Optically Active Helical Substituted Polyacetylenes Showing Reversible Helix Inversion in Emulsion and Solution State

Huang, Yingying; Zhang, Yuanyuan; Yang, Wantai; Deng, Jianping

doi:10.1002/marc.201100646

Cited by 16 publications

(9 citation statements)

References 44 publications

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“…Moreover, compared with the polymer emulsion ( λ max , 350nm), pronounced red shifts took place in the CD and UV‐Vis absorptions of polymer solution ( λ max , 390 nm). The red shifts resulted from the prolonged effective conjugation length in helical polymer chains in solution state, as ever observed and discussed in detail in our earlier studies . We further characterized the copolymers with different compositions in THF by CD technique, and the corresponding CD spectra are shown in Supporting Information Figure S3.…”

Section: Resultssupporting

confidence: 59%

Emulsion copolymerization of substituted acetylenes for constructing optically active helical polymer nanoparticles. Synergistic effects and helicity inversion

Zhao

Deng

Yang

2016

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

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Copolymerizations of substituted acetylenes have been intensively studied in solution polymerization for constructing chirally helical polymers, while emulsion copolymerizations of the kind of monomers have been only scarcely reported. In the present study, chiral substituted acetylene monomer containing cholic acid group underwent emulsion copolymerizations with an achiral acetylenic monomer in the presence of rhodium catalyst, providing optically active helical copolymer nanoparticles. Synergistic effects were found in the resulting helical copolymers, enabling one certain copolymer to show the maximum CD signal intensity. Moreover, the helicity of the helical copolymers in nanoparticle state was opposite to that in solution state. This is the first demonstration that synergistic effects and helicity inversion simultaneously occurred in helical copolymers prepared by emulsion copolymerization process. To deepen the understanding of the unique phenomena, corresponding solution copolymerization and emulsification process were also investigated. Different from "Sergeant and Soldiers rule" approach, the present study provides a new strategy for preparing chirally helical polymer particles by making full use of achiral monomers.

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Section: Resultssupporting

confidence: 59%

Emulsion copolymerization of substituted acetylenes for constructing optically active helical polymer nanoparticles. Synergistic effects and helicity inversion

Zhao

Deng

Yang

2016

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

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“…In the studies of Deng and coworkers, 86 the polymer particles of monomer 3(R or S) showed an opposite sign in CD effects when 60 compared to the corresponding polymers obtained by solution polymerization. Namely, "chirality" inversion occurred to the polymer particles.…”

Section: (3) Chirality Inversionmentioning

confidence: 94%

Particles of polyacetylene and its derivatives: preparation and applications

Huang

et al. 2014

Polym. Chem.

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How to prepare polymeric particles from acetylene and its derivatives, in particular in aqueous media, has remained as a challenging research topic for a rather long period. In recent years, this research area has achieved exciting progress and a variety of novel functional particles have been reported. However, there has not yet a review article exclusively summarizing the progress. This article presents an overview on the advanced particles with emphasis on the preparation and their applications. The state-of-the-art preparation methods fall into two major groups: emulsion, precipitation, suspension polymerization approaches by starting from monomers; and post-treatment of 10 pre-formed polymers (i.e. self-assembly). The polymer particles were investigated in such applications as circuits, sensors, drug release and chiral-related processes for instance asymmetric catalysis, enantioselective crystallization, enantioselective release, amongst many others. The review article is expected to stimulate more unprecedented functional particles derived from acetylene and its derivatives.

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“…However, this is not always true for all the polymer emulsions and PCPs. A pair of polymer emulsions (polymer 3 S and polymer 3 R , derived from M 3 S and M 3 R , respectively, in Figure ) exhibited CD signals in the opposite sign to that of the same polymer solution . It is well known that the CD signal of the polymer emulsion resulted from the predominant one‐handed macromolecular helicity of the polymer chains forming the nanoparticles .…”

Section: Particles Of Chiral Polymersmentioning

confidence: 97%

Optically Active Particles of Chiral Polymers

Song

Liu

et al. 2013

Macromol. Rapid Commun.

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Particles constructed by chiral polymers (defined as PCPs) have emerged as a rapidly expanding research field in recent years because of their potentially wide-ranging applications in asymmetric catalysis, enantioselective crystallization, enantioselective release, amongst many others. The particles show considerable optical activity, due to the chirality of the corresponding polymers from which the particles are derived. This review article presents an overview on PCPs with emphasis on our group's recent achievements in the preparation of PCPs derived from optically active helical polymers and their applications. PCPs can be prepared via emulsion polymerization, precipitation polymerization, and suspension polymerization by starting from monomers. Emulsification of preformed chiral polymers and self-assembly approaches also can lead to PCPs. Chiral polymer-based core/shell particles, hollow particles, and magnetic particles are also covered because of their remarkable properties and significant potential applications.

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Optically Active Helical Substituted Polyacetylenes Showing Reversible Helix Inversion in Emulsion and Solution State

Cited by 16 publications

References 44 publications

Emulsion copolymerization of substituted acetylenes for constructing optically active helical polymer nanoparticles. Synergistic effects and helicity inversion

Emulsion copolymerization of substituted acetylenes for constructing optically active helical polymer nanoparticles. Synergistic effects and helicity inversion

Particles of polyacetylene and its derivatives: preparation and applications

Optically Active Particles of Chiral Polymers

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