A Versatile and Scalable Strategy to Discrete Oligomers

Lawrence, Jimmy; Lee, Sang‐Ho; Abdilla, Allison; Nothling, Mitchell D.; Ren, Jing; Knight, Abigail; Fleischmann, Carolin; Li, Youli; Abrams, Austin S.; Schmidt, Bernhard V. K. J.; Hawker, Michael C.; Connal, Luke A.; McGrath, Alaina J.; Clark, Paul G.; Gutekunst, Will R.; Hawker, Craig J.

doi:10.1021/jacs.6b03127

Cited by 124 publications

(144 citation statements)

References 45 publications

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“…[6][7][8] This allows the study of thermal and physical characteristics of oligomers with as table hydrocarbon backbone that are chemically identical to well-known disperse synthetic polymers. [6][7][8] This allows the study of thermal and physical characteristics of oligomers with as table hydrocarbon backbone that are chemically identical to well-known disperse synthetic polymers.…”

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confidence: 99%

Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

et al. 2019

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The separation of an oligo(methyl acrylate) distribution, obtained from reversible addition-fragmentation chain transfer (RAFT) polymerization, in ad iscrete (dispersity = 1) oligomeric library (degree of polymerization between 1a nd 22) is presented. The properties of this library in terms of diffusivity,g lass transition temperature,a nd viscosity are determined, filling as ignificant knowledge gap associated with these materials.T he obtained oligomer library is used to construct artificial oligomer distributions on demand. These artificial oligomer distributions are used to highlight the potential to tailor physical properties of am aterial, while concomitantly demonstrating the limitations associated with size-exclusion chromatography analysis of molecular weight and dispersity in particular.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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confidence: 99%

Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

et al. 2019

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“…The total AE value from all raw materials to the libraries of the discrete oligomers was 63.2 % (Supporting Information, Table S2 and Equation S1). The high AE values indicated the high productivity of the radical polymerization and scalable separation processes . Conversely, the AE values of the di‐block oligomers were around 1.2 to 5.9 %, which are not very high.…”

Section: Methodsmentioning

confidence: 95%

“…Lawrence, Hawker, et al. reported a versatile and scalable method to isolate discrete oligomers prepared via RAFT polymerization and ATRP, using automated flash chromatography . They further revealed that the physical, optical, and electronic properties of discrete oligomers differed greatly, and depended on the degree of polymerization (DP) .…”

Section: Methodsmentioning

confidence: 99%

“…CPDOTT contains hydroxyl groups in its end group, which allow it to avoid hydrophobic and/or electrostatic interactions with melittin. Oligomers that contain hydroxyl groups on their end group also enabled the isolation of discrete oligomers that contained hydrophobic groups on their side chains, by low‐pressure reverse‐phase chromatography . Furthermore, the leaving cyanoisopropyl radical from CPDOTT in the first chain‐transfer reaction was designed to have the same structure as the initiator radical derived from azobisisobutyronitrile (AIBN) to avoid the formation of oligomers with non‐uniform end groups.…”

Section: Methodsmentioning

confidence: 99%

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Homogeneous Oligomeric Ligands Prepared via Radical Polymerization that Recognize and Neutralize a Target Peptide

et al. 2019

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Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences.

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“…The controlled synthesis of polymers is a subject of ever increasing importance, focusing on the discovery of general and reliable techniques for obtaining polymers with target sequences and molecular weight ranges with low dispersity. One of the techniques available for achieving these uniform (or monodisperse) materials is the stringent purification of low dispersity polymer samples from controlled polymerization processes, such as described by Lawrence et al1,2 This “top‐down” approach is complemented by iterative coupling (IC), a “bottom‐up” process where a planned sequence of reactions and purifications can result in a single product with precisely known structure 3…”

Section: Introductionmentioning

confidence: 99%

Theoretical Aspects of Iterative Coupling for Linear Oligomers and Polymers

Neto

Jones

Wong

2020

Macro Theory & Simulations

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A conceptual study of iterative coupling (IC) is performed, providing a unified description and new research directions. IC chain growth rates and functional group choice are analyzed, guiding construction of efficient schemes. The concept of cycle efficiency is defined as a more complete metric of experimental implementations of IC, and then applied to the main linear and exponential IC processes. The mathematical relations between individual reactions, cycles, and the iterative process as a whole are studied. Finally, macromolecule IC is proposed as a strikingly complementary process to standard IC, with potential to reduce the dispersity of non‐uniform samples. Due to its connection with the central limit theorem of statistics, it provides an unusually robust, powerful, and general method for scalable production of polymer samples with narrow distribution. In all, this contribution assists development of improved IC processes targeting low dispersity linear oligomers and polymers.

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A Versatile and Scalable Strategy to Discrete Oligomers

Cited by 124 publications

References 45 publications

Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

Homogeneous Oligomeric Ligands Prepared via Radical Polymerization that Recognize and Neutralize a Target Peptide

Theoretical Aspects of Iterative Coupling for Linear Oligomers and Polymers

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