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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Polymers02:34

Polymers

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Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
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Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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Radicals01:27

Radicals

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Roots, often written as radicals, identify the quantity that must be raised to a specific exponent to produce a given value. A radical expression consists of two main components: the radicand, which is the value placed inside the root symbol, and the index, which indicates the degree of the root being taken. The notation n√a indicates the principal nth root of a. If n equals 2, the operation is the square root, while n = 3 defines the cube root. When n is even, a negative radicand does...
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Radical Equations01:26

Radical Equations

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Radical equations are mathematical expressions in which the variable is found within a radical, most commonly a square root or cube root. These equations frequently arise in science, engineering, and real-world measurements involving nonlinear relationships. To solve a radical equation, the standard procedure is to isolate the radical expression and then eliminate the radical by raising each side to a power equal to the index of the radical. This process may lead to extraneous...
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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
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Radical Approach to Thioester-Containing Polymers.

Ronald A Smith1, Guanyao Fu1, Owen McAteer1

  • 1School of Chemistry and Biochemistry , Georgia Institute of Technology , 901 Atlantic Drive NW , Atlanta , Georgia 30332 , United States.

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|January 15, 2019
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Researchers developed a novel thionolactone monomer for radical ring-opening polymerization, creating degradable thioester polymers. This breakthrough overcomes reactivity challenges, enabling versatile copolymer synthesis and well-defined macromolecular structures.

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Area of Science:

  • Polymer Chemistry
  • Organic Synthesis
  • Materials Science

Background:

  • Radical ring-opening polymerization (RROP) is a valuable technique for polymer synthesis.
  • Thiolactone monomers have presented reactivity challenges in RROP, limiting their incorporation.
  • Developing new monomers is crucial for expanding the scope and applications of RROP.

Purpose of the Study:

  • To introduce a novel thionolactone monomer for efficient RROP.
  • To synthesize polymers with thioester-containing backbones.
  • To demonstrate the degradability and versatility of the resulting polymers.

Main Methods:

  • Synthesis of a new thionolactone monomer.
  • Radical ring-opening polymerization using the thionolactone monomer.
  • Copolymerization with acrylate monomers.
  • Investigation of hydrolytic and cysteine-mediated degradation.
  • Compatibility studies with reversible addition-fragmentation chain transfer (RAFT) polymerization.

Main Results:

  • Complete ring-opening and quantitative monomer incorporation were achieved.
  • Thioester-containing polymers were successfully synthesized.
  • Copolymers exhibited facile degradation under hydrolytic conditions.
  • Cysteine-mediated degradation via transthioesterification was confirmed.
  • Block copolymers with well-defined structures were prepared using RAFT polymerization.

Conclusions:

  • The new thionolactone monomer provides an effective strategy for RROP.
  • The synthesized polymers possess tunable degradability.
  • This approach enables the creation of advanced macromolecular architectures.