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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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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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Stimuli-activated drug delivery systems are designed to release drugs in response to specific physical, chemical, or biological stimuli. These systems often utilize hydrogels—three-dimensional, hydrophilic polymer networks capable of swelling in aqueous environments and retaining significant fluid volumes. Upon exposure to particular stimuli, these hydrogels undergo structural transitions that allow the embedded drug to be released. Due to this adaptive behavior, such systems are also called...
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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.
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Polymers

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 properties that they exhibit. Additionally,...

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Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties
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New stimuli-responsive polymers derived from morpholine and pyrrolidine.

Diego Velasco1, Carlos Elvira, Julio San Román

  • 1Department of Biomaterials, Institute of Polymer Science and Technology, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain.

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Researchers developed novel ionizable monomers and their polymers for smart hydrogels. These materials exhibit significant swelling changes with pH, showing promise for drug delivery and tissue engineering applications.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Biomedical Engineering

Background:

  • Development of advanced materials for biomedical applications like drug delivery and tissue engineering is crucial.
  • Ionizable polymers offer tunable properties, making them attractive for smart hydrogel systems.

Purpose of the Study:

  • To synthesize and characterize three new ionizable monomers: N-ethyl morpholine methacrylate (EMM), N-ethyl morpholine methacrylamide (EMA), and N-ethyl pyrrolidine methacrylamide (EPA).
  • To investigate the properties of their corresponding homopolymers and crosslinked networks, focusing on their potential as smart hydrogels.

Main Methods:

  • Radical polymerization in solution was used to prepare homopolymers (poly-EMM, poly-EMA, poly-EPA).
  • Characterization involved NMR, FTIR spectroscopy, Differential Scanning Calorimetry (DSC) for glass transition temperatures, and pKa determination.
  • Crosslinked samples were synthesized using N,N-methylene bisacrylamide (BAam) and 1,3,5-triacryloylhexa-hydro-1,3,5-triazine (135-T) as crosslinkers.
  • Swelling kinetics were studied in pH buffer solutions (2, 7.4, 10) at 37°C.

Main Results:

  • The synthesized monomers and polymers were successfully characterized.
  • Glass transition temperatures and pKa values were determined for the systems.
  • Crosslinked hydrogels exhibited significant and pH-dependent swelling, with hydration degrees ranging from approximately 200% to 2,600%.
  • Swelling behavior varied based on pH and the type of crosslinker used.

Conclusions:

  • The new ionizable monomers and their derived polymers form hydrogel systems with tunable swelling properties.
  • These smart hydrogels demonstrate significant potential for applications in controlled drug delivery and tissue engineering.
  • The pH-responsive nature of these hydrogels allows for tailored material design based on specific application requirements.