A bolaamphiphilic amino acid appended photo-switching supramolecular gel and tuning of photo-switching behaviour

Roy, Subhasish; Maiti, Dibakar Kumar; Panigrahi, Shrabani; Basak, Durga; Banerjee, Arindam

doi:10.1039/c3cp55108c

Cited by 26 publications

(32 citation statements)

References 72 publications

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“…The authors demonstrated that the incorporation of graphene oxide or reduced graphene oxide into the hydrogels enhances the photoresponsiveness of the hydrogel of 106 . 391 Zang et al also reported that a perylenebisimide derivative ( 107 ) forms a hydrogel via pH triggering. The authors found that the addition of hydrochloric acid in the 4.4 mM (about 0.2 wt %) solution of 107 (in the presence of 26.4 mM triethylamine) results in a dark red hydrogel, 392 which agrees with the formation of a charge transfer complex.…”

Section: Molecular Designmentioning

confidence: 99%

Supramolecular Hydrogelators and Hydrogels: From Soft Matter to Molecular Biomaterials

et al. 2015

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In this review we intend to provide a relatively comprehensive summary of the work of supramolecular hydrogelators after 2004 and to put emphasis particularly on the applications of supramolecular hydrogels/hydrogelators as molecular biomaterials. After a brief introduction of methods for generating supramolecular hydrogels, we discuss supramolecular hydrogelators on the basis of their categories, such as small organic molecules, coordination complexes, peptides, nucleobases, and saccharides. Following molecular design, we focus on various potential applications of supramolecular hydrogels as molecular biomaterials, classified by their applications in cell cultures, tissue engineering, cell behavior, imaging, and unique applications of hydrogelators. Particularly, we discuss the applications of supramolecular hydrogelators after they form supramolecular assemblies but prior to reaching the critical gelation concentration because this subject is less explored but may hold equally great promise for helping address fundamental questions about the mechanisms or the consequences of the self-assembly of molecules, including low molecular weight ones. Finally, we provide a perspective on supramolecular hydrogelators. We hope that this review will serve as an updated introduction and reference for researchers who are interested in exploring supramolecular hydrogelators as molecular biomaterials for addressing the societal needs at various frontiers.

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Section: Molecular Designmentioning

confidence: 99%

Supramolecular Hydrogelators and Hydrogels: From Soft Matter to Molecular Biomaterials

et al. 2015

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“…photo-switching can be seen in the current over time as the light source is turned on and off (Figure1.22b). Similar results with photo-switching behavior were seen for a gel made from a bolaamphiphile amino acid comprised of a tyrosine moiety tethered to the PDI core by a hydrophobic 11-carbon alkyl linker 77. …”

