An autonomously oscillating supramolecular self-replicator

Howlett, Michael G.; Engwerda, Anthonius H. J.; Scanes, Robert J. H.; Fletcher, Stephen P.

doi:10.1038/s41557-022-00949-6

Cited by 71 publications

(65 citation statements)

References 41 publications

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“…The ultrasensitive response of the coacervates in our work is attributable to the competition of the reactive radicals between the methacrylate monomer and molecular oxygen. , As described above, molecular oxygen diffused from the air effectively quenches reactive radical species at a lower frequency to generate a threshold, whereas the amount of the radicals produced at a higher frequency becomes higher than that of molecular oxygen to proceed radical polymerization, resulting in the ultrasensitive response. Such an ultrasensitive response based on the competitive mechanism is considered as a new example of light-fueled dissipative systems. ,− To date, it has been reported that coacervates can provide a microenvironment to accelerate catalytic reactions mainly through molecular sequestration ,− and to realize stimulus responses towards reactive molecules ( e.g. , assembly–disassembly). ,,,,,− Compared with these examples, one of the important aspects of our work is to combine the rate enhancement effect with competitive inhibition via continuous supply of diffusing O 2 , which establishes a unique system in response to temporally distinct stimulus patterns.…”

Section: Resultsmentioning

confidence: 99%

Temporal Stimulus Patterns Drive Differentiation of a Synthetic Dipeptide-Based Coacervate

2022

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The fate of living cells often depends on their processing of temporally modulated information, such as the frequency and duration of various signals. Synthetic stimulus-responsive systems have been intensely studied for >50 years, but it is still challenging for chemists to create artificial systems that can decode dynamically oscillating stimuli and alter the systems’ properties/functions because of the lack of sophisticated reaction networks that are comparable with biological signal transduction. Here, we report morphological differentiation of synthetic dipeptide-based coacervates in response to temporally distinct patterns of the light pulse. We designed a simple cationic diphenylalanine peptide derivative to enable the formation of coacervates. The coacervates concentrated an anionic methacrylate monomer and a photoinitiator, which provided a unique reaction environment and facilitated light-triggered radical polymerizationeven in air. Pulsed light irradiation at 9.0 Hz (but not at 0.5 Hz) afforded anionic polymers. This dependence on the light pulse patterns is attributable to the competition of reactive radical intermediates between the methacrylate monomer and molecular oxygen. The temporal pulse pattern-dependent polymer formation enabled the coacervates to differentiate in terms of morphology and internal viscosity, with an ultrasensitive switch-like mode. Our achievements will facilitate the rational design of smart supramolecular soft materials and are insightful regarding the synthesis of sophisticated chemical cells.

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Section: Resultsmentioning

confidence: 99%

Temporal Stimulus Patterns Drive Differentiation of a Synthetic Dipeptide-Based Coacervate

2022

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“…Meanwhile, limited experimental parameters are involved in tuning the diffusion instead of the complex kinetic matching and harsh reaction selectivity requirements in homogeneous systems. This strategy can be further extended to multi-compartment systems 45,46 and liquidliquid phase separation systems. [47][48][49][50] Passive diffusion and active transport can be developed in controlling the transport of chemical fuels or deactivators between compartments.…”

Section: Discussionmentioning

confidence: 99%

Construction of transient supramolecular polymers controlled by mass transfer in biphasic systems

Zhang

et al. 2022

Chem. Sci.

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“…Various synthetic analogs achieving structural diversities and functions have been introduced including emulsions, 38 hydrogels, 39 nanoreactors, 40 molecular motors, 41 polymersomes 42 and steady-state supramolecular polymers. 43 Use of diverse types of fuels has created a repertoire of complex biomimetic out-of-equilibrium systems such as enzyme-catalyzed pH cycles for the transient control of polymer fluids 44 and breathing microgel, 45 carbodiimide for self-selection of primitive reaction-network, 46 thiols for self-replicating micelles, 47 and DNA for constructing nanodevices for drug release and reaction networks. 31,[48][49] While these fuels provide a structural component for generating the nonequilibrium phases, utilization of the fuels to perform biomolecular functions in the time domain would further enrich our understanding of systems chemistry and produce effective biomimetic scaffolds including molecular adhesives.…”

Section: Introductionmentioning

confidence: 99%

A Dissipative Supramolecular Glue for Temporal Control of Amplified Enzyme Activity and Biocatalytic Cascades

Kamra

Das

Bhatt

et al. 2022

Preprint

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Regulation of enzyme activity is key to the adaptation of cellular processes such as signal transduction and metabolism in response to varying external conditions. Synthetic molecular glues have provided effective systems for enzyme inhibition and regulation of protein-protein interactions. So far, all the molecular glue systems based on covalent interactions operated in equilibrium conditions. To emulate dynamic far-from-equilibrium biological processes, we introduce herein a transient supramolecular glue with controllable lifetime. The transient system uses multivalent supramolecular interactions between guanidium group-bearing surfactants and adenosine triphosphates (ATP), resulting in bilayer vesicle structures. Unlike the conventional fuels for non-equilibrium assemblies, ATP here plays the dual role of providing a structural component for the assembly as well as presenting active functional groups to “glue” enzymes on the surface. While gluing of the enzymes on the vesicles achieves augmented catalysis, oscillation of ATP concentration allows temporal control of the catalytic activities. We further demonstrate temporal activation and control of biocatalytic cascade networks on the vesicles, which represents an essential cellular component. Altogether, the temporal activation of biocatalytic cascades on the dissipative vesicular glue presents an adaptable and dynamic system emulating heterogeneous cellular processes, opening up avenues for effective protocell construction and therapeutic interventions.

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An autonomously oscillating supramolecular self-replicator

Abstract: A key goal of chemistry is to develop synthetic systems that mimic biology, such as selfassembling, self-replicating models of minimal life forms. Oscillations are often observed in complex biological networks, but oscillating, self-replicating species are unknown, and how to

Cited by 71 publications

References 41 publications

Temporal Stimulus Patterns Drive Differentiation of a Synthetic Dipeptide-Based Coacervate

Temporal Stimulus Patterns Drive Differentiation of a Synthetic Dipeptide-Based Coacervate

Construction of transient supramolecular polymers controlled by mass transfer in biphasic systems

A Dissipative Supramolecular Glue for Temporal Control of Amplified Enzyme Activity and Biocatalytic Cascades

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