Exploiting and controlling gel-to-crystal transitions in multicomponent supramolecular gels

Giuri, Demetra; Marshall, Libby J.; Dietrich, Benjamin; McDowall, Daniel; Thomson, Lisa; Newton, Jenny Y.; Wilson, Claire; Schweins, Ralf; Adams, Dave J.

doi:10.1039/d1sc02347k

Cited by 15 publications

(17 citation statements)

References 45 publications

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“…The product’s self-protection mechanism is effectively a feedback mechanism. Excitingly, the feedback relies on a phase separation mechanism and is, due to its rudimentary nature, frequently observed in chemically fueled assemblies 35 – 37 . The metastable zone in the phase diagram combined with the feedback of the crystals are the core mechanism of the bistability in this work.…”

Section: Resultsmentioning

confidence: 99%

Memory, switches, and an OR-port through bistability in chemically fueled crystals

et al. 2022

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The ability to store information in chemical reaction networks is essential for the complex behavior we associate with life. In biology, cellular memory is regulated through transcriptional states that are bistable, i.e., a state that can either be on or off and can be flipped from one to another through a transient signal. Such memory circuits have been realized synthetically through the rewiring of genetic systems in vivo or through the rational design of reaction networks based on DNA and highly evolved enzymes in vitro. Completely bottom-up analogs based on small molecules are rare and hard to design and thus represent a challenge for systems chemistry. In this work, we show that bistability can be designed from a simple non-equilibrium reaction cycle that is coupled to crystallization. The crystals exert the necessary feedback on the reaction cycle required for the bistability resulting in an on-state with assemblies and an off-state without. Each state represents volatile memory that can be stored in continuously stirred tank reactors indefinitely even though molecules are turned over on a minute-timescale. We showcase the system’s abilities by creating a matrix display that can store images and by creating an OR-gate by coupling several switches together.

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Section: Resultsmentioning

confidence: 99%

Memory, switches, and an OR-port through bistability in chemically fueled crystals

et al. 2022

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“…6Br2NapAV and 2NapAA have been reported previously by our group and were chosen as they exhibit unusual gelation behaviour in the bulk (specifically, syneresis and a gel-to-crystal transition, see below). 32,35,42 Stock solutions of all gelators were prepared at a concentration of 5 mg mL À1 and adjusted to pH 8. To grow the hydrogels, 5 mg mL À1 of HQ was added to the gelator solutions immediately prior to gel deposition.…”

Section: Resultsmentioning

confidence: 99%

“…2 Chemical structure and names used throughout of gelator molecules; the gelation of 6Br2NapAV and 2NapAA have been described previously. 32,35,42 dissolved, the gelator/HQ solution was transferred to the dish containing the three-electrode set up within the desiccator. It is important to note that the procedure was performed in a desiccator as it could be fully degassed prior to running the experiment.…”

Section: Resultsmentioning

confidence: 99%

“…32 Despite both gelators showing the same trend, we believe this behaviour is due to two separate phenomena, unique to each gel network. Giuri et al 42 have recently shown that gels formed from 2NapAA exhibit unusual ageing properties, undergoing a gel-tocrystal transition when triggered by certain concentrations of glucono-d-lactone (GdL). Their results show that the degree of crystallisation increases with decreasing pH, driven by the excess protonation of the carboxylic acid groups on the gel network.…”

Section: Resultsmentioning

confidence: 99%

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Electrofabrication of large volume di- and tripeptide hydrogels via hydroquinone oxidation

et al. 2022

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“…The product's self-protection mechanism is effectively a feedback mechanism. However, unlike autocatalysis, it relies on a simple phase separation mechanism and is, due to its rudimentary nature, frequently observed in chemically fueled assemblies [33][34][35] . The metastable zone in the phase diagram combined with the feedback of the crystals are the core mechanism of the bistability in this work.…”

Section: Resultsmentioning

confidence: 99%

Memory, switches, and logic gates through bistability in chemically fueled crystals

Schnitter¹,

Rieß²,

Boekhoven³

2021

Preprint

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The ability to store information in chemical reaction networks is essential for evolution, calculations, and, more generally, for the complex behavior, we associate with life. In biology, cellular memory is regulated through transcriptional states that are bistable, i.e., a state that can either be on or off and can be flipped from one to another through a transient signal. Such memory circuits have been realized synthetically through the rewiring of genetic systems in vivo or through the rational design of reaction networks based on DNA and highly evolved enzymes in vitro. Completely bottom-up analogs based on small molecules are rare and hard to design and thus represent a challenge for systems chemistry. In this work, we show that bistability can be designed from an extremely simple non-equilibrium reaction cycle that is coupled to crystallization. The crystals exert the necessary feedback on the reaction cycle required for the bistability resulting in an on-state with assemblies and an off-state without. We can switch the state on and off, such that each state represents volatile memory that can be stored in continuously stirred tank reactors indefinitely despite the fact that molecules are turned over on a minute-timescale. We showcase the system’s abilities by creating a matrix display that can store images and by performing Boolean logic by coupling several switches together.

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Exploiting and controlling gel-to-crystal transitions in multicomponent supramolecular gels

Abstract: Multicomponent supramolecular gels provide opportunities to form materials that are not accessible when using the single components alone. Different scenarios are possible when mixing multiple components, from complete co-assembly (mixing...

Cited by 15 publications

References 45 publications

Memory, switches, and an OR-port through bistability in chemically fueled crystals

Memory, switches, and an OR-port through bistability in chemically fueled crystals

Electrofabrication of large volume di- and tripeptide hydrogels via hydroquinone oxidation

Memory, switches, and logic gates through bistability in chemically fueled crystals

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