Substrate‐Induced Self‐Assembly of Cooperative Catalysts

Muñana, Pablo Solís; Ragazzon, Giulio; Dupont, Julien; Ren, Chloe Z.‐J.; Prins, Leonard J.; Chen, Jack L.‐Y.

doi:10.1002/ange.201810891

Cited by 37 publications

(10 citation statements)

References 56 publications

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“…In the past, the close proximity of TACN⋅ Zn 2+ groups needed for catalysis have been achieved by their direct covalent attachment to dendrimers or immobilization onto nanoparticles . Recently, we demonstrated that cooperativity between TACN⋅ Zn 2+ groups can also be achieved within substrate‐induced vesicular assemblies . Marked differences in catalytic activity were observed between the non‐assembled state (at concentrations below the critical assembling concentration; CAC) and the assembled state (above the CAC).…”

Section: Figurementioning

confidence: 99%

Reversible Formation of a Light‐Responsive Catalyst by Utilizing Intermolecular Cooperative Effects

et al. 2019

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A photoresponsive system where structure formation is coupled to catalytic activity is presented. The observed catalytic activity is reliant on intermolecular cooperative effects that are present when amphiphiles assemble into vesicular structures. Photoresponsive units within the amphiphilic pre‐catalysts allow for switching between assembled and disassembled states, thereby modulating the catalytic activity. The ability to reversibly form cooperative catalysts within a dynamic self‐assembled system represents a conceptually new tool for the design of complex artificial systems in water.

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Section: Figurementioning

confidence: 99%

Reversible Formation of a Light‐Responsive Catalyst by Utilizing Intermolecular Cooperative Effects

et al. 2019

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“…52 Therefore, due to their ability to provide a hydrophobic environment, nanoscopic scale, chemical promiscuity, diffusional interactions, and polarity gradients, micelles have been widely exploited as models for microcompartments. In this regard, a number of dynamic systems presenting complex behavior have been reported: dissipative fueled self-assemblies of nanoreactors 53,54 with catalytic activities, 55,56 micelles based on the reversible self-assembly of imine-based surfactants, 57 amphiphilic imines 58 displaying self-replication 59 and autopoietic properties 60 as well as out-of-equilibrium self-replicating micelles, 61 able to generate autonomously supramolecular oscillations. 62 Autocatalysis and self-replication are essential for the organization and outcomes of both artificial 63−66 and biological 67,68 reaction networks.…”

Section: Introductionmentioning

confidence: 99%

Triple Adaptation of Constitutional Dynamic Networks of Imines in Response to Micellar Agents: Internal Uptake–Interfacial Localization–Shape Transition

Rieu,

Osypenko,

Lehn

2024

J. Am. Chem. Soc.

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Understanding the behavior of complex chemical reaction networks and how environmental conditions can modulate their organization as well as the associated outcomes may take advantage of the design of related artificial systems. Microenvironments with defined boundaries are of particular interest for their unique properties and prebiotic significance. Dynamic covalent libraries (DCvLs) and their underlying constitutional dynamic networks (CDNs) have been shown to be appropriate for studying adaptation to several processes, including compartmentalization. However, microcompartments (e.g., micelles) provide specific environments for the selective protection from interfering reactions such as hydrolysis and an enhanced chemical promiscuity due to the interface, governing different processes of network modulation. Different interactions between the micelles and the library constituents lead to dynamic sensing, resulting in different expressions of the network through pattern generation. The constituents integrated into the micelles are protected from hydrolysis and hence preferentially expressed in the network composition at the cost of constitutionally linked members. In the present work, micellar integration was observed for two processes: internal uptake based on hydrophobic forces and interfacial localization relying on attractive electrostatic interactions. The latter drives a complex triple adaptation of the network with feedback on the shape of the self-assembled entity. Our results demonstrate how microcompartments can enforce the expression of constituents of CDNs by reducing the hydrolysis of uptaken members, unravelling processes that govern the response of reactions networks. Such studies open the way toward using DCvLs and CDNs to understand the emergence of complexity within reaction networks by their interactions with microenvironments.

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“…A common approach for constructing new chemical reaction cycles is to combine multiple reactions (Figure 1A, Left). The individual reactions can be either catalytic [25][26][27][28][29][30][31][32][33][34] or non-catalytic, [35][36][37][38][39][40][41][42][43] and can incorporate enzymatic reactions. [44][45][46][47][48][49] With biomolecules such as nucleic acids and enzymes, high specificity can be achieved and multiple reactions proceed concurrently under the same conditions.…”

Section: Introductionmentioning

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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Substrate‐Induced Self‐Assembly of Cooperative Catalysts

Cited by 37 publications

References 56 publications

Reversible Formation of a Light‐Responsive Catalyst by Utilizing Intermolecular Cooperative Effects

Reversible Formation of a Light‐Responsive Catalyst by Utilizing Intermolecular Cooperative Effects

Triple Adaptation of Constitutional Dynamic Networks of Imines in Response to Micellar Agents: Internal Uptake–Interfacial Localization–Shape Transition

Repurposing a catalytic cycle for transient self-assembly

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