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confidence: 75%

Peptide-Directed Supramolecular Self-Assembly of N-Substituted Perylene Imides

Eakins¹

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<p>Synthetic peptides offer enormous potential to encode the assembly of molecular electronic components, provided that the complex range of interactions is distilled into simple design rules. Herein is reported a spectroscopic investigation of aggregation in an extensive series of peptide-perylene imide conjugates designed to interrogate the effect of structural variations. Throughout the course of this study, the self-assembly and photophysical properties of the compounds are explored to better understand the behavior and application of these materials. Three principal avenues of inquiry are applied: (1) the evaluation of structure-property relationships from a thermodynamic perspective, (2) the examination of peptide chiral effects upon properties and self-assembly, and (3) an application of the understanding gained from rationally designed systems to effectively utilize naturally optimized peptides in bio-organic electronics. By fitting different contributions to temperature-dependent optical absorption spectra, this study quantifies both the thermodynamics and the nature of aggregation for peptides with incrementally varying hydrophobicity, charge density, length, amphiphilic substitution with a hexyl chain, and stereocenter inversion. Coarse effects like hydrophobicity and hexyl substitution are seen to have the greatest impact on binding thermodynamics, which are evaluated separately as enthalpic and entropic contributions. Moreover, significant peptide packing effects are resolved via stereocenter inversion studies, particularly when examining the nature of aggregates formed and the coupling between π-electronic orbitals. Peptide chirality overall is seen to influence the self-assembly of the perylene imide cores into chiral nanofibers, and peptide stereogenic positions, stereochemical configurations, amphiphilic substitution, and perylene core modification are evaluated with respect to chiral assembly. Stereocenters in peptide residue positions proximal to the perylene core (1-5 units) are seen to impart helical chirality to the perylene core, while stereocenters in more distal residue positions do not exert a chiral influence. Diastereomers involving stereocenter inversions within the proximal residues consequently manifest spectroscopically as pseudo-enantiomers. Increased side-chain steric demand in the proximal positions gives a similar chiral influence but exhibits diminished Cotton Effect intensity with additional longer wavelength features attributed to interchain excimers. Amphiphilic substitution of a peptide with an alkyl chain disrupts chiral self-assembly, while an amphiphilic structure achieved through the modification of the perylene imide core with a bisester moiety prompts strongly exciton-coupled, chiral, solvent-responsive self-assembly into long nanofilaments. Informed by rationally designed sequences, and capitalizing upon the optimization seen in many natural systems, specific peptide sequences designed by inspection of protein-protein interfaces have been identified and used as tectons in hybrid functional materials. An 8-mer peptide derived from an interface of the peroxiredoxin family of self-assembling proteins is exploited to encode the assembly of perylene imide-based organic semiconductor building blocks. By augmenting the peptide with additional functionality to trigger aggregation and manipulate the directionality of peptide-semiconductor coupling, a series of hybrid materials based on the natural peptide interface is presented. Using spectroscopic probes, the mode of self-assembly and the electronic coupling between neighboring perylene units is shown to be strongly affected by the number of peptides attached, and by their backbone directionality. The disubstituted material with peptides extending in the N-C direction away from the perylene core exhibits strong coupling and long-range order, which are both attractive properties for electronic device applications. A bio-organic field-effect transistor is fabricated using this material, highlighting the possibilities of exploiting natural peptide tectons to encode self-assembly in other functional materials and devices. These results advance the development of a quantitative framework for establishing structure-function relationships that will underpin the design of self-assembling peptide electronic materials. The results further advance a model for adapting natural peptide sequences resident in β-continuous interfaces as tectons for bio-organic electronics.</p>

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“…Like the previous semiconducting gel example from Muthusamy et al, the optoelectronic response of this gel can be tuned with the inclusion of graphene. Specifically, incorporation of graphene oxides into the gel allows for a more distinct “on” current state to be accessed upon white light exposure, opening the possibility of a logic gate-esque system based on these self-assembled gels [25]. However, such a material was only shown to cycle four times before a roughly 33% degradation in distinction between “on” and “off” states.…”

Section: Supramolecular Gels For Optoelectronic Applicationsmentioning

confidence: 99%

“…Selected gelators developed for optoelectronic applications: ( A ) a conductive, self-healing PNAGA-PAMPS/PEDOT/PSS-3-49 gelator [21]; ( B ) a fluorescent gelator with hydrophobic moieties of pyrenebutyric acid and a hydrophilic moiety of an ethyleneoxy unit coupled with 1-(3-aminopropyl)imidazole [23]; ( C ) a photocatalytic chromophore amphiphile gelator [24]; and ( D ) a dipeptide-based perylene bisimide derivative gelator whose xerogel exhibits current photo-switching properties [25]. …”

Section: Figurementioning

confidence: 99%

Beyond Covalent Crosslinks: Applications of Supramolecular Gels

Christoff‐Tempesta

Lew

Ortony

2018

Gels

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Traditionally, gels have been defined by their covalently cross-linked polymer networks. Supramolecular gels challenge this framework by relying on non-covalent interactions for self-organization into hierarchical structures. This class of materials offers a variety of novel and exciting potential applications. This review draws together recent advances in supramolecular gels with an emphasis on their proposed uses as optoelectronic, energy, biomedical, and biological materials. Additional special topics reviewed include environmental remediation, participation in synthesis procedures, and other industrial uses. The examples presented here demonstrate unique benefits of supramolecular gels, including tunability, processability, and self-healing capability, enabling a new approach to solve engineering challenges.

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A bolaamphiphilic amino acid appended photo-switching supramolecular gel and tuning of photo-switching behaviour

Cited by 26 publications

References 72 publications

Supramolecular Hydrogelators and Hydrogels: From Soft Matter to Molecular Biomaterials

Supramolecular Hydrogelators and Hydrogels: From Soft Matter to Molecular Biomaterials

Peptide-Directed Supramolecular Self-Assembly of N-Substituted Perylene Imides

Beyond Covalent Crosslinks: Applications of Supramolecular Gels

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