Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 3

1 February 2013

Volume 51, Issue 3

Pages i–iv, 471–742

  1. Cover Image

    1. Top of page
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    3. Highlight
    4. Rapid Communication
    5. Articles
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    1. You have free access to this content
      Cover Image, Volume 51, Issue 3 (pages i–ii)

      Article first published online: 22 DEC 2012 | DOI: 10.1002/pola.26509

      Thumbnail image of graphical abstract

      The image shows a representative one-handed helical structure of poly(naphthalenecarboxamide) obtained by DFT calculation. On page 739, Koichiro Mikami and Tsutomu Yokozawa present the synthesis and chiral amplification of a helical aromatic polyamide, poly(naphthalenecarboxamide), with alkyl side chains. The helical polyamide is synthesized by means of chain-growth condensation polymerization. The folding of the polymer is exemplified using UV and CD spectroscopy. The copolymer of monomers having a chiral alkyl side chain and an achiral alkyl side chain shows a significant chiral amplification on the basis of the sergeants and soldiers principle in a hydrophobic environment even with only a tiny incorporation of chiral units.

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      Inside Cover, Volume 51, Issue 3 (pages iii–iv)

      Article first published online: 22 DEC 2012 | DOI: 10.1002/pola.26510

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      The combination of UV curing and a new phosphonium borate salt has enabled the production of tough polyelectrolyte films in a single step, as described by B. M. Berven, P. J. Ragogna, et al. on page 499. A series of new polymerizable anions Na[BPhxSty4-x], x = 0–3, are prepared in high yields with 1–4 para-vinylphenyl units incorporated onto the boron atom, and these borates have the potential to be paired with a wide variety of cationic units. Pairing with a polymerizable phosphonium cation gives a series of organic salts that are directly polymerized by UV curing, affording highly crosslinked polyelectrolyte films that do not require the usual substrate pre-treatment (glass) or instillation of an anchoring layer. The mechanical properties of the polymeric materials could also be tailored by the anion functionality, as demonstrated by the increased scratch resistance as the crosslink density increased.

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      Cationic polymerization of isobutylene at room temperature (pages 471–486)

      Sergei V. Kostjuk, Hui Yee Yeong and Brigitte Voit

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26423

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      Highly reactive polyisobutylene (HR PIB) can be successfully prepared by cationic polymerizaion at room temperature using special initiating and catalyst systems like modified Lewis acids and metal complexes associated with weakly coordinating anions. Successful systems allow chain transfer to be regulated and protic activity to be reduced.

  3. Rapid Communication

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    1. Spotlight Article

      Post-functionalization of a ROMP polymer backbone via radical thiol-ene coupling chemistry (pages 487–492)

      Johannes Arend van Hensbergen, Robert P. Burford and Andrew B. Lowe

      Article first published online: 8 NOV 2012 | DOI: 10.1002/pola.26433

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      The radical thiol-ene reaction is used to modify the backbone of a common ROMP-prepared homopolymer. Hydrothiolation is successful in most instances in facilitating the ready introduction of a range of functionality including OH, pyrrole, alkyl, ester, and POSS species while still retaining the well-defined characteristics of the parent polymer.

    2. New bifunctional catalyst based on cobalt–porphyrin complex for the copolymerization of propylene oxide and CO2 (pages 493–498)

      Wei Wu, Yusheng Qin, Xianhong Wang and Fosong Wang

      Article first published online: 15 NOV 2012 | DOI: 10.1002/pola.26434

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      A novel bifunctional cobalt-porphyrin catalyst which contains a Lewis acidic metal center and a quaternary ammonium salt unit in a molecule has been developed. This new catalyst system exhibits superior copolymerization activity in comparison to a traditional binary system.

  4. Articles

    1. Top of page
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    3. Highlight
    4. Rapid Communication
    5. Articles
    6. Notes
    1. Self-crosslinking borate anions for the production of tough UV-cured polyelectrolyte surfaces (pages 499–508)

      Bradley M. Berven, Richard O. Oviasuyi, Robert J. Klassen, Mike Idacavage, Elizabeth R. Gillies and Paul J. Ragogna

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26388

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      Tough polyelectrolyte coatings have been produced in a single step by UV-curing novel phosphonium-borate monomers. The new tetrakis(styryl)borate anion enables high crosslink density upon rapid photopolymerization. The full series of borates NaBPhxSty4− x, x = 0−3, have also been prepared and incorporated into the phosphonium borate salt monomers. As the number of styrene groups in the monomer increases, the polymer films become more mechanically resilient. Analysis by nanoindentation showed an increase in the film hardness while scratch tests showed an increased scratch resistance of the polyelectrolyte surface.

