Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

15 December 2006

Volume 44, Issue 24

Pages 6895–7081

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      Poly(glycoamidoamine)s: Cationic glycopolymers for DNA delivery (pages 6895–6908)

      Theresa M. Reineke

      Version of Record online: 8 NOV 2006 | DOI: 10.1002/pola.21697

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      Polymeric materials show promise as novel nucleic acid delivery vehicles because they can be chemically tailored to encapsulate nucleic acids and facilitate cellular delivery. This article highlights our efforts to synthesize and study a novel class of cationic glycopolymers termed poly(glycoamidoamine)s. These materials incorporate a variety of carbohydrate comonomers to lower the toxicity and various oligoamine moieties to facilitate strong DNA binding, compaction, cellular uptake, and delivery of genetic material. Through structure–bioactivity studies, it has been discovered that subtle chemical changes play a large role in the observed delivery efficacy. (Artwork reproduced in part from Y. Liu and T. M. Reineke, J Am Chem Soc, 2005, 127, 3004–3015, © 2005 American Chemical Society, reproduced by permission.)

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    1. Dimensionally and thermally stable polymer, containing disordered graphitic structure and adamantane (pages 6909–6925)

      Kikue S. Burnham, Robert Roth, Faith Zhou, Wenya Fan, Emma Brouk and Mehari Stifanos

      Version of Record online: 13 NOV 2006 | DOI: 10.1002/pola.21788

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      Thermal treatment of oligomer O-1:4, derived from 1,3,5,7-tetrakis[3/4-ethynylphenyl]adamantine (4), results in the formation of the polycyclic aromatics via crosslinking of the diphenyldiethynyl groups at 380 °C and the disordered graphitic structure at 450 °C. The proposed structure of P-1:4(450) shows adamantine moiety surrounded by a number of nano-sized disordered graphitic clusters, which are stacks of fused polycyclic aromatic layers.

    2. Ring-opening polymerization of ϵ-caprolactone initiated with different ruthenium derivatives: Kinetics and mechanism studies (pages 6926–6942)

      José Luis Mata-Mata, J. Alfredo Gutiérrez, M. Angeles Paz-Sandoval, Amira R. Madrigal and Antonio Martínez-Richa

      Version of Record online: 2 NOV 2006 | DOI: 10.1002/pola.21787

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      The initiation step in the ring-opening polymerization of poly(ϵ-caprolactone) by catalysis with TpRuCl(PPh3)2 and TpRuCl (PHPh2)(PPh3) involves the formation of active species B. This is followed by an attack to the carbonyl group through an alcoxide group transfer, and ring-opening of lactone. An oxygen-acyl bond cleavage takes place with the formation of a growing species with an ester end group and an alkoxy group bound to the metal (C).

    3. Synthesis and cationic photopolymerization of new fluorinated, polyfunctional propenyl ether oligomers (pages 6943–6951)

      Marco Sangermano, Roberta Bongiovanni, Giulio Malucelli, Aldo Priola, Richard R. Thomas, Charles M. Kausch and Yongsin Kim

      Version of Record online: 2 NOV 2006 | DOI: 10.1002/pola.21807

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      Fluorinated, polyfunctional propenyl ether functionalized resins were synthesized, and their behavior in cationic photopolymerization was investigated. A fluorinated resin was also employed as a reactive additive in the cationic photopolymerization of trimethylolpropane tripropenyl ether.

    4. Synthesis and properties of fluorene-based polyheteroarylenes for photovoltaic devices (pages 6952–6961)

      Raja Shahid Ashraf, Harald Hoppe, Munazza Shahid, Gerhard Gobsch, Steffi Sensfuss and Elisabeth Klemm

      Version of Record online: 7 NOV 2006 | DOI: 10.1002/pola.21645

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      Novel polyheteroarylenes consisting of fluorene and thieno[3,4-b]pyrazine/quinoxaline were prepared in high yields by Suzuki cross-coupling reactions. Photovoltaic devices based on one of the novel polymers in combination with the well-known fullerene acceptor [6,6]-phenyl C61–butyric acid methyl ester showed power conversion efficiencies of 0.5%.

