Chemically Fueled Self-sorted Hydrogels

Singh, Neeloo; Lopéz-Acosta, Álvaro; Formon, Georges; Hermans, Thomas M.

doi:10.26434/chemrxiv-2021-n8lt5

Cited by 3 publications

(3 citation statements)

References 28 publications

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“…To create chemically fueled assemblies, we and others used a strategy in which a chemical reaction cycle transiently negates the charges on a molecule (Scheme 1D). [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] Upon activation, an anionic, well-soluble precursor becomes charge-neutral, which induces product assembly. The deactivation occurs while the building block is assembled; it reinstates the negative charges and thus leads to its disassembly.…”

Section: Scheme 1 A) Scheme Of a Fuel-driven Reaction Cyclementioning

confidence: 99%

Kinetic traps in chemically fueled self-assembly and how to overcome them.

Kriebisch

Bergmann

et al. 2022

Preprint

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Nature uses dynamic, molecular self-assembly to create cellular architectures that adapt to their environment. For example, a guanosine triphosphate (GTP)-driven reaction cycle activates and deactivates tubulin for assembly into microtubules and disassembly. Inspired by dynamic self-assembly in biology, multiple studies have developed synthetic analogs of assemblies regulated by chemical chemically fueled reaction cycles. A challenge in most of these studies is that molecules assemble upon activation but do not disassemble upon deactivation. In other words, they remain kinetically trapped, and the resulting assemblies are not dynamic. In this work, we show how molecular design dictates the tendency of deactivated molecules to remain trapped in the assembled state. We also show how molecular design can be used to tune the dynamics of the reaction cycle. Our work should result in chemically fueled assemblies that are truly dynamic in that dis-assembly immediately follows deactivation.

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Section: Scheme 1 A) Scheme Of a Fuel-driven Reaction Cyclementioning

confidence: 99%

Kinetic traps in chemically fueled self-assembly and how to overcome them.

Kriebisch

Bergmann

et al. 2022

Preprint

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“…Dynamic light scattering (DLS) measurements demonstrated the presence of large assembled structures of aldehyde 1 even at [1]0 = 0.2 mM (Figure 4D). This suggests that the increase of [1]0 beyond 0.2 mM led to formation of more of assembled structures, while keeping the concentration of monomeric aldehyde nearly constant, because the self-assembly mechanism of this aldehyde is cooperative: 57 in the cooperative formation of supramolecular polymer, the concentration of a non-assembling monomer remains constant once the total monomer concentration exceeds the critical aggregation concentration. 58,59 Therefore, the increase of the catalysis rate at higher [1]0 is most likely the consequence of the increase in the amount of assembled structures, and we conclude that the catalysis of the fuel hydrolysis involves not only the monomeric aldehyde 1 but also their assemblies.…”

Section: Investigation Of the System's Mechanismmentioning

confidence: 99%

Repurposing a catalytic cycle for transient self-assembly

Amano,

Hermans

2024

Preprint

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Life operates out of equilibrium to enable various sophisticated behaviors. Synthetic chemists have strived to mimic biological non-equilibrium systems in such fields as autonomous molecular machines and dissipative self-assembly. Central to these efforts has been development of new chemical reaction cycles, which drive systems out of equilibrium by conversion of chemical fuel into waste species. However, construction of reaction cycles has been challenging due to the difficulty of finding compatible reactions that constitute a cycle. Here, we realized an alternative approach of repurposing a known catalytic cycle as a chemical reaction cycle for driving dissipative self-assembly. This approach can overcome the compatibility problem, because all steps involved in a catalytic cycle are already known to proceed concurrently under the same conditions. Our repurposing approach is applicable to diverse combinations of catalytic cycles and systems to drive out of equilibrium, which will substantially broaden the scope of out-of-equilibrium systems.

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“…As such, at higher GdL concentrations the authors observed a fast gel−sol−gel conversion, whereas at lower GdL concentrations, the sol state was maintained for much longer. In more recent work, 105 the authors looked at three chemically similar gelators and showed that self-assembly into fibers can shield monomers from deactivation (by dithionite).…”

Section: Literature Examplesmentioning

confidence: 99%

Insights into Chemically Fueled Supramolecular Polymers

et al. 2022

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Supramolecular polymerization can be controlled in space and time by chemical fuels. A nonassembled monomer is activated by the fuel and subsequently self-assembles into a polymer. Deactivation of the molecule either in solution or inside the polymer leads to disassembly. Whereas biology has already mastered this approach, fully artificial examples have only appeared in the past decade. Here, we map the available literature examples into four distinct regimes depending on their activation/deactivation rates and the equivalents of deactivating fuel. We present increasingly complex mathematical models, first considering only the chemical activation/deactivation rates (i.e., transient activation) and later including the full details of the isodesmic or cooperative supramolecular processes (i.e., transient self-assembly). We finish by showing that sustained oscillations are possible in chemically fueled cooperative supramolecular polymerization and provide mechanistic insights. We hope our models encourage the quantification of activation, deactivation, assembly, and disassembly kinetics in future studies.

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Chemically Fueled Self-sorted Hydrogels

Cited by 3 publications

References 28 publications

Kinetic traps in chemically fueled self-assembly and how to overcome them.

Kinetic traps in chemically fueled self-assembly and how to overcome them.

Repurposing a catalytic cycle for transient self-assembly

Insights into Chemically Fueled Supramolecular Polymers

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