    2. A facile one-pot reactive solution blending approach for main-chain donor–acceptor polymeric materials (pages 509–524)

      S. Kumari Nisha and S. K. Asha

      Article first published online: 31 OCT 2012 | DOI: 10.1002/pola.26412

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      A high-temperature reactive solution blending approach was successfully used to covalently incorporate fluorescent chromophores such as perylenebisimide (PBI) oligo(p-phenylene vinylene) (OPV) into the backbone of an engineering thermoplastic polyester [poly(1,4-cyclohexylenedimethylene-1,4-cyclohexanedicarboxylate)] (PCCD). The chemical incorporation of these chromophores into PCCD was confirmed by carrying out the melt condensation using 1,4-cyclohexanedimethanol and 1,4-dimethylcyclohexane dicarboxylate with varying mole ratios of terminal hydroxyl-functionalized PBI and OPV derivatives. The advantages of this solution blending approach over melt condensation were its ease of synthesis and high incorporation of the desired chromophore (>30 mol % of PBI) with thin film processability.

    3. Non-isocyanate synthesis and application of telechelic polyurethanes via polycondensation of diurethanes obtained from ethylene carbonate and diamines (pages 525–533)

      Bungo Ochiai and Tomohisa Utsuno

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26418

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      Aliphatic polyurethanes could be obtained in high yields via a non-isocyanate method based on the self-polycondensation of dihydroxyurethanes obtained by the reaction of diamines and ethylene carbonate. Two-step polycondensation, consisting of the polycondensation under a N2 atmosphere followed by that under reduced pressure, was effective. The resulting polyurethane having hydroxyl groups at both of the end groups was converted to polyurethane methacrylate that served as a crosslinker for radical polymerization of methyl acrylate.

    4. Emulsion polymerization of vinyl acetate using iodine-transfer and RAFT radical polymerizations (pages 534–545)

      Naoki Nomura, Keiji Shinoda, Akinori Takasu, Kenji Nagata and Katsuhiro Inomata

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26424

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      This study deals with control of the molecular weight of polyvinyl acetate (PVAc) emulsion by iodine-transfer radical polymerization and RAFT polymerization. Emulsion polymerization using ethyl iodoacetate more closely approximates the theoretical molecular weights than does the free radical polymerization. On the other hand, RAFT polymerizations reveal that the dithiocarbamate controls the polymer molecular weight more than xanthate under the same condition. Seed-emulsion polymerization is also performed using the chiral polyester seed to fabricate emulsions with core-shell structures.

    5. Cationic polymerization of isobutyl vinyl ether coinitiated with heteropolyacid or its salts in aqueous medium (pages 546–556)

      Qiang Huang, Yixian Wu and Jie Dan

      Article first published online: 8 NOV 2012 | DOI: 10.1002/pola.26431

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      Suspension cationic polymerization of IBVE coinitiated by AlPW12O40 in aqueous medium could be achieved to synthesize poly(IBVE) with m diad of around 60% in the presence of a sufficient amount of HCl. The cationic polymerization of IBVE in aqueous medium in the presence of HCl proceeded extremely rapidly even at very low concentration of AlPW12O40. All the poly(IBVE) growing chains were terminated by H2O and further transferred to aldehyde and alkenal terminal groups.

    6. Influence of fluorinated substituent and terminal length on phase behavior of mesogen-jacketed liquid crystalline polymers with a biphenyl mesogen (pages 557–564)

      Guoliang Jiang, Huanhuan Cai, Zhihao Shen, Xinghe Fan and Qifeng Zhou

      Article first published online: 15 NOV 2012 | DOI: 10.1002/pola.26436

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      Two series of mesogen-jacketed liquid crystalline polymers, PF3Cm and PC4Cm, were synthesized. Wide-angle X-ray diffraction measurements show that the mesophase structures of these polymers are dependent on the number of the carbon atoms in the fluorocarbon substituent and the property of the other terminal substituent. Polymers with fluorocarbon substituents enter into columnar nematic phases when m ≥ 4, whereas the polymer PF3C1 exhibits no liquid crystallinity. For polymers with butyl substituents, columnar nematic phases form when the number of carbon atoms at both ends of the side chain is not equal at high temperatures and disappear after the polymers are cooled to ambient temperature. However, when the polymer has the same number of carbon atoms at both ends of the side chain, a hexagonal columnar phase develops, and this phase remains after the polymer is cooled.

