Impact of charge switching stimuli on supramolecular perylene monoimide assemblies

Dannenhoffer, Adam J.; Sai, Hiroaki; Huang, Dongxu; Nagasing, Benjamin; Harutyunyan, Boris; Fairfield, Daniel J.; Aytun, Taner; Chin, Stacey M.; Bedzyk, Michael J.; Cruz, Mónica Olvera de la; Stupp, Samuel I.

doi:10.1039/c8sc05595e

Cited by 23 publications

(21 citation statements)

References 52 publications

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“…Our laboratory has demonstrated the use of peptide amphiphile (PA) and chromophore amphiphile (CA) building blocks to create chemically diverse and mechanically tunable hydrogels for various functions. [ 19–24 ] The PA nanofiber‐shaped supramolecular polymers developed in our laboratory are known to form liquid crystalline domains in aqueous solutions which can be aligned by shear forces and fixed into monodomain gels while pipetting into salty media. [ 25 ] The resulting gels exhibit bulk anisotropic properties due to the macroscopic alignment of the supramolecular assemblies.…”

Section: Introductionmentioning

confidence: 99%

3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure

Sather

Sai

Sasselli

et al. 2021

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Liquid crystalline hydrogels are an attractive class of soft materials to direct charge transport, mechanical actuation, and cell migration. When such systems contain supramolecular polymers, it is possible in principle to easily shear align nanoscale structures and create bulk anisotropic properties. However, reproducibly fabricating and patterning aligned supramolecular domains in 3D hydrogels remains a challenge using conventional fabrication techniques. Here, a method is reported for 3D printing of ionically crosslinked liquid crystalline hydrogels from aqueous supramolecular polymer inks. Using a combination of experimental techniques and molecular dynamics simulations, it is found that pH and salt concentration govern intermolecular interactions among the self‐assembled structures where lower charge densities on the supramolecular polymers and higher charge screening from the electrolyte result in higher viscosity inks. Enhanced hierarchical interactions among assemblies in high viscosity inks increase the printability and ultimately lead to greater nanoscale alignment in extruded macroscopic filaments when using small nozzle diameters and fast print speeds. The use of this approach is demonstrated to create materials with anisotropic ionic and electronic charge transport as well as scaffolds that trigger the macroscopic alignment of cells due to the synergy of supramolecular self‐assembly and additive manufacturing.

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Section: Introductionmentioning

confidence: 99%

3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure

Sather

Sai

Sasselli

et al. 2021

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“…[33] Stupp's group has shown a range of self-assembled PMIs can be effective as part of a photocatalytic hydrogen evolution reaction (HER). [20,[34][35][36] Recently, they have also published work studying hybrid polyelectrolyte and supramolecular systems in which PMIs are entrapped in a crosslinked polyelectrolyte hydrogel. [37] Once deposited in the hydrogel network, self-assembly of the PMI is triggered through a solvent switch and the photocatalytic hydrogen production of these systems studied.…”

Section: Introductionmentioning

confidence: 99%

Controlling Photocatalytic Activity by Self‐Assembly – Tuning Perylene Bisimide Photocatalysts for the Hydrogen Evolution Reaction

McDowall

Greeves

Clowes

et al. 2020

Advanced Energy Materials

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usually strongly absorbing in the visible light region and many possess n-type semiconductor behavior when aggregated. [8,9] PBIs often self-assemble in solution at high concentrations or when given a suitable trigger. They typically self-assemble into 1D structures such as nanofibers or nanotubes, a process driven by non-covalent interactions such as hydrogen bonding, van der Waals interactions, and π-π stacking. [2,3,10-14] The electronic properties of PBIs can be tuned by how they are functionalized and by the type of self-assembled aggregate that is formed. [10,15] Using solar energy to generate H 2 and O 2 from water is highly desirable to form part of a "green economy". [16-18] H 2 can be used as a fuel for combustion, within fuel cells and both H 2 and O 2 are also important chemical feedstocks. [17,18] PBIs and the related perylene monoimides (PMIs) have shown promise in the utilization of solar energy to drive chemical reactions, and have been shown to be able to act as effective photocatalysts for both H 2 evolution and O 2 evolution reactions. [19-23] Some of these systems use perylene mono or bis imides in a self-assembled state, but other self-assembled photocatalysts

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“…30 Stupp's group has shown a range of self-assembled PMIs can be effective as part of a photocatalytic hydrogen evolution reaction (HER). 17,[31][32][33] Recently, they have also published work studying hybrid polyelectrolyte and supramolecular systems in which PMIs are entrapped in a crosslinked polyelectrolyte hydrogel. 34 Once deposited in the hydrogel network, selfassembly of the PMI is triggered through a solvent switch and the photocatalytic hydrogen production of these systems studied.…”

Section: Introductionmentioning

confidence: 99%

Controlling Activity by Self-Assembly – Tuning Perylene Bisimide Photocatalysts for the Hydrogen Evolution Reaction

McDowall¹,

Greeves²,

McAulay³

et al. 2020

Preprint

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Amino acid functionalised perylene bisimides (PBIs) form self-assembled structures in solution, the nature of which depends on the local environment. Using a high throughput photocatalysis set-up, we have studied five PBIs for the hydrogen evolution reaction (HER) under a range of conditions (pH and hole scavenger concentration) across 350 experiments to explore the relationship between supramolecular structure and photocatalytic activity. Using small angle X-ray scattering (SAXS), we show that photocatalytic activity is determined by the nature of the self-assembled aggregate that is formed with a correlation between the presence of charged flexible cylindrical aggregates and high levels of H2. Our work highlights the complexity of designing supramolecular photocatalysts, and also the power of tuning activity by the type of aggregate that is formed.

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Impact of charge switching stimuli on supramolecular perylene monoimide assemblies

Abstract: A switchable perylene monoimide which undergoes reversible morphological and electronic changes controlled by the ionization state of the phenolic oxygen.

Cited by 23 publications

References 52 publications

3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure

3D Printing of Supramolecular Polymer Hydrogels with Hierarchical Structure

Controlling Photocatalytic Activity by Self‐Assembly – Tuning Perylene Bisimide Photocatalysts for the Hydrogen Evolution Reaction

Controlling Activity by Self-Assembly – Tuning Perylene Bisimide Photocatalysts for the Hydrogen Evolution Reaction

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