Sequence-regulated vinyl copolymers with acid and base monomer units <i>via</i> atom transfer radical addition and alternating radical copolymerization

Soejima, Takamasa; Satoh, Kotaro; Kamigaito, Masami

doi:10.1039/c6py00965d

Cited by 32 publications

(12 citation statements)

References 59 publications

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“…Precise control of a monomer sequence in synthetic polymers is an attractive goal in polymer science because monomer sequence can affect polymer properties and may impart special functions as is seen for highly sequence‐regulated natural polymers, such as proteins. Though progress has been made in the development of sequence‐controlled synthetic polymers using various approaches, mainly based on iterative methods, monomer sequence control is quite challenging, especially for vinyl copolymers in terms of single monomer unit over the long polymer chains …”

Section: Methodsmentioning

confidence: 99%

BAB‐random‐C Monomer Sequence via Radical Terpolymerization of Limonene (A), Maleimide (B), and Methacrylate (C): Terpene Polymers with Randomly Distributed Periodic Sequences

2017

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An aturally abundant terpene,l imonene (A), was radically polymerized with am aleimide derivative (B) and methacrylate (C) in af luorinated alcohol to give terpolymers with unprecedented BAB-random-C sequences in whicht he BABm onomer sequence was randomly copolymerized with aC unit. In eachb inary system, limonene was hardly copolymerized with methacrylate while it was efficiently copolymerized with maleimide to result in a1 :2-alternating BABp eriodic sequence,i np art due to the penultimate effects and hydrogen-bonding interactions with fluoroalcohol. Methacrylate and maleimide were randomly copolymerized to give copolymers rich in methacrylate units with minimal amounts of maleimide-maleimide sequences.T heir terpolymerization resulted in aB AB-r-C sequence as ac onsequence of the selective BABp olymerization between limonene and maleimide,the random copolymerization between methacrylate and maleimide,a nd the lacko fc opolymerization between limonene and methacrylate.

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Section: Methodsmentioning

confidence: 99%

BAB‐random‐C Monomer Sequence via Radical Terpolymerization of Limonene (A), Maleimide (B), and Methacrylate (C): Terpene Polymers with Randomly Distributed Periodic Sequences

2017

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“…Alternating radical polymerization has been achieved with nearly perfect sequence control . Along these lines, we have recently introduced alternating nitroxide‐mediated polymerization (NMP) of 1,1,1,3,3,3‐hexafluoroisopropyl acrylate (HFIPA) 1 and (7‐octenyl)vinyl ether (OVE).…”

Section: Methodsmentioning

confidence: 99%

Orthogonal Click Postfunctionalization of Alternating Copolymers Prepared by Nitroxide‐Mediated Polymerization

Tesch

Kudruk

Letzel

et al. 2017

Chemistry A European J

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Nitroxide-mediated polymerization (NMP) was applied to prepare alternating copolymers using 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) 1 and ((6-trimethylsilyl)-hex-5-yn-1-yl)vinyl ether (THVE) 2 as monomers. The alternating sequence of the resulting poly(HFIPA-alt-THVE) 3 was proved by using tandem mass spectrometry (MS/MS) and further supported by H NMR spectroscopy. Alternating alkyne and activated ester moieties of copolymer 3 were further functionalized with organic azides and amines using sequential Cu-catalyzed azide-alkyne click (CuAAC) and amidation reactions, providing dually functionalized poly(acrylamide-alt-triazole) polymers 5. Water-soluble alternating poly(acrylic acid-alt-triazole) copolymers 9 were obtained by saponification of HFIP esters. H and F NMR spectroscopy, IR spectroscopy as well as gel permeation chromatography (GPC) were used to characterize the polymers before and after functionalization.

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“…34 Outlook. Other than the approaches described above, the sequence in polymer chains has been imposed by exploiting differences in reactivity between specific functional groups in polymer chains, as demonstrated by Kamigaito in polymerization of maleimide and styrene (or limonene) units, whereby the maleimide units were further functionalized with sequencedefined side chains, 35 or by Sawamoto, whose group demonstrated individual addition of bulky methacrylate units followed by their transesterification with different alcohols to obtain sequence-defined polymers. 36 A major step towards illumination-controlled oligomer sequence emergence has been hinted at by the Boyer group, who have shown that illumination can impose sequence control on the level of individual monomer units.…”

Section: 2mentioning

confidence: 99%

Exploring Strategies To Bias Sequence in Natural and Synthetic Oligomers and Polymers

2018

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Millions of years of biological evolution have driven the development of highly sophisticated molecular machinery found within living systems. These systems produce polymers such as proteins and nucleic acids with incredible fidelity and function. In nature, the precise molecular sequence is the factor that determines the function of these macromolecules. Given that the ability to precisely define sequence emerges naturally, the fact that biology achieves unprecedented control over the unit sequence of the monomers through evolved enzymatic catalysis is incredible. Indeed, the ability to engineer systems that allow polymer synthesis with precise sequence control is a feat that technology is yet to replicate in artificial synthetic systems. This is the case because, without access to evolutionary control for finely tuned biological catalysts, the inability to correct errors or harness multiple competing processes means that the prospects for digital control of polymerization have been firmly bootstrapped to biological systems or limited to stepwise synthetic protocols. In this Account, we give an overview of strategies that have been used over the last 5 years in efforts to program polymer synthesis with sequence control in the laboratory. We also briefly explore how the use of robotics, algorithms, and stochastic chemical processes might lead to new understanding, mechanisms, and strategies to achieve full digital control. The aim is to see whether it is possible to go beyond bootstrapping to biological polymers or stepwise chemical synthesis. We start by describing nonenzymatic techniques used to obtain sequence-controlled natural polymers, a field that lends itself to direct application of insights gleaned from biology. We discuss major advances, such as the use of rotaxane-based molecular machines and templated approaches, including the utilization of biological polymers as templates for purely synthetic chains. We then discuss synthetic polymer chemistry, whose array of techniques allows the production of polymers with enormous structural and functional diversity, but so far with only limited control over the unit sequence itself. Synthetic polymers can be subdivided into multiple classes depending on the nature of processes used to synthesize them, such as by addition or condensation. Consequently, varied approaches for sequence control have been demonstrated in the area, including but not limited to click reactions, iterative solid-phase chemistry, and exploiting the chemical affinity of the monomers themselves. In addition to those, we highlight the importance of environmental bias in possible control of polymerization at the single-unit level, such as using catalyst switching or external stimuli. Even the most successful experimental sequence control approach needs appropriate tools to verify its scope and validity; therefore, we devote part of the present Account to possible analytical approaches to sequence readout, starting with well-established tandem mass spectrometry techniques and touching on those...

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Sequence-regulated vinyl copolymers with acid and base monomer units via atom transfer radical addition and alternating radical copolymerization

Abstract: Sequence-regulated vinyl copolymers with acid and base monomer units were prepared via atom transfer radical addition and alternating radical copolymerization.

Cited by 32 publications

References 59 publications

BAB‐random‐C Monomer Sequence via Radical Terpolymerization of Limonene (A), Maleimide (B), and Methacrylate (C): Terpene Polymers with Randomly Distributed Periodic Sequences

BAB‐random‐C Monomer Sequence via Radical Terpolymerization of Limonene (A), Maleimide (B), and Methacrylate (C): Terpene Polymers with Randomly Distributed Periodic Sequences

Orthogonal Click Postfunctionalization of Alternating Copolymers Prepared by Nitroxide‐Mediated Polymerization

Exploring Strategies To Bias Sequence in Natural and Synthetic Oligomers and Polymers

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