    7. Donor–acceptor-integrated conjugated polymers based on carbazole[3,4-c:5,6-c]bis[1,2,5]thiadiazole with tight π–π stacking for photovoltaics (pages 565–574)

      Daijun Zha, Lie Chen, Feiyan Wu, Hongming Wang and Yiwang Chen

      Article first published online: 27 NOV 2012 | DOI: 10.1002/pola.26438

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      An original strategy to construct a new donor–acceptor-integrated structure has been developed. Extremely short π–π stacking distance of 0.32 nm has been achieved for PCBTT in solid states. A broadened light harvesting of the resulting copolymer coversthe solar flux from 300 to 750 nm with a low-lying HOMO energy level of −5.30eV.

    8. Solution-processable colorless polyimides derived from hydrogenated pyromellitic dianhydride with controlled steric structure (pages 575–592)

      Masatoshi Hasegawa, Daiki Hirano, Mari Fujii, Misako Haga, Eiichiro Takezawa, Shinya Yamaguchi, Atsushi Ishikawa and Takashi Kagayama

      Article first published online: 31 OCT 2012 | DOI: 10.1002/pola.26407

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      This work presents novel polyimides (PIs) derived from 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride (H″-PMDA). In particular, the PI system derived from H″-PMDA and 4,4′-oxydianiline simultaneously achieved excellent optical transparency, a very high Tg exceeding 300 °C, high toughness (elongation at break > 70%), and good solution processability as plotted within the target area in this figure. The results suggest that the H″-PMDA-based PI systems can be promising candidates for novel high-temperature plastic substrate materials in electronic paper displays.

    9. Propylene polymerization by C1-symmetric {ONNO′}-type salan zirconium complexes (pages 593–600)

      Ad Cohen, Geoffrey W. Coates and Moshe Kol

      Article first published online: 29 OCT 2012 | DOI: 10.1002/pola.26408

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      The polymerization of propylene by C1-symmetric dibenzyl zirconium complexes of nonsymmetric Salan ligands that feature a halo-substituted phenolate ring and a bulky alkyl-substituted phenolate ring is described for the first time. Polypropylene of average isotacticity and enantiomorphic site control signature typical of C2-symmetric catalysts imply a facile polymeryl site epimerization and propylene insertion from both directions. The Mw of the polymers was low and depended on the size of the halo groups.

    10. New polymer matrix system for phosphorescent organic light-emitting diodes and the role of the small molecular co-host (pages 601–613)

      Beatrice Ch. D. Salert, Hartmut Krueger, Sergey A. Bagnich, Thomas Unger, Frank Jaiser, Mahmoud Al-Sa'di, Dieter Neher, Anna Hayer and Thomas Eberle

      Article first published online: 31 OCT 2012 | DOI: 10.1002/pola.26409

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      A new matrix system for phosphorescent OLEDs based on an electron transporting component attached to an inert polymer backbone, an electronically neutral co-host, and a phosphorescent dye that serves as both emitter and hole conductor are presented. The inert co-host is used either as small molecules or covalently connected to the same chain as the electron-transporting host. It is found that to get highest device performance the co-host must present in the matrix in small molecular phase.

    11. (Co)polymers of oligo(ethylene glycol) methacrylates—temperature-induced aggregation in aqueous solution (pages 614–623)

      Barbara Trzebicka, Dawid Szweda, Stanislav Rangelov, Agnieszka Kowalczuk, Barbara Mendrek, Alicja Utrata-Wesołek and Andrzej Dworak

      Article first published online: 1 NOV 2012 | DOI: 10.1002/pola.26410

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      The aggregation of a series of linear oligo(ethylene glycol) methacrylate (co)polymers with low molar mass dispersities and well-defined structure was followed in aqueous solutions using light scattering and turbidimetry. The influence of the molar mass, copolymer composition, length of the oligo(ethylene glycol) side chain, concentration of aqueous solution, and heating rate onto the mesoglobule sizes was investigated.

