Synthesis, self-assembly, and photomechanical actuator performance of a sequence-defined polyviologen crosslinker

Delawder, Abigail O.; Natraj, Anusree; Colley, Nathan D.; Saak, Tiana M.; Greene, Angelique F.; Barnes, Jonathan C.

doi:10.1080/10610278.2019.1632453

Cited by 13 publications

(14 citation statements)

References 32 publications

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“…It is important to note that although the smaller molecular weight oligomersnamely, 2V 2+ , 2V 4+ -St, and 4V 6+displayed narrow elution bands by GPC, the hexaviologen macrocrosslinker and its corresponding precursor (6V 12+ -St and 6V 10+ , respectively) exhibited considerable peak broadening. However, this has been observed in previous reports by us, 75,76 and is expected as more positive charges are built into the higher molecular weight oligomers, thus allowing for increased counterion exchange to occur on the column (mobile phase: H 2 O with 0.025 M Na 2 SO 4 at 23 C). To corroborate the purity and unimolecular nature of each oligoviologen intermediate and the nal macrocrosslinker, end-group analysis was performed using 1 H NMR spectroscopy ( Fig.…”

Section: Synthesis and Characterization Of The Viologen-based Crosslimentioning

confidence: 61%

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

Amir

Gruschka

et al. 2020

Chem. Sci.

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Section: Synthesis and Characterization Of The Viologen-based Crosslimentioning

confidence: 61%

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

Amir

Gruschka

et al. 2020

Chem. Sci.

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“…It is important to note that although the smaller molecular weight oligomers -namely, 2V 2+ , 2V 4+ -St, and 4V 6+ -displayed narrow elution bands by GPC, the hexaviologen macrocrosslinker and its corresponding precursor (6V 12+ -St and 6V 10+ , respectively) exhibited considerable peak broadening. However, this has been observed in previous reports by us, 75,76 and is expected as more positive charges are built into the higher molecular weight oligomers, thus allowing for increased counterion exchange to occur on the column (mobile phase: H2O with 0.025 M Na2SO4 at 23 o C). To corroborate the purity and unimolecular nature of each oligoviologen intermediate and the final macrocrosslinker, end-group analysis was performed using 1 H NMR spectroscopy (Figure 2c, S9).…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 62%

Dynamic, Multimodal Hydrogel Actuators Using Porphyrin-Based Visible Light Photoredox Catalysis in a Thermoresponsive Polymer Network

Amir

Gruschka

et al. 2020

Preprint

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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 over several cycles while changing their mechanical properties in response to blue and red light, as well as heat (~50 °C). The light-responsive behavior was achieved through a photoredox-based mechanism consisting of photoinduced electron transfer from a zinc porphyrin photocatalyst in its excited state to oligoviologen-based macrocrosslinkers, both of which were integrated into the hydrogel polymer network during gel formation. Orthogonal thermoresponsive properties were also realized by introducing N-isopropyl acrylamide (NIPAM) monomer simultaneously with hydroxyethyl acrylate (HEA) in the pre-gel mixture to produce a statistical 60:40 HEA:NIPAM polymer network. The resultant hydrogel actuators – crosslinked with either a styrenated viologen dimer (2V4+-St) or hexamer (6V12+-St) – were exposed to red or blue light, or heat, for up to 5 h, and their rate of contraction, as well as the corresponding changes in their physical properties (i.e., stiffness, tensile strength, Young’s modulus, etc.), were measured. The combined application of blue light and heat to the 6V12+-St-based hydrogels was also demonstrated, resulting in hydrogels with more than two-fold faster contraction kinetics and dramatically enhanced mechanical robustness when fully contracted. We envision that the reported materials and the corresponding methods of remotely manipulating the dynamic hydrogels may serve as a useful blueprint for future adaptive materials used in biomedical applications.

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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%

“…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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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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Synthesis, self-assembly, and photomechanical actuator performance of a sequence-defined polyviologen crosslinker

Cited by 13 publications

References 32 publications

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

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

Dynamic, Multimodal Hydrogel Actuators Using Porphyrin-Based Visible Light Photoredox Catalysis in a Thermoresponsive Polymer Network

Redox of Viologen for Powering and Coloring

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