Designed Negative Feedback from Transiently Formed Catalytic Nanostructures

Abstract

Highly dynamic and complex systems of microtubules undergo a substrate‐induced change of conformation that leads to polymerization. Owing to the augmented catalytic potential at the polymerized state, rapid hydrolysis of the substrate is observed, leading to catastrophe, thus realizing the out‐of‐equilibrium state. A simple synthetic mimic of these dynamic natural systems is presented, where similar substrate induced conformational change is observed and a transient helical morphology is accessed. Further, augmented catalytic potential of these helical nanostructures leads to rapid hydrolysis of the substrate providing negative feedback on the stability of the nanostructures and realization of an out‐of‐equilibrium state. This simple system, made from amino acid functionalized lipids, demonstrates a substrate‐induced self‐assembled state, where the fuel‐to‐waste conversion leads to the temporal presence of helical nanostructures.

On the use of catalysis to bias reaction pathways in out-of-equilibrium systems

“…The analogy to microtubules is also exemplied in follow-up works where the system shows designed negative feedback from the assembled structure, even harnessing temporal regulation of crossb amyloid network electronic properties. 27,28 Although this example from Das relies on organocatalysis, it is distinctly different from the simulation described here, because the catalyst (i.e. the histidine moiety) is integrated in the transient product.…”

“…Moreover, coupling catalysis to a dissipative CRN containing assembling products could give rise to unusual assembly behaviour and feedback. [26][27][28]44 Here, instead of using enzymes, with limited operational stability and high specicity, it would be recommended to start exploring small molecules and metal catalysts. This way organocatalysis in combination with metal catalysis in non-natural systems can play similar roles as enzymes in nature and provide new systems with a high degree of control and an adaptive character.…”

Non-Equilibrium Generation of Catalytic Supramolecular Polymers of Pre-RNA Nucleobases

“…1,3,8,9 To support a general theory of biopolymer evolution that predated the emergence of life working far from equilibrium, a systems chemistry approach is essential to study a relatively simple set of monomers under a flux of energy and subsequently probe the possibility of generation of complex oligomers with useful and emergent properties such as catalysis. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] Far from equilibrium behaviour involving repeated breaking and making of such simple precursors can result in temporal generation of aggregated structures with emergent functions which in principle could have assisted in selection and adaptation. 3,8 Herein, we show the dissipative self-assembly of supramolecular polymers of proto-RNA building blocks based on melamine that is driven by a thermodynamically activated ester.…”

“…One of the important prerequisites of non-equilibrium dissipative self-assembly is the installation of kinetic asymmetry in energy consumption pathways that necessitates dissipation of energy predominantly from the high-energy assembled state. 8,17,19,24,[26][27][28][29] For this purpose, we first investigated the rates of hydrolysis of MB* in presence of ImCHO only. Expectedly, due to the presence of imidazole moiety, we observed a modest hydrolytic rate of 0.59 ± 0.3 M.min -1 .…”

Emergence of a Promiscuous Peroxidase Under Non-Equilibrium Conditions

“…10 From the context of chemical origin of life working far from equilibrium, it is tempting to investigate mixtures of simple molecules under a flux of energy and subsequently probe the emergence of primitive catalytic machineries with latent functions that could be important for early metabolism. [18][19][20][21][22][23][24][25][26][27][28][29][30] Herein, we show substrate driven generation of an artificial peroxidase via the dissipative self-assembly of a minimal amphiphile in presence of a cofactor (hemin) in an oxidizing environment (Fig. 1).…”