Density-tunable pathway complexity in a minimalistic self-assembly model

Becchi, Matteo; Capelli, Riccardo; Perego, Claudio; Pavan, Giovanni M.; Micheletti, Cristian

doi:10.1039/d2sm00968d

“…Biomimicking the benefits of nonequilibrium drive has attracted great technological interest, with numerous demonstrations such as artificial light-harvesting systems, natural viral capsids, , target-specific delivery of drugs and genes, , formation of supramolecular hydrogels, ,− colloidal diamond photonic crystals, and more. ,,,− Realizing a nonequilibrium self-assembly system would further benefit from control protocols that could assist in navigating the system to the desired target while monitoring its state over time. ,,,− Nevertheless, experimental realizations of these protocols are challenging and require quantitative, coarse-grained observables of the self-assembly process. ,, The time to the first self-assembly can be viewed from the perspective of a mean-first passage time problem, − where control protocols generally aim to reduce the assembly time. Previous works have examined this analogy to study first self-assembly times. − …”

Section: Introductionmentioning

confidence: 99%

Nonequilibrium Self-Assembly Time Forecasting by the Stochastic Landscape Method

Faran

¹

,

Bisker

²

2023

J. Phys. Chem. B

6

0

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Many biological systems rely on the ability to self-assemble target structures from different molecular building blocks using nonequilibrium drives, stemming, for example, from chemical potential gradients. The complex interactions between the different components give rise to a rugged energy landscape with a plethora of local minima on the dynamic pathway to the target assembly. Exploring a toy physical model of multicomponents nonequilibrium self-assembly, we demonstrate that a segmented description of the system dynamics can be used to provide predictions of the first assembly times. We show that for a wide range of values of the nonequilibrium drive, a log-normal distribution emerges for the first assembly time statistics. Based on data segmentation by a Bayesian estimator of abrupt changes (BEAST), we further present a general data-based algorithmic scheme, namely, the stochastic landscape method (SLM), for assembly time predictions. We demonstrate that this scheme can be implemented for the first assembly time forecast during a nonequilibrium self-assembly process, with improved prediction power compared to a naïve guess based on the mean remaining time to the first assembly. Our results can be used to establish a general quantitative framework for nonequilibrium systems and to improve control protocols of nonequilibrium self-assembly processes.

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Complex Pathways Drive Pluripotent Fmoc‐Leucine Self‐Assemblies

Paul,

Gayen,

Cantavella

et al. 2024

Angewandte Chemie

0

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Nature uses complex self‐assembly pathways to access distinct functional non‐equilibrium self‐assemblies. This remarkable ability to steer same set of biomolecules into different self‐assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over ‘Pathway Complexity’ to access self‐assemblies different from equilibrium structures remains challenging. Here we show versatile non‐equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non‐classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)‐crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft‐materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self‐assembly states can find potential use in similar biomimetic systems to access new materials for various applications.

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Complex Pathways Drive Pluripotent Fmoc‐Leucine Self‐Assemblies

Paul,

Gayen,

Cantavella

et al. 2024

Angew Chem Int Ed

1

0

View full text Add to dashboard Cite

Nature uses complex self‐assembly pathways to access distinct functional non‐equilibrium self‐assemblies. This remarkable ability to steer same set of biomolecules into different self‐assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over ‘Pathway Complexity’ to access self‐assemblies different from equilibrium structures remains challenging. Here we show versatile non‐equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non‐classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)‐crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft‐materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self‐assembly states can find potential use in similar biomimetic systems to access new materials for various applications.

show abstract

Density-tunable pathway complexity in a minimalistic self-assembly model

Abstract: An open challenge in self-assembly is learning how to design systems that can be conditionally guided towards different target structures depending on externally-controlled conditions. Using a theoretical and numerical approach,...

Cited by 6 publications

References 88 publications

Nonequilibrium Self-Assembly Time Forecasting by the Stochastic Landscape Method

Nonequilibrium Self-Assembly Time Forecasting by the Stochastic Landscape Method

Complex Pathways Drive Pluripotent Fmoc‐Leucine Self‐Assemblies

Complex Pathways Drive Pluripotent Fmoc‐Leucine Self‐Assemblies

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