    12. A novel planar D-A alternating copolymer with D-A integrated structures exhibiting H-aggregate behaviors for polymer solar cells (pages 624–634)

      Shujiao Cai, Lie Chen, Daijun Zha and Yiwang Chen

      Article first published online: 31 OCT 2012 | DOI: 10.1002/pola.26411

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      A novel copolymer PCBTBDT with architecture D-A integrated structure is developed. The planar D-A integrated structure favors the strong intermolecular interaction. The typical H-aggregation is beneficial for charge transportation and collection. The copolymer has a low-lying HOMO energy level of −5.41 eV and a broadened absorption. Without any treatment, the PCBTBDT exhibits efficiency of 2% and a relatively high Voc value of 0.77 V.

    13. Depth characterization by confocal raman microscopy of oxygen inhibition in free radical photopolymerization of acrylates: Contribution of the thiol chemistry (pages 635–643)

      François Courtecuisse, Javier Cerezo, Céline Croutxé-Barghorn, Céline Dietlin and Xavier Allonas

      Article first published online: 31 OCT 2012 | DOI: 10.1002/pola.26413

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      An illustration by confocal Raman microscopy of the oxygen-affected layer in a photopolymer cured under air and with visible light is provided. Addition of thiol decreases the OAL and increases the conversion at the surface.

    14. Spotlight Article

      Rapid, metal-free room temperature vulcanization produces silicone elastomers (pages 644–652)

      Amanda S. Fawcett, John B. Grande and Michael A. Brook

      Article first published online: 31 OCT 2012 | DOI: 10.1002/pola.26414

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      Silicone elastomers are rapidly formed at room temperature using B(C6F5)3 as a catalyst that ligates H-terminated silicone chains with alkoxysilane crosslinkers. The metal free process is extremely rapid: normally the process is slowed down by the addition of small amounts of solvent, which also facilitates the formation of bubble-free transparent elastomers.

    15. Synthetic control of cage/network ratio of poly(methylsilsesquioxane)s for storage stability, hardness, and weather resistance of coating films (pages 653–663)

      Satoshi Urano, Rie Tomita and Kiyoharu Tadanaga

      Article first published online: 29 OCT 2012 | DOI: 10.1002/pola.26415

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      The cage/network ratio of PMSQ, having both cage structure and network structure monitored using 29Si NMR and GPC, can be controlled by altering the condensation reaction conditions. Results demonstrate that PMSQ must be designed with a larger cage/network ratio to produce good storage stability and a coating film that has good weather resistance. Additionally, PMSQ must be designed with a smaller cage/network ratio to produce a coating film having high hardness.

    16. Iron-mediated AGET ATRP of MMA with sulfosalicylic acid as a ligand (pages 664–671)

      Zhijun Deng, Jiangna Guo, Lihua Qiu, Chao Yuan, Yinxia Zhou and Feng Yan

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26417

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      The iron (III)-mediated AGET ATRP of MMA using sulfosalicylic acid (SSA) as the ligand was successfully developed. Addition of SSA as the ligand could enhance the polymerization rate and produce PMMA with controllable molecular weights and narrow molecular weight distributions (Mw/Mn = 1.30–1.50). The polymerizations showed characteristics of “living”/controlled free-radical polymerization.

    17. Alternating, gradient, block, and block–gradient copolymers of ethylene and norbornene by Pd–Diimine-Catalyzed “living” copolymerization (pages 672–686)

      Peng Xiang and Zhibin Ye

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26419

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      A novel range of ethylene–norbornene copolymers having various composition distributions, including alternating, gradient, block, and block–gradient, have been synthesized by copolymerization with a “living” Pd–diimine catalyst. The tuning of the composition distribution is achieved conveniently by controlling norbornene feed concentration and/or using two- or three-stage polymerization with sequential norbornene feeding.

    18. Acceleration of the imine base/isocyanate (IBI)-mediated polymerization of MMA caused by ionic liquid traces (pages 687–695)

      Ingmar Polenz, Friedrich Georg Schmidt and Stefan Spange

      Article first published online: 6 NOV 2012 | DOI: 10.1002/pola.26422

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      Traces of ionic liquids (ILs) accelerate the novel imine base/isocyanate (IBI)-mediated radical polymerization of methyl methacrylate (MMA). Both the brutto polymerization rate constant kBr,0 and the activation temperature of IBI mixtures are influenced. Herein, results are reported on the polymerization kinetics of several IBI combinations in the presence of selected ILs whereas a comparison with non-IL containing initiator mixtures is given. The interaction strength of the IL with each IBI component and MMA was determined by means of ATR FT MIR spectroscopy.

