Helix Formation of Poly(phenylacetylene)s Bearing Azide Groups through Click Polymer Reaction with Optically Active Acetylenes

Itomi, Ken; Kobayashi, Shinzo; Morino, Kazuhide; Iida, Hiroki; Yashima, Eiji

doi:10.1295/polymj.pj2008213

Cited by 8 publications

(6 citation statements)

References 29 publications

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“…Polymer reactions have been widely used to modify material properties and have been applied also for some synthetic helical polymers. However, examples involving reactive helical polymers whose conformation is intact through side-chain reactions are limited. − In addition, almost quantitative side-chain modification of a synthetic helical polymer having pendent vinyl group has not been reported.…”

Section: Introductionmentioning

confidence: 99%

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A Reactive Helix: Synthesis, Chemical Modification, and Polymerization of an Optically Active Polymethacrylate

et al. 2010

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1-( p-Vinylphenyl)dibenzosuberyl methacrylate (VDBSMA) having two reactive vinyl groups in a molecule was synthesized and polymerized using R,R 0 -azobis(isobutyronitrile) as a radical initiator and using the complexes of 9-fluorenyllithium with (S)-(þ)-1-(2-pyrrolidinylmethyl)pyrrolidine, (-)-sparteine, and (S,S)-(þ)-2,3-dimethoxy-1,4-bis(dimethylamino)butane as optically active anionic initiators. The free radical polymerization led to an insoluble material, indicating that both methacrylic and styrenic moieties participated in the polymerization and a cross-linked gel was produced. In contrast, the anionic polymerization proceeded exclusively through the addition reaction of methacrylic moiety leaving the styrenic vinyl group intact leading to soluble polymers. The resulting poly(VDBSMA)s having a polymethacrylate-type main-chain structure were highly isotactic and showed high optical activity and intense circular dichroism (CD) spectra, indicating that the polymers have a single-handed helical conformation. Thus, a single-handed helical polymer having side-chain vinyl groups, which can be chemically modified, was successfully synthesized. The side-chain vinyl group was converted to 2-hydroxyethyl group, 1,2-dihydroxyethyl group, and carboxylic acid group by polymer reaction without seriously deteriorating the single-handed helical conformation of the polymer. In this way, single-handed helical polymers with side-chain protonic groups which would be difficult to be prepared by direct asymmetric anionic polymerization of the corresponding monomers were conveniently synthesized. In addition, radical polymerization of poly(VDBSMA) as a macromonomer afforded an optically active adduct consisting of single-handed helical chains.

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Section: Introductionmentioning

confidence: 99%

“…However, examples involving reactive helical polymers whose conformation is intact through side-chain reactions are limited. [9][10][11][12][13] In addition, almost quantitative side-chain modification of a synthetic helical polymer having pendent vinyl group has not been reported.…”

Section: Introductionmentioning

confidence: 99%

A Reactive Helix: Synthesis, Chemical Modification, and Polymerization of an Optically Active Polymethacrylate

et al. 2010

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“…Other amino acids like L-alanine, L-isoleucine, L-valine, L-phenylalanine, and L-glutamic acid have been introduced instead of L-aspartic acid in 39. 59 These polymers (40) show different CD signals and similar absorptions below 500 nm in THF solution. In the presence of F ¡ salt, they show CD signals of different magnitudes but similar shapes, and absorption maxima appear around 480 nm.…”

Section: Anion-responsive Pasmentioning

confidence: 99%

“…40 The resultant PPAs generate a preferred-handed helical structure caused by the covalently bonded chiral triazole moieties, and exhibit ICDs whose sign can be used to sense the chirality of the chiral acetylenes. An optically active, cis-transoidal PPA carrying L-proline pendant groups (25) exhibits intense CD signals in the UV-vis region of the polymer backbone in water, originating from the predominant one-handed helical structure based on the covalent-bonded chiral LChart 3.…”

Section: Chirality-responsive Pasmentioning

confidence: 99%

Stimuli-Responsive Polyacetylenes and Dendronized Poly(phenylacetylene)s

Masuda

Zhang

2016

Polymer Reviews

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Combination of stimuli responsiveness with p-conjugated polymers possesses probabilities not only to provide these polymers with unique interesting properties but also to promote new functions including various optoelectronic properties, catalysis, ionic sensing, and chiral recognition. In the former part of this review, recent developments of stimuli-responsive polyacetylenes are surveyed, which act as receptors towards external stimuli such as solvent, temperature, pH, chiral compounds, metal cations, various anions, electricity, light, etc., to transduce to other signals or energies, which leads to a wide range of intriguing properties to mimic biological processes or applications to smart or intelligent materials. In the latter part, we introduce dendronized poly(phenylacetylene)s (PPAs) exhibiting interesting thermoresponsive and chiroptical properties. Thermoresponsiveness of these dendronized conjugated polymers shows synchronous influence on their helical and hydrated conformations.

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“…Nevertheless, there are fairly limited reports on polymeric sensors incorporating the triazole moiety. Lately, Yashima and coworkers developed a facile method to prepare optically active helical poly(phenylacetylene)s via the click polymer reaction of optically inactive azide‐bound poly(phenylacetylene)s with chiral acetylenes. The resulting polymers formed a preferred‐handed helical conformation and exhibited characteristic induced circular dichroisms (CDs) whose Cotton effect (CE) signs can be used to sense the chirality of the chiral acetylenes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and selective recognition toward zinc ion of chiral poly(imine-triazole)

Zhou

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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A novel AB type of clickable monomer, (S)-2-[(2azido-1-phenylethylimino)methyl]-5-propargyloxyphenol (AMPP) was designed and polymerized to yield a class of main-chain chiral poly(imine-triazole)s through the metal-free click reaction. With the thermally induced polymerization, the desired polytriazoles can be easily prepared in high yields by a stepwise heating-up process and have the number-average molecular masses ranging from 5.1 3 10 3 to 58.1 3 10 3 (polydispersity indices 5 1.3821.68). The polymers were characterized by Fourier Transform Infrared spectroscopy (FTIR), 1 H Nuclear Magnetic Resonance (NMR), and gel permeation chromatography, and their optical properties were studied by fluorescence and circular dichroism (CD) spectroscopies. As a chemosensor, these polymers exhibited a selective "turn-on" fluorescence enhance-ment response toward Zn 21 ion over other cations such as Na 1 , K 1 , Mg 21 , Ca 21 , Ag 1 , Pb 21 , Cd 21 , Hg 21 , Mn 21 , and Ni 21 in dimethyl sulfoxide. However, the Zn 21 -induced fluorescence signal was subject to serious interference by Al 31 , Cu 21 , Cr 31 , and Fe 31 ions. Interestingly, the chiral polymer showed distinctive changes in the CD spectra on complexation with Zn 21 , which allowed for the discrimination of this ion in the presence of other species tested including those interfering ions observed in the fluorescent detection.

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Helix Formation of Poly(phenylacetylene)s Bearing Azide Groups through Click Polymer Reaction with Optically Active Acetylenes

Cited by 8 publications

References 29 publications

A Reactive Helix: Synthesis, Chemical Modification, and Polymerization of an Optically Active Polymethacrylate

A Reactive Helix: Synthesis, Chemical Modification, and Polymerization of an Optically Active Polymethacrylate

Stimuli-Responsive Polyacetylenes and Dendronized Poly(phenylacetylene)s

Synthesis and selective recognition toward zinc ion of chiral poly(imine-triazole)

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