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Polymer Classification: Stereospecificity01:26

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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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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 mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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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.
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Chirality-controlled polymerization-induced self-assembly.

Haolan Li1, Erik Jan Cornel1, Zhen Fan1

  • 1Department of Polymeric Materials, School of Materials Science and Engineering, Tongji University 4800 Caoan Road Shanghai 201804 China 20310048@tongji.edu.cn jzdu@tongji.edu.cn.

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|December 21, 2022
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Summary
This summary is machine-generated.

Chiral monomer ratio controls nanoparticle properties in polymerization-induced self-assembly (PISA). This chirality-controlled PISA method offers tunable nanoparticles for biomedical uses, impacting morphology and degradation.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Biodegradable nanoparticles are efficiently prepared using N-carboxyanhydrides-induced self-assembly (NCA-PISA).
  • The influence of chiral monomer ratios on NCA-PISA formulations and nanoparticle characteristics remains underexplored.

Purpose of the Study:

  • To investigate the effect of chiral monomer ratios on the morphology, secondary structure, and biodegradation rate of PISA nanoparticles.
  • To establish a chirality-controlled PISA (CC-PISA) method for creating adjustable nanoparticles for biomedical applications.

Main Methods:

  • Ring-opening polymerization (ROP) of l- and d-phenylalanine N-carboxyanhydrides (Phe-NCA) using a PEG macro-initiator.
  • Preparation of homo- and hetero-chiral Phe-peptide block copolymers and their in situ self-assembly into nanoparticles.
  • Analysis of nanoparticle morphology, secondary structure (α-helix/β-sheet ratio), and enzymatic biodegradation rates.

Main Results:

  • Altering the chiral ratio of core-forming monomers controlled nanoparticle morphology, secondary structure, and biodegradation.
  • Homo-chiral formulations formed vesicles at high phenylalanine degrees of polymerization (DP).
  • Hetero-chiral formulations yielded larger nanoparticles with varied morphologies; an equal enantiomer ratio inhibited PISA, resulting in a polymer solution.

Conclusions:

  • The CC-PISA method enables tunable nanoparticle fabrication by controlling chiral monomer ratios.
  • Secondary peptide structure and π-π stacking influence polymer self-assembly.
  • This PISA approach is valuable for developing chiral nanoparticles for disease treatment.