Organocatalytic Control over a Fuel‐Driven Transient‐Esterification Network**

Helm, Michelle P. van der; Wang, Chang‐Lin; Fan, Boyu; Macchione, Mariano; Mendes, Eduardo; Eelkema, Rienk

doi:10.1002/ange.202008921

Cited by 10 publications

(3 citation statements)

References 60 publications

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“…We will limit our analysis to one-dimensional supramolecular polymers in homogeneous environments but include literature examples that are somewhat broader. In particular, we would like to point the reader to many other efforts addressing higher dimensional systems such as vesicles, nanoparticles, nanoparticle superlattices, DNA origami, etc. − Before going into detail in sections –, we first explain what we mean by “coupling” and introduce the important processes needed later on.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

confidence: 99%

Insights into Chemically Fueled Supramolecular Polymers

et al. 2022

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“…Examples include a rotaxane molecular shuttle capable of catalyzing a transfer hydrogenation process in the activated state, reached by the addition of pulses of trichloroacetic acid, [23] and an out‐of‐equilibrium cyclic reaction network, temporarily activated to generate transient host−guest complexes to control catalytic activity [24] . Catalysis has also been incorporated as control switches into cyclic reaction networks, allowing control of yields and lifetimes of the transient species via variation of the ratio of catalysts for the forward and backward reactions [25,26] …”

Section: Introductionmentioning

confidence: 99%

Dissipative Cyclic Reaction Networks: Mechanistic Insights into a Minor Enantiomer Recycling Process

Margarita,

Nash,

Ahlstrand

et al. 2023

ChemSystemsChem

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An analysis of an out‐of‐equilibrium cyclic reaction network which continuously converts a minor undesired product enantiomer to the desired major enantiomer by irreversible addition of chemical fuel and irreversible elimination of spent fuel is presented. The reaction network is maintained as long as fuel is added; interrupted fuel addition drives the system towards equilibrium, but the cyclic process restarts upon resumed fuel addition, as demonstrated by three consecutive fuel cycles. The process is powered by the hydrolysis of methyl cyanoformate to HCN and monomethyl carbonic acid, which decomposes to CO2 and MeOH. The time it takes to reach steady state depends on the rate of conversion of the fuel and decreases with increased conversion rate. Three catalysts, one metal catalyst and two enzymes, together constitute an efficient regulation system allowing control of the forward, backward and waste‐forming steps, thereby assuring the production of high yields of products with high enantiopurity.

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“…By taking inspiration from nature, there has been significant progress in the design of relatively simple, chemically fueled self‐assemblies using CRNs and ERNs based on a diversity of fuels, building blocks and approaches [10–23] . However, connecting different fuel‐driven modules and achieving cross‐regulation is challenging.…”

Section: Introductionmentioning

confidence: 99%

Communication and Cross‐Regulation between Chemically Fueled Sender and Receiver Reaction Networks**

2022

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Nature connects multiple fuel-driven chemical/enzymatic reaction networks (CRNs/ERNs) via cross-regulation to hierarchically control biofunctions for a tailored adaption in complex sensory landscapes. Herein, we introduce a facile example of communication and cross-regulation among two fuel-driven DNA-based ERNs regulated by a concatenated RNA transcription regulator. ERN1 ("sender") is designed for the fuel-driven promoter formation for T7 RNA polymerase, which activates RNA transcription. The produced RNA can deactivate or activate DNA in ERN2 ("receiver") by toehold-mediated strand displacement, leading to a communication between two ERNs. The RNA from ERN1 can repress or promote the fuel-driven state of ERN2; ERN2 in turn feedbacks to regulate the lifetime of ERN1. Furthermore, the incorporation of RNase H allows for RNA degradation and enables the autonomous recovery of ERN2. We believe that concatenation of multiple CRNs/ERNs provides a basis for the design of more elaborate autonomous regulatory mechanisms in systems chemistry and synthetic biology.

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Organocatalytic Control over a Fuel‐Driven Transient‐Esterification Network**

Cited by 10 publications

References 60 publications

Insights into Chemically Fueled Supramolecular Polymers

Insights into Chemically Fueled Supramolecular Polymers

Dissipative Cyclic Reaction Networks: Mechanistic Insights into a Minor Enantiomer Recycling Process

Communication and Cross‐Regulation between Chemically Fueled Sender and Receiver Reaction Networks**

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