Liquid Chromatography of Theta-Shaped and Three-Armed Star Poly(tetrahydrofuran)s: Theory and Experimental Evidence of Topological Separation

Vakhrushev, Andrey V.; Горбунов, А.А.; Tezuka, Yasuyuki; Tsuchitani, Akiko; Oike, Hideaki

doi:10.1021/ac801229f

Cited by 27 publications

(27 citation statements)

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“…These polymeric topological isomers, as well as a pair of linear and ring polymers, were separated by reversed phase chromatography under critical and near-critical interaction conditions. [18][19][20][21][22] The chemical assignment of the polymeric topological isomers with either y or manacle construction has subsequently been performed by using polymers containing a cleavable olefinic group in a backbone segment (Scheme 3a). 23 Thus, a pair of y-and manacle-shaped polymeric isomers with a metathesis-cleavable olefinic unit at the specified position were synthesized by the ESA-CF process by using a linear precursor with an inner olefinic group at the center position.…”

Section: Geometrical Classification and Isomeric Properties Of Cyclicmentioning

confidence: 99%

Topological polymer chemistry for designing multicyclic macromolecular architectures

Tezuka

2012

Polym J

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The geometrical conception and current synthetic challenges of topological polymer chemistry have been reviewed. On the basis of the systematic classification and isomeric properties of polymer chain topologies, a variety of novel multicyclic macromolecular constructions have now been rationally designed and subsequently realized by intriguing synthetic protocols. In particular, cyclic and multicyclic polymer products are effectively produced by an electrostatic polymer self-assembly of telechelic precursors that contain cyclic ammonium salt groups accompanying polyfunctional carboxylate counteranions and the subsequent covalent conversion through the ring-opening or through the ring-emitting reaction of the cyclic ammonium salt groups by carboxylate counteranions (Electrostatic Self-assembly and Covalent Fixation (ESA-CF) process). Furthermore, the ESA-CF process, in conjunction with effective linking/cleaving chemistry (including the metathesis condensation (clip) and alkyne-azide addition (click) reactions), has been demonstrated as a new synthetic protocol for unprecedented multicyclic macromolecular topologies.

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Section: Geometrical Classification and Isomeric Properties Of Cyclicmentioning

confidence: 99%

Topological polymer chemistry for designing multicyclic macromolecular architectures

Tezuka

2012

Polym J

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“…13 A theoretical study has shown the basis of the separation of topologically distinctive polymers by means of size-exclusion chromatography (SEC), liquid adsorption chromatography, and liquid chromatography at the critical condition. 20 In particular, the separation of q-shaped polymers from their three-armed star analogues has been discussed in detail (Figure 1). 20 The simulation chromatogram has first been produced for model mixtures of q-and star-polymers, and subsequently been compared with the experimental results on star-and q-shaped poly(THF)s in RPC.…”

Section: Polymeric Topological Isomers: Concept Synthesis and Separamentioning

confidence: 99%

“…20 In particular, the separation of q-shaped polymers from their three-armed star analogues has been discussed in detail (Figure 1). 20 The simulation chromatogram has first been produced for model mixtures of q-and star-polymers, and subsequently been compared with the experimental results on star-and q-shaped poly(THF)s in RPC. A good qualitative agreement between theory and experiment has been observed (Figure 1).…”

Section: Polymeric Topological Isomers: Concept Synthesis and Separamentioning

confidence: 99%

“…20 In particular, the separation of q-shaped polymers from their three-armed star analogues has been discussed in detail (Figure 1). 20 The simulation chromatogram has first been produced for model mixtures of q-and star-polymers, and subsequently been compared with 1139 Vol.67 No.11 2009 51 Scheme 6. Cyclic polymer topologies constructed by electrostatic self-assembly and covalent fixation.…”

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Topological Polymer Chemistry in Pursuit of Elusive Polymer Ring Constructions

