It Is the Outside That Counts: Chemical and Physical Control of Dynamic Surfaces

Brosnan, Sarah M.; Brown, Andrew H.; Ashby, Valerie Sheares

doi:10.1021/ja308080g

Cited by 29 publications

(34 citation statements)

References 41 publications

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“…After click reaction (Figure 4b), the peak at 404.48 eV is reduced and the peak at 400.76 eV is shifted to 400.49 eV, which corresponds to the appearance of the triazole. This modification of the N1s, in good agreement with the literature, indicated the formation of the triazole [22][23][24].…”

Section: Xps Analysissupporting

confidence: 92%

Chemical Modification of Poly(Vinyl Alcohol) in Water

2015

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Partial chemical modification of poly(vinyl alcohol) (PVA) was performed through tosylation followed by azidation. Amine functional PVA was also prepared by grafting propargylamine using click chemistry reaction. Through this approach, a tosyl group (a good leaving group), azide group (a group used in click chemistry) and amine group (a group used for amidation) were attached to PVA polymer chains. The three chemical modifications were performed in water. FTIR and XPS analysis confirmed the chemical modification after each step. Thermogravimetric analysis (TGA) was used to study the thermal stability of the modified PVA.

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Section: Xps Analysissupporting

confidence: 92%

Chemical Modification of Poly(Vinyl Alcohol) in Water

2015

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“…Additionally by formulating a polymer based on a non-stoichiometeric ratio of alkyne to azide, residual azides or alkynes remain in the network and are available for any subsequent reactions, thus exploiting the self-limiting nature of the reaction in a similar approach to the one taken by Nair and coworkers[22]. Traditionally, azides and alkynes are used commonly to modify polymer backbones chemically because the reaction proceeds efficiently under dilute conditions[2, 31]. Thus, by implementing the CuAAC click reactions to build a SMP network, the material is also inherently amenable to subsequent chemical modification.…”

Section: Resultsmentioning

confidence: 99%

“…These smart materials have found a variety of applications including biomedical devices[1], functional surfaces[2], textiles[3], and aerospace structures. [4] The traditional thermally activated shape memory cycle in polymers requires heating the material above a transition temperature associated with the polymer network such as a glass transition (T g ) or melting temperature (T m ) followed by the deformation of the material into a temporary shape followed by cooling below the transition temperature to fix the temporary shape.…”

Section: Introductionmentioning

confidence: 99%

“…[20] The CuAAC reaction in particular has been used to chemically modify dynamic surfaces of a SMP by incorporating azide-containing monomers into the backbone that were then further functionalized with alkyne dyes. [2] CuAAC has also been used to chemically crosslink an otherwise linear polyphenol resin by functionalizing the resin with alkynes and reacting them with a bisphenol A based di-azide. [21] In this approach the crosslinked polymer could be used for shape memory because it now had a permanent network structure.…”

Section: Introductionmentioning

confidence: 99%

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Photo-mediated copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” reactions for forming polymer networks as shape memory materials

McBride

Gong

Nair

et al. 2014

Polymer

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The formation of polymer networks polymerized with the Copper (I) – catalyzed azide – alkyne cycloaddition (CuAAC) click reaction is described along with their accompanying utilization as shape memory polymers. Due to the click nature of the reaction and the synthetic accessibility of azide and alkyne functional-monomers, the polymer architecture was readily controlled through monomer design to manipulate crosslink density, ability for further functionalization, and the glass transition temperature (55 to 120°C). Free strain recovery is used to quantify the shape memory properties of a model CuAAC network resulting in excellent shape fixity and recovery of 99%. The step growth nature of this polymerization results in homogenous network formation with narrow glass transitions ranges having half widths of the transition close to 15°C for these materials resulting in shape recovery sharpness of 3.9 %/°C in a model system comparable to similarly crosslinked chain growth polymers. Utilization of the CuAAC reaction to form shape memory materials opens a range of possibilities and behaviors that are not readily achieved in other shape memory materials such as (meth) acrylates, thiolene, thiol-Michael, and poly(caprolactone) based shape memory materials.

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“…25 Brosnan et al, have designed a shape memory thermoset polymer consists of SMP and functionalizable polymer, in which the SMP act as actuator for topography control and the surface of the material was easily functionalized with a variety of alkynes, thus realizing a new way to control both of surface chemistry and its topography. 26 To the best of our knowledge, because of the different polarity between polymer Al coating compacting Remove…”

Section: Introductionmentioning

confidence: 99%

Facile hydrophobicity/hydrophilicity modification of SMP surface based on metal constrained cracking

et al. 2015

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This study demonstrates an easy way to change surface characteristics, the water contact angle on styrene based shape memory polymer (SMP) surface alters before and after cracking formation and recovery. The contact angle of water on the original SMP surface is about 85 degree, after coating with Al and then kneading from side face at glass transition temperature T g , cracking appeared both on Al film and SMP; cooling down and removing the Al film, cracks remain on SMP surface while the contact angle reduced to about 25 degree. When reheated above T g , the cracks disappeared, and the contact angle go back to about 85 degree. The thin Al film bonded on SMP surface was coated by spurting, that constrains the deformation of SMP. Heating above T g , there are complex interactions between soft SMP and hard metal film under kneading. The thin metal film cracked first with the considerable deformation of soft polymer, whereafter, the polymer was ripped by the metal cracks thus polymer cracked as well. Cracks on SMP can be fixed cooling down T g , while reheated, cracks shrinking and the SMP recovers to its original smooth surface. Surface topography changed dramatically while chemical composition showed no change during the deformation and recovery cycle, as presented by SEM and EDS. Furthermore, the wetting cycle is repeatable. This facile method can be easily extended to the hydropobicity/hydrophilicity modification of other stimuli-responsive polymers and put forward many potential applications, such as microfluidic switching and molecule capture and release.

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It Is the Outside That Counts: Chemical and Physical Control of Dynamic Surfaces

Cited by 29 publications

References 41 publications

Chemical Modification of Poly(Vinyl Alcohol) in Water

Chemical Modification of Poly(Vinyl Alcohol) in Water

Photo-mediated copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) “click” reactions for forming polymer networks as shape memory materials

Facile hydrophobicity/hydrophilicity modification of SMP surface based on metal constrained cracking

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