Dynamic, multimodal hydrogel actuators using porphyrin-based visible light photoredox catalysis in a thermoresponsive polymer network

Amir, Faheem; Li, Xuesong; Gruschka, Max; Colley, Nathan D.; Li, Lei; Li, Ruihan; Linder, Houston R.; Sell, Scott A.; Barnes, Jonathan C.

doi:10.1039/d0sc04287k

Cited by 25 publications

(20 citation statements)

References 88 publications

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“…In comparison, the PLLV‐GA‐gel recorded a much higher contraction rate; as for water egress, PLLV‐GA‐gel joins the class of gels of the largest swelling ratio. Photo‐induced reduction of viologens to lead the gel conduction has been also demonstrated, [53–56] while our direction is the deformation on an electrode even in the dark. For a series of various poly‐viologen hydrogels, photo‐induced contractions to 40 % volume in 300 min, [53,55] 10 % in 240 min, [54] and 18 % in 75 min, [56] all being slower than PLLV‐GA‐gel, have been reported.…”

Section: Powering and Dynamics By Redoxmentioning

confidence: 73%

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Redox of Viologen for Powering and Coloring

Sagara

Tahara

2021

The Chemical Record

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Viologen is among the most attractive and easiest‐to‐use organic redox active group in many functional molecular assemblies. It plays crucial roles as an electron transfer mediator in the artificial photo‐energy conversion systems and electron‐transfer protein assemblies and as a building block of supramolecules. Its features include electrochemically reversible redox activity and stability. Strong blue color and tendency to dimerization of the one‐electron reduced form, viologen mono‐radical mono‐cation, are remarkable. In this Account, we describe the use of viologen to give a powered movement of small molecules and motion of millimetre‐sized macroscopic soft‐matters and the use of viologen ionic liquid as electrochromic materials. Attractivities of the use of viologen units for powering and coloring are demonstrated and discussed. In particular, we highlight driving of mechanical movements by π–π stacking dimerization, incorporation in a hydrogel to attain highly deformable material, induction of 2D phase transformation, and sharp color change of very thin ionic liquid layer in a compartment‐less electrochromic display.

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Section: Powering and Dynamics By Redoxmentioning

confidence: 73%

“…Recently, Barnes and colleagues have developed viologen‐incorporated hydrogel [18,53–56] . One of their hydrogels is composed of unimolecular viologen‐based oligomeric links in a three‐dimensional network [18] .…”

Section: Powering and Dynamics By Redoxmentioning

confidence: 99%

Redox of Viologen for Powering and Coloring

Sagara

Tahara

2021

The Chemical Record

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“…Photoactive polymers can also be made by adding a chemical that will undergo an isomerization reaction when light of a certain wavelength is absorbed (e.g., azobenzenes [100] and spiropyrans [60,101] ) or they contain a photocatalyst that will initiate a reaction that leads to the shape change. [102,103] Many of these chemistries are not efficient when it comes to converting light energy to mechanical work. We feel that there is a particular need to develop chemistries compatible with 4D fabrication techniques that are capable of efficiently converting light to mechanical work.…”

Section: Development Of Responsive Chemistries For Efficient Photomec...mentioning

confidence: 99%

Biomimetic and Biologically Compliant Soft Architectures via 3D and 4D Assembly Methods: A Perspective

