on molecular weight and solution concentration.

    5. Dynamic covalent polypeptides showing tunable secondary structures and thermoresponsiveness

      Jiatao Yan, Kun Liu, Xiuqiang Zhang, Wen Li and Afang Zhang

      Article first published online: 19 OCT 2014 | DOI: 10.1002/pola.27433

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      The imine condensation from poly(l-lysine)s and oligoethylene glycol (OEG)-based dendritic aldehydes afforded dynamic OEGylated polypeptides, which show enhanced helical conformation and superior thermoresponsive properties. Their phase transition temperatures were governed predominately by terminal groups and coverage of OEG dendrons, and could be tuned simply by varying ratios of OEG dendrons with different hydrophilicity. Furthermore, thermally induced dehydration and aggregation was found to enhance the imine formation and, at the same time, to switch helical conformations of polypeptides.

    6. Synthesis via ATRP, kinetics study and characterization (molecular-morphological) of 3-Arm star diblock copolymers of the (PS-b-P2VP)3 type

      George Polymeropoulos, Dimitrios Moschovas, Anastasia Kati, Apostolos Karanastasis, Styliani Pelekanou, Panagiotis Christakopoulos, Georgios Sakellariou and Apostolos Avgeropoulos

      Article first published online: 18 OCT 2014 | DOI: 10.1002/pola.27432

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      The successful synthesis via ATRP of 3-arm star homopolymers and corresponding diblock copolymers of the (PS)3 and (PS-b-P2VP)3 types, through an initiator bearing three –Br groups, is discussed. A kinetics study is performed for the synthesis of the star homopolymer to evaluate polymerization time versus polydispersity, molecular weight, and yield. Molecular characterization through various techniques verifies the preparation of both architectures and TEM studies confirm the microphase separation of the final copolymers.

  9. Rapid Communication

    1. Synthesis of Pyridine Chitosan and its Protonic Conductivity

      Yingxin Deng, Brett A. Helms and Marco Rolandi

      Article first published online: 18 OCT 2014 | DOI: 10.1002/pola.27430

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      The synthesis of a positively charged and water soluble chitosan derivative from chitosan is presented.

  10. Erratum

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      Erratum: Evaluation Of proton conductivity of sulfonated polyimide/dihydroxy naphthalene charge-transfer complex hybrid membranes

      Liana Christiani, Sandra Hilaire, Kazunari Sasaki and Masamichi Nishihara

      Article first published online: 30 SEP 2014 | DOI: 10.1002/pola.27419

      This article corrects:
  11. Articles

    1. Patterned growth of oriented 2D covalent organic framework thin films on single-layer graphene

      John W. Colson, Jason A. Mann, Catherine R. DeBlase and William R. Dichtel

      Article first published online: 29 SEP 2014 | DOI: 10.1002/pola.27399

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      Covalent organic frameworks (COFs) are crystalline network polymers that feature permanent porosity, high surface areas, and predictable organization of their monomers. COFs are typically isolated as insoluble powders, but high-quality thin films are needed to fully explore their potential applications. This manuscript demonstrates that suitable solvent mixtures promote COF growth selectively on single-layer graphene. Lithography of the graphene provides patterned COF films, offering unprecedented control of COF growth relevant to their incorporation into device architectures.

    2. A glucose sensor via stable immobilization of the GOx enzyme on an organic transistor using a polymer brush

      M. Elizabeth Welch, Thomas Doublet, Christophe Bernard, George G. Malliaras and Christopher K. Ober

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27392

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      A PEDOT:PSS based microelectrode, which measures neuronal activities in vivo, is enhanced through the incorporation of polymer brushes. This biosensor requires the tethering of glucose oxidase for specific charge exchange reactions to occur between the biological media and the conducting polymer sensor. Polymer brushes are used to anchor these molecules to the electrode surface without altering the conductivity of the transistor.

    3. 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

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      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.

    4. 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

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      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.

  12. 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

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      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.

  13. Articles

    1. 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

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      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.

  14. 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

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      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.

  15. 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

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      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. 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

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      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.

  16. 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

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      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.

  17. Articles

    1. 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

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      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.

    2. 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

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      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.

    3. 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

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      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.

  18. Foreword

  19. Articles

    1. 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

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      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.

    2. 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

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      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.

  20. 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

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      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.

  21. 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.

  22. 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

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      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.

  23. 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.

  24. 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

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      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.

  25. 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

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      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.

  26. 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

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      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.

  27. 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.

  28. 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.

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