Adachi

Tezuka

2009

J. Synth. Org. Chem. Jpn.

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Current challenges and future perspectives of topological polymer chemistry have been reviewed. A variety of novel cyclic and multicyclic macromolecular topologies has now been realized by intriguing synthetic protocols. In particular, the electrostatic polymer self-assembly of telechelic precursors having cyclic ammonium salt groups accompanying polyfunctional carboxylate counteranions has been exploited in dilution to produce topologically significant, non-covalent constructions of a dynamic nature. The subsequent covalent conversion through the ring-opening or through the ring-emitting reaction of cyclic ammonium salt groups by carboxylate counteranions provides cyclic and multicyclic polymer products effectively. Furthermore, the metathesis condensation process with functional cyclic polymer precursors has been demonstrated as a promising synthetic means to construct a variety of complex polymer topologies. Scheme 1. Single and multicyclic polymer topologies (ring family tree).tive properties in comparison with conventional linear or branched polyethylenes. 7a The "end-biting" chain transfer to eliminate the initiator species is a key to producing stable ring polymers. However, the chain transfer occurs concurrently during the propagation, and the chain length distribution (MWD) of the polymer products could not be controlled rigorously. By this ring-expansion process using a bulky, dendronized monomer, a ring-shaped nano-object has also been produced. 7e Ring poly(sulfide)s, free of the initiator fragment and having controlled size distributions have also been reported, in which the repetitive insertion of thiirane, a three-membered cyclic sulfide monomer into the thioester unit of a cyclic initiator proceeds with the concurrent chain transfer by intermolecular ester exchange reactions.7f More recently, ring polyesters with narrow size distributions have been obtained by a zwitterionic ring-opening polymerization of cyclic lactones and lactides with an N-heterocyclic carbene initiator (Scheme 2).7g-i In this process, the "end-biting" chain transfer is assumed to take place after the rapid propagation to eliminate the initiator species. Furthermore, ring-expansion polymerization has been combined with the end-linking reaction for the practical synthesis of ring polymers of high molar mass (Scheme 2). 10Thus, a cyclic initiator of stannous dialkoxide has been employed for the ring-opening polymerization of e-caprolactone. By taking advantage of the living nature of this process, a few units of a photo-crosslinkable, acrylate-functionalized e-caprolactone derivative have subsequently been introduced. Thereafter the intramolecular photo-crosslinking of acrylic groups has been conducted under dilution, and the stannous dialkoxide initiator fragment has finally been removed by hydrolysis, to produce ring polymers free of the initiator fragments.10a By this process, a twin-tail tadpole polymer comprised of a ring and two outward branch segments, has also been prepared by the re-initiation of ring-ope...

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“…[36], and by Gorbunov and Vakhrushev [37,38]. The theories are also available now for several types of complex macrocyclic structures, such as eightshaped and daisy-like macromolecules [39], and theta-shaped polymers [40].…”

Section: Introductionmentioning

confidence: 99%

Simulating chromatographic separation of topologically different polymers

Горбунов

Vakhrushev

2010

Procedia Chemistry

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Chromatography which is sensitive to the sizes of macromolecules and to their adsorption serves as an appropriate method to separate complex polymers. Unfortunately, the molar mass also influences the chromatographic retention, thus making quite difficult the problem of separation of polydisperse polymers by their topology. By using a theory of chromatographic behavior of macromolecules, we simulate chromatograms of polydisperse polymers that differ solely in their topology, and discuss possibilities to separate complex polymers (such as eight-, tadpole-, theta-, manacleshaped polymers, etc.) from their linear, branched, or macrocyclic precursors or topo-isomeric products. As follows from the simulations, two approaches towards the separation of polydisperse polymers by topology are especially promising. The first one is the chromatography at optimized (critical or near-critical) interaction conditions, where molar-mass effects are minimized; The second one consists in combing different chromatographic modes, which allows obtaining a separation by both molar mass and topology in a 2D chromatogram. Some of the simulated chromatographic separations are qualitatively very similar to the real ones, the others are the theoretical prediction.

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Liquid Chromatography of Theta-Shaped and Three-Armed Star Poly(tetrahydrofuran)s: Theory and Experimental Evidence of Topological Separation

Cited by 27 publications

References 76 publications

Topological polymer chemistry for designing multicyclic macromolecular architectures

Topological polymer chemistry for designing multicyclic macromolecular architectures

Topological Polymer Chemistry in Pursuit of Elusive Polymer Ring Constructions

Simulating chromatographic separation of topologically different polymers

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