et al. 2022

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synthetically. Studying structures found in nature has motivated and will continue to motivate the advancement of 3D fabrication strategies. Progress in this field has seen tremendous growth in recent years and structures that are made with relative ease today, a few decades ago would have seemed impossible. New developments, particularly in the construction of architectures made from soft materials or hybrid structures containing both soft and hard components are continuously emerging. Creation of soft synthetic structures that mimic the properties and functions of biological materials or can interact with, probe, and control living materials continue to drive research in this field.Here, recent contributions from the literature and our research are highlighted and the reports are used to highlight opportunities and current needs for advances in the chemistry of soft materials in the context of their functional integration into 3D architectures of complex form. The methods considered herein serve to highlight a recent paradigm for heterogeneous integration-methods of 4D fabrication exploiting directed assembly and printing to construct complex functional composite material structures.Recent progress in soft material chemistry and enabling methods of 3D and 4D fabrication-emerging programmable material designs and associated assembly methods for the construction of complex functional structures-is highlighted. The underlying advances in this science allow the creation of soft material architectures with properties and shapes that programmably vary with time. The ability to control composition from the molecular to the macroscale is highlighted-most notably through examples that focus on biomimetic and biologically compliant soft materials. Such advances, when coupled with the ability to program material structure and properties across multiple scales via microfabrication, 3D printing, or other assembly techniques, give rise to responsive (4D) architectures. The challenges and prospects for progress in this emerging field in terms of its capacities for integrating chemistry, form, and function are described in the context of exemplary soft material systems demonstrating important but heretofore difficult-to-realize biomimetic and biologically compliant behaviors.

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“…Next, a polymerizable photocatalyst was synthesized to imbue the microparticle with the ability to absorb visible light and reduce the viologen-based crosslinker through PET. To accomplish this, we modified a previous synthesis 21 Please do not adjust margins Please do not adjust margins acrylate-functionalized zinc tetraphenyl porphyrin with a PEG spacer (MW = 2000 g•mol -1 ) to facilitate water solubility. Hydroxy tetraphenyl porphyrin (TPP-OH) was synthesized by heating 3 equiv benzaldehyde, 1 equiv hydroxybenzaldehyde, and 4 equiv pyrrole in propionic acid at reflux for 4 h. The solution was cooled to -40 °C and the precipitate was collected and purified by silica column chromatography in a 5% yield.…”

Section: Synthesis Of Viologen-crosslinker and Photocatalystsmentioning

confidence: 99%

Electrostatic loading and photoredox-based release of molecular cargo from oligoviologen-crosslinked microparticles

Palmquist

Gruschka

Dorsainvil

et al. 2021

Preprint

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Although on-demand cargo release has been demonstrated in a wide range of microparticle platforms, many existing methods lack specific loading interactions and/or undergo permanent damage to the microparticle to release the cargo. Here, we report a novel method for electrostatically loading negatively charged molecular cargo in oligoviologen-crosslinked microparticles, wherein the cargo can be released upon activation by visible light. A water-in-oil (W/O) emulsion polymerization method was used to fabricate narrowly dispersed microparticles crosslinked by a dicationic viologen-based dimer and a poly(ethylene glycol) diacrylate. A zinc-tetraphenyl porphyrin photocatalyst was also polymerized into the microparticle and used to photochemically reduce the viologen subunits to their monoradical cations through a visible-light-mediated photoredox mechanism with triethanolamine (TEOA) as a sacrificial reductant. The microparticles were characterized by microscopy methods revealing uniform, spherical microparticles 481 ± 20.9 nm in diameter. Negatively charged molecular cargo (methyl orange, MO) was electrostatically loaded into the microparticles through counteranion metathesis. Upon irradiation with blue (450 nm) light, the photo-reduced viologen crosslinker subunits lose positive charges, resulting in release of the anionic MO cargo. Controlled release of the dye, as tracked by absorption spectroscopy, was observed over time, yielding release of up to 40% of the cargo in 2d and 60% in 5d in single dynamic dialysis experiment. However, full release of cargo was achieved upon transferring the microparticles to a fresh TEOA solution after the initial 5d period.

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Dynamic, multimodal hydrogel actuators using porphyrin-based visible light photoredox catalysis in a thermoresponsive polymer network

Abstract: Hydrogels that can respond to multiple external stimuli represent the next generation of advanced functional biomaterials. Here, a series of multimodal hydrogels were synthesized that can contract and expand reversibly...

Cited by 25 publications

References 88 publications

Redox of Viologen for Powering and Coloring

Redox of Viologen for Powering and Coloring

Biomimetic and Biologically Compliant Soft Architectures via 3D and 4D Assembly Methods: A Perspective

Electrostatic loading and photoredox-based release of molecular cargo from oligoviologen-crosslinked microparticles

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