Thermodynamic efficiency in dissipative chemistry

Penocchio, Emanuele; Rao, Riccardo; Esposito, Massimiliano

doi:10.1038/s41467-019-11676-x

Cited by 62 publications

(85 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The structure of such nonequilibrium systems is not a dissipative structure, according to Prigogine [3]. In this context, the supplied energy is consumed to sustain the assembly, but not for autonomous tasks [88,89]. To imitate living dynamics clearly, we have to employ one or more symmetry-breaking effects to replace the system from the equilibrium structure at the tentative state to a nonequilibrium resume [90]; according to Chapter 7 in reference 3 and the references therein, at least a cubic nonlinearity in the rate equations is required to destabilize the thermodynamic branch.…”

Section: Discussionmentioning

confidence: 99%

Robust Dynamics of Synthetic Molecular Systems as a Consequence of Broken Symmetry

Kageyama

2020

Symmetry

View full text Add to dashboard Cite

The construction of molecular robot-like objects that imitate living things is an important challenge for current chemists. Such molecular devices are expected to perform their duties robustly to carry out mechanical motion, process information, and make independent decisions. Dissipative self-organization plays an essential role in meeting these purposes. To produce a micro-robot that can perform the above tasks autonomously as a single entity, a function generator is required. Although many elegant review articles featuring chemical devices that mimic biological mechanical functions have been published recently, the dissipative structure, which is the minimum requirement for mimicking these functions, has not been sufficiently discussed. This article aims to show clearly that dissipative self-organization is a phenomenon involving autonomy, robustness, mechanical functions, and energy transformation. Moreover, it reports the results of recent experiments with an autonomous light-driven molecular device that achieves all of these features. In addition, a chemical model of cell-amplification is also discussed to focus on the generation of hierarchical movement by dissipative self-organization. By reviewing this research, it may be perceived that mainstream approaches to synthetic chemistry have not always been appropriate. In summary, the author proposes that the integration of catalytic functions is a key issue for the creation of autonomous microarchitecture.

show abstract

Section: Discussionmentioning

confidence: 99%

Robust Dynamics of Synthetic Molecular Systems as a Consequence of Broken Symmetry

Kageyama

2020

Symmetry

View full text Add to dashboard Cite

show abstract

“…[3,86] In this context, the supplied energy is consumed to sustain the assembly, but not for autonomous tasks. [87,88] To imitate the living dynamics clearly, we have to employ one or more symmetrybreaking effects to replace the system from the equilibrium structure at the tentative state to a nonequilibrium resume.…”

Section: Discussionmentioning

confidence: 99%

Robust Dynamics of Synthetic Molecular Systems as A Consequence of Broken Symmetry

Kageyama¹

2020

Preprint

View full text Add to dashboard Cite

The construction of molecular robotic-like objects that imitate living things is an important challenge for current chemists. Such molecular devices are expected to perform their duties robustly to carry out mechanical motion, process information, and make independent decisions. Dissipative self-organization plays an essential role in meeting these purposes. To produce a micro-robot that can perform the above tasks autonomously as a single entity, a function generator is required. Although many elegant review articles featuring chemical devices that mimic biological mechanical functions have been published recently, the dissipative structure, which is the minimum requirement, has not been sufficiently discussed. This article aims to show clearly that dissipative self-organization is a phenomenon involving autonomy, robustness, mechanical functions, and energy transformation. Moreover, the author details the recent experimental results of an autonomous light-driven molecular device that achieves all of these features. In addition, a chemical model of cell-amplification is also discussed to focus on the generation of hierarchical movement by dissipative self-organization. By reviewing this research, it may be perceived that mainstream approaches to synthetic chemistry have not always been appropriate. In summary, the author proposes that the integration of catalytic functions is a key issue for the creation of autonomous microarchitecture.

show abstract

“…The imidazole functionalized melamine via a dynamic bond demonstrated acceleration of hydrolytic ability and subsequent dissipation from assembled state, thus installing kinetic asymmetry in the energy consumption pathways. 8,[26][27][28][29] As thermodynamically uphill polymerization in biology is accessed by activated ester, we started our investigation with the 4-nitrophenol (PNP) ester (MB*) of an organic acid (4-hydroxy-3methoxybenzoic acid, MB) as the activated monomer. Melamine (MM) was used as the building block as it has been argued as the precursor of modern nucleobases (Fig.…”

Section: Non-equilibrium Generation Of Catalytic Supramolecular Polymers Of Pre-rna Nucleobasesmentioning

confidence: 99%

“…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 .…”

Section: Non-equilibrium Generation Of Catalytic Supramolecular Polymers Of Pre-rna Nucleobasesmentioning

confidence: 99%

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

Afrose¹,

Mahato²,

Sharma³

et al. 2021

Preprint

View full text Add to dashboard Cite

<p>Bioenergetics played critical roles for the chemical emergence of life where available energy resources drove the generation of primitive polymers and fueled early metabolism. Further, apart from information storage, the catalytic roles of primitive nucleic acid fragments have also been argued to be important for biopolymer evolution. Herein, we have demonstrated the non-equilibrium generation of catalytic supramolecular polymers of a possible proto-RNA building block (melamine) driven by a thermodynamically activated ester of low molecular weight. We utilized reversible covalent linkage to install a catalytic imidazole moiety in the polymer backbone. This resulted in energy dissipation via hydrolysis of the substrate predominantly from the assembled state and subsequent disassembly, thus installing kinetic asymmetry in the energy consumption cycle. Non-catalytic analogues led to kinetically stable polymers while inactivated substrates were unable to drive the polymerization. The non-equilibrium polymers of the pre-RNA bases were capable to spatiotemporally bind to a model cofactor. Notably, presence of an exogenous aromatic base augmented the stability of the polymers, reminiscent to what the molecular midwives did during early evolution. </p>

show abstract

Thermodynamic efficiency in dissipative chemistry

Cited by 62 publications

References 23 publications

Robust Dynamics of Synthetic Molecular Systems as a Consequence of Broken Symmetry

Robust Dynamics of Synthetic Molecular Systems as a Consequence of Broken Symmetry

Robust Dynamics of Synthetic Molecular Systems as A Consequence of Broken Symmetry

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

Contact Info

Product

Resources

About