Photo-responsive thiol–ene networks for the design of switchable polymer patterns

Radl, Simone; Schipfer, Christian; Kaiser, Simon; Möser, Andreas; Kaynak, Baris; Kern, Wolfgang; Schlögl, Sandra

doi:10.1039/c7py00055c

Cited by 35 publications

(46 citation statements)

References 54 publications

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“…It was shown that the curing of the monomers with o ‐NBE groups proceeds either upon deep UV or visible light exposure without inducing a premature photoisomerization of the o ‐NBE links. By combining versatile o ‐NBE chemistry with the salient features of a photoinduced “click” reaction, photopolymers were synthetized by the visible‐light induced step‐growth reaction between multi‐functional thiols and an alkene‐terminated o ‐NBE monomer . The spatially controlled cleavage of the thiol‐ene networks enabled the fabrication of defined relief structures by mask illumination.…”

Section: Introductionmentioning

confidence: 99%

Dual‐Responsive Polydimethylsiloxane Networks

Giebler

Radl

Ast

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Exploiting the salient features of o‐nitrobenzyl chemistry, this work aims at the preparation of polydimethylsiloxane networks that undergo well‐defined bond cleavage in response to either UV light or different pH values as external trigger. Polydimethylsiloxane (PDMS) oligomers with terminal anhydride groups are thermally crosslinked in the presence of a bi‐functional epoxy monomer containing a photolabile o‐nitrobenzyl ester (o‐NBE) group. The susceptibility of the ester groups toward hydrolytic cleavage reactions is used for a pH‐triggered network degradation. Sol–gel analysis confirms that the degradation time can be easily controlled by the base concentration over different time scales varying between hours and weeks. Along with classical ester hydrolysis, photoinduced degradation of the elastomeric networks is carried out by photoisomerization and cleavage of the o‐NBE links upon exposure with UV light. Positive‐tone patterns with a structure size of 100 μm are obtained by photolithographic techniques confirming the spatial control of solubility properties. However, by increasing the exposure dose, recrosslinking of the networks is observed due to side reactions of the primary photocleavage products. As the reformed crosslinks are less sensitive to ester hydrolysis, the side reactions are employed to inscribe negative‐tone microstructures in the PDMS network. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2319–2329

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Section: Introductionmentioning

confidence: 99%

Dual‐Responsive Polydimethylsiloxane Networks

Giebler

Radl

Ast

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…(2‐nitro‐1,4‐phenylene) bis(methylene) acetate (vinyl‐NBE) was synthesized as reported in previous work. [ 21 ]…”

Section: Methodsmentioning

confidence: 99%

“…The photosensitive thiol‐ene network formed by the visible light induced click reaction between trimethylolpropane tris(3‐mercaptopropionate) (TMPMP) and vinyl‐NBE ((2‐nitro‐1,4‐phenylene) bis(methylene) acetate) was prepared according to literature (Figure S1, Supporting Information). [ 21 ] The formation of the network was confirmed by means of fourier‐transform infrared spectroscopy spectra, which were taken before and after the curing reaction. As described in detail in the Supporting Information, the thiol‐ene reaction occurs simultaneously by step‐growth reaction between the thiol moieties and vinyl double bonds.…”

Section: Figurementioning

confidence: 99%

“…At prolonged UV exposure, a re‐crosslinking of the cleaved polymer chains is observed through secondary reactions (e.g., formation of azobenzene groups by dimerization of nitroso‐benzaldehyde moieties) that leads to an increase in the gel content. [ 16–21 ]…”

Section: Figurementioning

confidence: 99%

“…[ 16–20 ] In this context, thiol‐ene networks containing o ‐NBE moieties were used as positive/negative tone photoresist with good resolution. [ 21 ] In addition to the use of o ‐NBE for producing photoresists, we also showed the possibility to modify surface properties of the network through UV‐induced photocleavage, by exploiting the formation of polar species such as carboxylic acids. [ 16 ] The high control obtained by light‐irradiation was further employed to move water droplets on gradually irradiated photopolymer surfaces.…”

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confidence: 99%

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Laser‐Triggered Writing and Biofunctionalization of Thiol‐Ene Networks

Romano

Angelini

Rossegger

et al. 2020

Macromol. Rapid Commun.

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The light responsivity of ortho‐nitrobenzyl esters (o‐NBE) is exploited to inscribe µ‐scale 2.5D patterns in thiol‐ene networks by direct laser writing. For this purpose, a multifunctional thiol and a photosensitive alkene with an o‐NBE chromophore are cured upon visible light exposure without inducing a premature photocleavage of the o‐NBE links. Once the network is formed, a laser beam source with a wavelength of 375 nm is used for selectively inducing the photocleavage reaction of the o‐NBE groups. Positive tone patterns are directly inscribed onto the sample surface without the requirement of a subsequent development step (removing soluble species in an appropriate organic solvent). Along with the realization of dry‐developable micropatterns, the chemical surface composition of the exposed areas can be conveniently adjusted since different domains with a tailored content of carboxylic groups are obtained simply by modulating the laser energy dose. In a following step, those are activated and exploited as anchor points for attaching an Alexa‐546 conjugated Protein A. Thus, the laser writable thiol‐ene networks do not only provide a convenient method for the fabrication of positive tone patterns but also open future prospectives for a wide range of biosensing applications.

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Photoinitiators in Specific Polymerization Processes

2021

Photoinitiators

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Photo-responsive thiol–ene networks for the design of switchable polymer patterns

Abstract: Photo-patternable thiol–ene networks are prepared by combining versatile o-NBE chemistry with the distinctive advantages of a typical “click” reaction.

Cited by 35 publications

References 54 publications

Dual‐Responsive Polydimethylsiloxane Networks

Dual‐Responsive Polydimethylsiloxane Networks

Laser‐Triggered Writing and Biofunctionalization of Thiol‐Ene Networks

Photoinitiators in Specific Polymerization Processes

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