Anthracene-Based Thiol–Ene Networks with Thermo-Degradable and Photo-Reversible Properties

Damme, Jonas Van; Berg, Otto; Brancart, Joost; Vlaminck, Laetitia; Huyck, C. Lee; Assche, Guy Van; Mele, Bruno Van; Prez, Filip Du

doi:10.1021/acs.macromol.6b02400

Cited by 67 publications

(75 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is reported that the rate of this dissociation, which is caused by anthracene dimers that dissociate cleanly at the elevated temperatures through a diradical transition state, depends on the substituents on the anthracene ring. 32 As expected, PAPMS-2 could be easily depolymerized than PAPMS-1 because the anthracene in PAPMS-2 was linked to an electron-withdrawing group. Sunlight is a green energy source, which includes light of various wavelengths; when it comes to the application in chemistry, sunlight is primarily used in the eld of photocatalysis.…”

Section: Resultssupporting

confidence: 51%

Light- and heat-triggered reversible luminescent materials based on polysiloxanes with anthracene groups

Han

et al. 2017

RSC Adv.

View full text Add to dashboard Cite

show abstract

Section: Resultssupporting

confidence: 51%

Light- and heat-triggered reversible luminescent materials based on polysiloxanes with anthracene groups

Han

et al. 2017

RSC Adv.

View full text Add to dashboard Cite

show abstract

“…Therefore, this thiol was not suited for unambiguous design of dynamic materials that are solely relying on dynamic thiol exchange. Hence, an aliphatic trifunctional thiol (trithiol) was synthesized and used as a reference building block to produce dynamic polymer materials.…”

Section: Resultsmentioning

confidence: 99%

Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross‐Linking

et al. 2020

View full text Add to dashboard Cite

The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross‐linkers for thiols. The click‐like thiol–yne cross‐linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross‐linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne‐based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross‐linker.

show abstract

“…The photocycloaddition, or photodimerization, of anthracene has been well‐known for a long time . Recently, it has experienced a renaissance as it has been used in a variety of material applications, including self‐healing materials, single‐chain nanoparticles, and in the formation of completely degradable networks . One reason anthracene was employed in the current resist, is the fact that it has been shown recently that the photodimerization of certain anthracene systems can be triggered in the visible light regime .…”

Section: Methodsmentioning

confidence: 99%

Tailoring the Mechanical Properties of 3D Microstructures Using Visible Light Post‐Manufacturing

et al. 2019

View full text Add to dashboard Cite

the laser, where the square of the optical intensity exceeds the threshold needed to initiate polymerization. In this way, very small feature sizes of less than 100 nm can be achieved. [3,4] Microstructures pre pared via DLW have for example been used in microfluidic chips, [5,6] metama terials, [7] or as 3D microscaffolds for cell and tissue engineering. [8] Commercial resist mixtures are available that are well suited for the rapid generation of stable structures. However, when using standard resists, the resulting microstructures are static. In order to further expand the rep ertoire of applications of DLW, new photo resists have to be designed that directly impart functionality onto the structures emerging from the writing process. [9] Our group has been pursuing this goal, pro ducing resists that, e.g., lead to conduc tive, [10] stimuliresponsive, [11] and erasable structures. [12] The mechanical properties of microstructures are critical for their application, especially when used as cell scaf folds. [13] The mechanical properties of microstructures created via DLW can certainly be tuned by careful adjustment of the writing parameters (i.e., laser power and scan speed), but only to a limited extent. [14] Herein, we present the first photoresist for DLW that is capable of generating microstructures whose mechanical properties can be adjusted postwriting, solely The photochemistry of anthracene, a new class of photoresist for direct laser writing, is used to enable visible-light-gated control over the mechanical properties of 3D microstructures post-manufacturing. The mechanical and viscoelastic properties (hardness, complex elastic modulus, and loss factor) of the microstructures are measured over the course of irradiation via dynamic mechanical analysis on the nanoscale. Irradiation of the microstructures leads to a strong hardening and stiffening effect due to the generation of additional crosslinks through the photodimerization of the anthracene functionalities. A relationship between the loss of fluorescence-a consequence of the photodimerization-and changes in the mechanical properties isestablished. The fluorescence thus serves as a proxy read-out for the mechanical properties. These photoresponsive microstructures can potentially be used as "mechanical blank slates": their mechanical properties can be readily adjusted using visible light to serve the demands of different applications and read out using their fluorescence. 3D MicrostructuresDirect laser writing (DLW) is the only manufacturing tech nique capable of producing truly 3D structures on the micro scopic scale. [1] What differentiates DLW from conventional 3Dprinting techniques is the fact that it exploits twophoton absorption (TPA) to initiate polymerizations. While single photon absorption (SPA) is proportional to the optical inten sity, TPA is proportional to the square of the optical intensity. [2] Thus, polymerization will only take place in the focal volume of

show abstract

Anthracene-Based Thiol–Ene Networks with Thermo-Degradable and Photo-Reversible Properties

Cited by 67 publications

References 22 publications

Light- and heat-triggered reversible luminescent materials based on polysiloxanes with anthracene groups

Light- and heat-triggered reversible luminescent materials based on polysiloxanes with anthracene groups

Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross‐Linking

Tailoring the Mechanical Properties of 3D Microstructures Using Visible Light Post‐Manufacturing

Contact Info

Product

Resources

About