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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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The Replisome03:01

The Replisome

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DNA replication is carried out by a large complex of proteins that act in a coordinated matter to achieve high-fidelity DNA replication. Together this complex is known as the DNA replication machinery or the replisome.
The synthesis of the leading and lagging strands is a highly coordinated process. To explain this, the “Trombone model” was proposed by Bruce Alberts in 1980. The DNA loop formation starts when a primer is synthesized on the parent lagging strand. The loop grows with...
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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Related Experiment Video

Updated: Aug 29, 2025

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
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Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly

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H-Bond Templated Oligomer Synthesis Using a Covalent Primer.

Diego Núñez-Villanueva1, Christopher A Hunter1

  • 1Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.

Journal of the American Chemical Society
|September 9, 2022
PubMed
Summary
This summary is machine-generated.

Researchers developed a new method for templated synthesis of triazole oligomers using a primer attached via a covalent ester base-pair. This method enables efficient replication cycles through hydrogen-bonding interactions and template regeneration.

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Area of Science:

  • Chemical Synthesis
  • Supramolecular Chemistry
  • Polymer Chemistry

Background:

  • Template-directed synthesis mimics biological nucleic acid replication.
  • Primer extension is a key step in polymerase chain reaction (PCR).
  • Developing efficient methods for synthesizing novel oligomers is crucial.

Purpose of the Study:

  • To implement primer attachment for templating triazole oligomer synthesis.
  • To investigate the role of hydrogen-bonding in template-directed reactions.
  • To demonstrate a complete replication cycle with template regeneration.

Main Methods:

  • Covalent ester base-pair formation to attach a primer to a template.
  • Utilizing phenol recognition units for noncovalent base-pairing with phosphine oxide monomers.
  • Employing competition reactions to assess template effects and binding affinities.
  • 31P NMR spectroscopy to confirm product structure and hydrogen-bonding.

Main Results:

  • Successful templated synthesis of triazole oligomers was achieved.
  • Hydrogen-bonding interactions between template phenols and phosphine oxide monomers significantly accelerated the reaction rate.
  • Higher affinity binding of phosphine oxide monomers led to greater rate acceleration.
  • 31P NMR confirmed the presence of H-bonds in the product duplex, indicating compatibility of covalent and noncovalent base-pairs.
  • A formal replication cycle was completed via hydrolysis of the ester base-pair.

Conclusions:

  • A novel method for template-directed synthesis of triazole oligomers was established.
  • Hydrogen-bonding plays a critical role in enhancing reaction rates and specificity.
  • The developed system demonstrates geometric compatibility between covalent and noncovalent base-pairing strategies.
  • This work provides a foundation for developing artificial replication systems.