Radical mediated thiol-ene/yne dispersion polymerizations

Alimohammadi, Farbod; Wang, Chen; Durham, Olivia Z.; Norton, Hannah R.; Bowman, Christopher N.; Shipp, Devon A.

doi:10.1016/j.polymer.2016.10.016

Cited by 18 publications

(17 citation statements)

References 34 publications

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“…Addition of a single thiol to a cycloalkyne is relatively rapid and this reaction can be performed spontaneously even in the absence of light and photoinitiator in an unpurged atmosphere. Cyclooctynes used for SPAAC (shown in Figure S1 in the Supporting Information) can be usable for doing click reaction with thiol as well …”

Section: Introductionmentioning

confidence: 99%

Site‐Specific Surface Functionalization via Microchannel Cantilever Spotting (µCS): Comparison between Azide–Alkyne and Thiol–Alkyne Click Chemistry Reactions

Dadfar

Sekula-Neuner

Bog

et al. 2018

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Different types of click chemistry reactions are proposed and used for the functionalization of surfaces and materials, and covalent attachment of organic molecules. In the present work, two different catalyst-free click approaches, namely azide-alkyne and thiol-alkyne click chemistry are studied and compared for the immobilization of microarrays of azide or thiol inks on functionalized glass surfaces. For this purpose, the surface of glass is first functionalized with dibenzocyclooctyne-acid (DBCO-acid), a cyclooctyne with a carboxyl group. Then, the DBCO-terminated surfaces are functionalized via microchannel cantilever spotting with different fluorescent and nonfluorescent azide and thiol inks. Although both routes work reliably for surface functionalization, the protein binding experiments reveal that using a thiol-alkyne route will obtain the highest surface density of molecular immobilization in such spotting approaches. The obtained achievements and results from this work can be used for design and manufacturing of microscale patterns suitable for biomedical and biological applications.

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Section: Introductionmentioning

confidence: 99%

Site‐Specific Surface Functionalization via Microchannel Cantilever Spotting (µCS): Comparison between Azide–Alkyne and Thiol–Alkyne Click Chemistry Reactions

Dadfar

Sekula-Neuner

Bog

et al. 2018

Small

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“…Previously, we and others developed radical‐mediated thiol‐ene and thiol‐yne polymerizations for the production of colloidal polymer particles . Synthesis of colloidal polymers have been shown to work in different dispersed polymerization modes, such as emulsions, dispersions, miniemulsions and suspensions . In these prior cases, the particles were emulsified or stabilized using common surfactants, such as sodium dodecyl sulfate (SDS), or natural gums .…”

Section: Introductionmentioning

confidence: 99%

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

Cassidy

Durham

Shipp

2019

Macro Reaction Engineering

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Pickering stabilization is a facile method to create composite colloidal particles. Inorganic colloidal SiO2 nanoparticles are often used as the stabilizer for particles instead of the more common amphiphilic surfactants. Here the use of this approach in radical‐mediated thiol‐ene suspension polymerizations using monomers 1,3,5‐triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TTT) and pentaerythritol tetrakis (3‐mercaptopropionate) (PETMP) is described. The resulting micron‐sized crosslinked poly(thioether) colloidal particles are coated with 80 nm silica nanoparticles. The addition of a small amount of various costabilizers is examined (hexadecane, cetyl alcohol and toluene), and while all yielded particles, cetyl alcohol provide more consistent results. Scanning electron microscopy and thermal analysis of the composite particles demonstrate morphologies that are consistent with a raspberry‐like structure. No significant changes to the glass transition temperature are observed, which is consistent with the silica nanoparticles being located at the surface of the polymer particles.

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“…Tyson et al reported thiol‐ene reactions initiated by visible light in presence of a transition metal polypyridyl photocatalyst and p ‐toluidine as an additive. Critically, thiol‐ene chemistry is widely used for a variety of applications such as the synthesis of crosslinked functional polymeric microspheres as well as the functionalization of microspheres . Dispersion polymerization based on thiol‐ene/thiol‐yne chemistry features some characteristics associated with the “click” principle, i.e., high reactivity with monomers, excellent yields, selectivity, and reaction orthogonality .…”

Section: Introductionmentioning

confidence: 99%

“…Recently, Bowman and co‐workers synthesized photoresponsive polymeric particles by photoinduced nitrile imine‐mediated tetrazole‐ene cycloaddition (NITEC) and thiol‐Michael addition dispersion polymerization in which the polymeric particles feature an inherent tetrazole‐ene functionality for postparticle formation chemistry. Alimohammadi et al synthesized polymeric particles by thiol‐ene and thiol‐yne free radical dispersion polymerization studying the effect of initiator (photo, thermal, and redox) on the particle size. Durham et al synthesized polymeric microspheres using thiol‐ene/thiol‐yne suspension polymerization in presence of thermal and photoinitiator, while Tan et al developed porous polymer particles using water born thiol‐ene suspension polymerization and studied the effect of polymerization conditions and porogen amounts on the morphology of particles and their sizes.…”

Section: Introductionmentioning

confidence: 99%

TEMPO Driven Mild and Modular Route to Functionalized Microparticles

Hafeez

Barner

Nebhani

2018

Macromol. Rapid Commun.

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The synthesis of crosslinked polymeric microspheres (3.8-15.0 µm) via (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) initiated thiol-ene dispersion polymerization under ambient conditions is reported for the first time. The initiating ability of TEMPO for the thiol-ene reaction is validated by electron paramagnetic resonance (EPR) and H nuclear magnetic resonance (NMR) spectroscopy on model reactions between 1-octadecanethiol and two electron deficient enes, n-butylacrylate and divinyl sulfone. Critically, the TEMPO resonance observed in the EPR spectra decreases with time when TEMPO is mixed with thiol and an electron deficient ene. The H NMR spectra demonstrate formation of up to 90% of thioether under ambient conditions. Based on these model reactions, a variety of crosslinked polymeric microspheres are synthesized with excellent morphological stability using poly(vinyl pyrrolidone) as surfactant. The ability of the microspheres for a second TEMPO initiated thiol-ene reaction is demonstrated by the ligation of fluorescein-5-maleimide (an ene) to the microspheres' surface containing excess of thiol functionality and by ligation of cysteine (containing a thiol group) to the microspheres' surface containing an excess of ene functionality. The synthesized polymeric microspheres are characterized using scanning electron microscopy, differential scanning calorimetry, Fourier-transform infrared spectroscopy, zeta potential, and X-ray photoelectron spectroscopy.

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Radical mediated thiol-ene/yne dispersion polymerizations

Cited by 18 publications

References 34 publications

Site‐Specific Surface Functionalization via Microchannel Cantilever Spotting (µCS): Comparison between Azide–Alkyne and Thiol–Alkyne Click Chemistry Reactions

Site‐Specific Surface Functionalization via Microchannel Cantilever Spotting (µCS): Comparison between Azide–Alkyne and Thiol–Alkyne Click Chemistry Reactions

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

TEMPO Driven Mild and Modular Route to Functionalized Microparticles

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