    19. Ring-opening polymerization of lactides catalyzed by magnesium complexes coordinated with NNO-tridentate pyrazolonate ligands (pages 696–707)

      Hui-Ju Chuang, Hsiao-Li Chen, Jian-Li Ye, Zn-Yun Chen, Pei-Ling Huang, Tzu-Ting Liao, Tsung-En Tsai and Chu-Chieh Lin

      Article first published online: 8 NOV 2012 | DOI: 10.1002/pola.26426

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      A series of magnesium complexes have been synthesized and their activities toward ROP of lactides were investigated. Kinetic studies and factors affected their activities are also presented.

    20. Facile synthesis of dendrimers combining aza-Michael addition with Thiol-yne click chemistry (pages 708–715)

      Yong Shen, Yinan Ma and Zhibo Li

      Article first published online: 15 NOV 2012 | DOI: 10.1002/pola.26429

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      Dendrimers are a unique class of synthetic macromolecules with highly branched and globular architecture with promising biomedical applications. A highly efficient strategy was developed to make a fifth generation dendrimer within five steps using a combination of aza-Michael addition and Thiol-yne click reactions. All reactions are conducted under benign conditions in the absence of metal catalyst.

    21. Emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP): Effect of monomer hydrophilicity (pages 716–723)

      Yukiya Kitayama, Kazuya Kishida and Masayoshi Okubo

      Article first published online: 15 NOV 2012 | DOI: 10.1002/pola.26430

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      The effect of monomer hydrophilicity was investigated in emulsifier-free, organotellurium-mediated living radical polymerization (emulsion TERP) using methyl methacrylate and butyl methacrylate. When hydrophilic monomer was used, MWD control was good only at an efficient and inefficient stirring rates. However, when hydrophobic monomer was used, good MWD control was obtained only at an efficient stirring rate. These results suggest that monomer transportation from droplets to polymerizing particles via aqueous medium is important for good MWD control.

    22. Synthesis and microstructural study of stereoblock elastomeric polypropylenes from metallocene catalyst (2-PhInd)2ZrCl2 activated with cocatalyst mixtures (pages 724–731)

      Gholam-Reza Nejabat, Mehdi Nekoomanesh, Hassan Arabi, Hamid Salehi-Mobarakeh, Gholam-Hossein Zohuri, Mojtaba Omidvar and Stephen A. Miller

      Article first published online: 15 NOV 2012 | DOI: 10.1002/pola.26432

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      Various elastomeric polypropylenes (PPs) are synthesized with metallocene catalyst (2-PhInd)2ZrCl2 in the presence of different cocatalyst mixtures. The catalyst stereoselectivity is sensitive to the nature and amount of included trialkylaluminum. Stereochemical microstructure, molecular weight, melting temperature, glass transition temperature, heat of melt, and elastic damping ability are all polymer properties that can be tuned by controlling the cocatalyst formula. For example, the PP tacticity can be switched from purely atactic to isotactic/atactic stereoblock by the addition of triisobutylaluminum.

    23. Chiral and water-soluble poly(2-oxazoline)s (pages 732–738)

      Robert Luxenhofer, Stephan Huber, Julia Hytry, Jing Tong, Alexander V. Kabanov and Rainer Jordan

      Article first published online: 27 NOV 2012 | DOI: 10.1002/pola.26437

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      In this article, the synthesis and characterization of the first water-soluble and chiral poly(2,4-disubstituted-2-oxazoline)s is described.

  5. Notes

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Articles
    6. Notes
    1. Spotlight Article

      Helical folding of poly(naphthalenecarboxamide) in apolar solvent (pages 739–742)

      Koichiro Mikami and Tsutomu Yokozawa

      Article first published online: 27 NOV 2012 | DOI: 10.1002/pola.26420

      Thumbnail image of graphical abstract

      Helical folding of poly(naphthalenecarboxamide)s with aliphatic side chains in hydrophobic solvents is investigated. The CD spectra of the polyamide showed a predominant left-handed helical structure in chloroform, THF, and cyclohexane. Furthermore, the sergeants and soldiers experiment in cyclohexane showed a clear chiral amplification. These results indicate that the helical structure was stabilized by an intramolecualr self-association based on the solvophobic effect, and that there is cooperativity between the monomer units constituting the helical structure.

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