    5. Incubation period in the 2,2,4,4-tetramethyl-1-piperidinyloxy-mediated thermal autopolymerization of styrene: Kinetics and simulations (pages 6962–6979)

      Enrique Saldívar-Guerra, José Bonilla, Gregorio Zacahua and Martha Albores-Velasco

      Version of Record online: 2 NOV 2006 | DOI: 10.1002/pola.21759

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      Simulations with a global model, including the induction and postinduction (polymerization) regimes, are compared with previously published experimental data for the kinetics of the thermal polymerization of styrene with different 2,2,4,4-tetramethyl-1-piperidinyloxy (TEMPO) concentrations at 125 °C. The model includes for the first time the important reactions of the Mayo dimer with TEMPO [the kinetic constant of hydrogen abstraction (kh)] and of the direct attack of TEMPO against styrene to generate initiating radicals (kinetic constant kad). Estimations for kh and kad are provided.

    6. Thermal stability of reversible addition–fragmentation chain transfer/macromolecular architecture design by interchange of xanthates chain-transfer agents (pages 6980–6987)

      Thomas M. Legge, Andrew T. Slark and Sébastien Perrier

      Version of Record online: 2 NOV 2006 | DOI: 10.1002/pola.21803

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      The relationship between the structure of reversible addition–fragmentation chain-transfer agents and thermal stability was investigated with the aid of thermogravimetric analysis and gas chromatography/mass spectrometry. All classes of reversible addition–fragmentation chain-transfer agents commonly used in living radical polymerizations were investigated to provide useful information for synthetic polymer chemists wishing to work at elevated temperatures.

    7. Synthesis and polymerization of a new nitrogen-containing bis-ortho-diynylarene monomer (pages 6988–6996)

      Huseyin Zengin, Gulay Zengin and Dennis W. Smith Jr

      Version of Record online: 2 NOV 2006 | DOI: 10.1002/pola.21774

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      Preparation, characterization, and optical properties of new bis-(3,4-diphenylethynylphenyl)phenylamine was carried out. This is the first nitrogen-containing bis-ortho-diynylarene (BODA) monomer having a nitrogen atom as the spacer group. The structure of the monomer and its polymer were characterized using different spectroscopic techniques. Polymerizations were studied by differential scanning calorimeter and electrical conductivity of neat HCl doped BODA-derived polymer film was measured.

    8. Benzophenone-functionalized, starlike polystyrenes as organic supports for a tridentate bis(imino)pyridinyliron/trimethylaluminum catalytic system for ethylene polymerization (pages 6997–7007)

      Cécile Bouilhac, Henri Cramail, Eric Cloutet, Alain Deffieux and Daniel Taton

      Version of Record online: 7 NOV 2006 | DOI: 10.1002/pola.21779

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      Starlike polystyrenes composed of a microgel core and arms terminated with benzophenone groups were synthesized by atom transfer radical polymerization, including a subsequent treatment necessary to displace the bromo end group. These bromine-free, functionalized polystyrene stars were tested as organic supports for the tridentate bis(imino)pyridinyliron/trimethylaluminum catalytic system for ethylene polymerization. The polyethylene beads presented a spherical morphology and a high bulk density. The catalytic activity remained high compared with that under homogeneous conditions, and the polyethylene molar mass distribution was narrow, suggesting a limited transfer reaction to trimethylaluminum.

    9. Synthesis of hydrophilic isotactic polypropylenes promoted by metallocene catalysts (pages 7008–7013)

      Lucia Caporaso and Leone Oliva

      Version of Record online: 13 NOV 2006 | DOI: 10.1002/pola.21790

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      Isotactic polypropylenes modified with [BOND]OH groups in sides (iPP-OH) were obtained by combination of polyinsertion ansa-metallocene catalysis and ring opening of propene oxide. Isotactic polypropylene sequences interrupted by isolated ethylene/p-methylstyrene were synthesized as backbones, by using ansa-metallocene catalysts. Afterwards, the p-Me groups of the backbone were reacted with sec-BuLi to generate anionic centres. iPP-OH were the results of the monoaddition reaction of propene oxide (PO) on the anionic centers followed by hydrolysis with acidified methanol. By changing experimental conditions, iPP samples with a different number of [BOND]OH groups for the backbone were synthesized.

