Step-Growth Control in Template-Directed Polymerization

Li, Xiaoyü; Hernandez, Andres F.; Grover, Martha A.

doi:10.3987/com-10-s(e)99

Cited by 4 publications

(2 citation statements)

References 24 publications

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“…7 Alternatively, dynamic polymerizations involving short oligomers as the polymerizing unit (step growth) rather than monomers (chain growth) also have the potential to improve the fidelity of copying. 81…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In addition, it may be possible in such systems for the concentration of certain products to be enriched, such as by adsorption to an immobilized template to affinity purify the mixture . Alternatively, dynamic polymerizations involving short oligomers as the polymerizing unit (step growth) rather than monomers (chain growth) also have the potential to improve the fidelity of copying …”

Section: Resultsmentioning

confidence: 99%

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Templated Self-Assembly of Dynamic Peptide Nucleic Acids

et al. 2017

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Template-directed macromolecule synthesis is a hallmark of living systems. Inspired by this natural process, several fundamentally novel mechanisms for template-directed assembly of nucleic acid analogues have been developed. Although these approaches have broad significance, including potential applications in biotechnology and implications for the origins of life, there are unresolved challenges in how to characterize in detail the complex assembly equilibria associated with dynamic templated reactions. Here we describe mechanistic studies of template-directed dynamic assembly for thioester peptide nucleic acid (tPNA), an informational polymer that responds to selection pressures under enzyme-free conditions. To overcome some of the inherent challenges of mechanistic studies of dynamic oligomers, we designed, synthesized, and implemented tPNA-DNA conjugates. The DNA primer region affords a high level of control over the location and register of the tPNA backbone in relation to the template strand. We characterized the degree and kinetics of dynamic nucleobase mismatch correction at defined backbone positions. Furthermore, we report the fidelity of dynamic assembly in tPNA as a function of position along the peptide backbone. Finally, we present theoretical studies that explore the level of fidelity that can be expected for an oligomer having a given hybridization affinity in dynamic templated reactions and provide guidance for the future development of sequence self-editing polymers and materials. As our results demonstrate, the use of molecular conjugates of constitutionally static and dynamic polymers establishes a new methodology for expediting the characterization of the complex chemical equilibria that underlie the assembly of dynamic informational polymers.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Templated Self-Assembly of Dynamic Peptide Nucleic Acids

et al. 2017

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Novel encoding methods for DNA-templated chemical libraries

Zheng

Liu

et al. 2015

Current Opinion in Chemical Biology

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Molecular Biodynamers: Dynamic Covalent Analogues of Biopolymers

Liu

Lehn

Hirsch³

2017

Acc. Chem. Res.

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ConspectusConstitutional dynamic chemistry (CDC) features the use of reversible linkages at both molecular and supramolecular levels, including reversible covalent bonds (dynamic covalent chemistry, DCC) and noncovalent interactions (dynamic noncovalent chemistry, DNCC). Due to its inherent reversibility and stimuli-responsiveness, CDC has been widely utilized as a powerful tool for the screening of bioactive compounds, the exploitation of receptors or substrates driven by molecular recognition, and the fabrication of constitutionally dynamic materials. Implementation of CDC in biopolymer science leads to the generation of constitutionally dynamic analogues of biopolymers, biodynamers, at the molecular level (molecular biodynamers) through DCC or at the supramolecular level (supramolecular biodynamers) via DNCC. Therefore, biodynamers are prepared by reversible covalent polymerization or noncovalent polyassociation of biorelevant monomers.In particular, molecular biodynamers, biodynamers of the covalent type whose monomeric units are connected by reversible covalent bonds, are generated by reversible polymerization of bio-based monomers and can be seen as a combination of biopolymers with DCC. Owing to the reversible covalent bonds used in DCC, molecular biodynamers can undergo continuous and spontaneous constitutional modifications via incorporation/decorporation and exchange of biorelevant monomers in response to internal or external stimuli. As a result, they behave as adaptive materials with novel properties, such as self-healing, stimuli-responsiveness, and tunable mechanical and optical character. More specifically, molecular biodynamers combine the biorelevant characters (e.g., biocompatibility, biodegradability, biofunctionality) of bioactive monomers with the dynamic features of reversible covalent bonds (e.g., changeable, tunable, controllable, self-healing, and stimuli-responsive capacities), to realize synergistic properties in one system. In addition, molecular biodynamers are commonly produced in aqueous media under mild or even physiological conditions to suit their biorelated applications.In contrast to static biopolymers emphasizing structural stability and unity by using irreversible covalent bonds, molecular biodynamers are seeking relative structural adaptability and diversity through the formation of reversible covalent bonds. Based on these considerations, molecular biodynamers are capable of reorganizing their monomers, generating, identifying, and amplifying the fittest structures in response to environmental factors. Hence, molecular biodynamers have received considerable research attention over the past decades. Accordingly, the construction of molecular biodynamers through equilibrium polymerization of nucleobase-, carbohydrate- or amino-acid-based monomers can lead to the fabrication of dynamic analogues of nucleic acids (DyNAs), polysaccharides (glycodynamers), or proteins (dynamic proteoids), respectively. In this Account, we summarize recent advances in developing different types of...

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Step-Growth Control in Template-Directed Polymerization

Cited by 4 publications

References 24 publications

Templated Self-Assembly of Dynamic Peptide Nucleic Acids

Templated Self-Assembly of Dynamic Peptide Nucleic Acids

Novel encoding methods for DNA-templated chemical libraries

Molecular Biodynamers: Dynamic Covalent Analogues of Biopolymers

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