    10. Use of a new methacrylic monomer, 4,4′-di(2-hydroxy-3-methacryloyloxypropoxy)benzophenone, in the synthesis of porous microspheres (pages 7014–7026)

      Beata Podkościelna, Barbara Gawdzik and Andrzej Bartnicki

      Version of Record online: 7 NOV 2006 | DOI: 10.1002/pola.21780

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      A new aromatic, tetrafunctional methacrylate monomer, 4,4′-di(2-hydroxy-3-methacryloyloxypropoxy)benzophenone, and its application to the synthesis of porous microspheres are presented. This new monomer was copolymerized with divinylbenzene in the presence of pore-forming diluents. The properties of the obtained highly crosslinked microspheres were investigated as column packing for high-performance liquid chromatography. Their porous structures in both dry and wet states were studied and compared with those of poly(divinylbenzene) and the less crosslinked copolymer of 2,3-epoxypropyl methacrylate and divinylbenzene.

    11. Ultrathin gradient films using thiol-ene polymerizations (pages 7027–7039)

      Vaibhav S. Khire, Danielle S. W. Benoit, Kristi S. Anseth and Christopher N. Bowman

      Version of Record online: 7 NOV 2006 | DOI: 10.1002/pola.21786

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      A decyltrichlorosilane gradient is deposited by diffusing the silane on the surface (step 1) and is backfilled with a MPTMS silane, resulting in a thiol gradient in the opposite direction (step 2). The thiol gradient is then modified in several ways (step 3) to obtain films with varying thickness, surface chain density, wettability and cell adhesion properties. A two-dimensional gradient is obtained by changing SAM concentration in one direction and polymerization conditions in the orthogonal direction. A cell adhesion peptide is attached to the thiol surface to obtain a surface with variable cell density.

    12. Synthesis of copolymers containing a spiro orthocarbonate moiety and evaluation of the volume change during their cationic crosslinking (pages 7040–7053)

      Makoto Kume, Yuya Maki, Bungo Ochiai and Takeshi Endo

      Version of Record online: 7 NOV 2006 | DOI: 10.1002/pola.21772

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      A spiro orthocarbonate having an exomethylene or allyl group was radically copolymerized with acrylonitrile, vinyl acetate, methyl acrylate, and glycidyl methacrylate at several feed ratios to obtain the corresponding copolymers having spiro orthocarbonate moieties in the side chain. The obtained copolymers could be crosslinked via the cationic double ring-opening polymerization of the spiro orthocarbonate moieties without volume shrinkage or with volume expansion.

    13. Synthesis and Rh(I)-catalyzed polymerization of 1,3-diphenylyne–calix[4]arene compounds: Novel conjugated, calixarene-based polymers (pages 7054–7070)

      Alexandra I. Costa and José V. Prata

      Version of Record online: 9 NOV 2006 | DOI: 10.1002/pola.21797

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      Appropriate calix[4]arene derivatives were successfully functionalized in the lower rim through an improved Sonogashira–Hagihara cross-coupling procedure, affording two syn–distal diphenylethynylcalix[4]arene compounds, 5,11, 17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(4-ethynylbenzyloxy)-26,28-dihydroxycalix[4]arene (1) and 25,27-bis(4-ethynylbenzyloxy)-26,28-dihydroxycalix[4]arene (2). The ability of these bifunctional monomers for the synthesis of conjugated polymers was examined. It was pleasantly found that such building blocks were efficiently polymerized with rhodium-based initiators, smoothly producing the expected conjugated polymers, poly{5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(4-ethynylbenzyloxy)-26,28-dihydroxycalix[4] arene} (poly 1) and poly{25,27-bis(4-ethynylbenzyloxy)-26,28-dihydroxycalix[4]arene} (poly 2).

    14. Cationic copolymerization of ε-caprolactone and L,L-lactide by an activated monomer mechanism (pages 7071–7081)

      Małgorzata Baśko and Przemysław Kubisa

      Version of Record online: 13 NOV 2006 | DOI: 10.1002/pola.21712

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      The cationic copolymerization of L,L-lactide with ε-caprolactone in the presence of alcohols proceeds by an activated monomer mechanism. The molecular weights and dispersities are controlled {number-average degree of polymerization = ([M]0 − [M]t)/[I]0, where [M]0 is the initial monomer concentration, [M]t is the monomer concentration at time t, and [I]0 is the initial initiator concentration; weight-average molecular weight/number-average molecular weight ∼ 1.1–1.3}. An analysis of 13C NMR spectra of the copolymers indicates that transesterification is slow in comparison with propagation, and the microstructure of the copolymers is governed by the relative reactivity of the comonomers.

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