scholarly journals Organocatalytic Control over a Fuel-Driven Transient Esterification Network

2020 ◽  
Author(s):  
Michelle van der Helm ◽  
Chang-Lin Wang ◽  
Mariano Macchione ◽  
Eduardo Mendes ◽  
Rienk Eelkema
Keyword(s):  
Chemical Change ◽  
Polymer System ◽  
Reaction Networks ◽  
Polymer Conformation ◽  
Controlled Processes ◽  
Full Control ◽  
Ester Formation ◽  
Driven System ◽  
Ester Yield ◽  
Non Equilibrium

<p>Signal transduction in living systems is the conversion of information into a chemical change and the principal process by which cells communicate. This process enables phenomena such as time-keeping and signal amplification. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. While these catalytically controlled processes are an integral part of biocatalytic pathways, man-made analogs are rare. Here, we incorporate catalysis in an artificial fuel driven out-of-equilibrium CRN. The study entails the design of an organocatalytically controlled fuel driven esterification CRN, where the forward (ester formation) and backward reaction (ester hydrolysis) are controlled by varying the ratio of two different organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. The fuel-driven strategy is subsequently used in the design of a responsive polymer system, where transient polymer conformation and aggregation can be controlled through variation of fuel and catalysts levels. Altogether, we show how organocatalysis is an important tool to exert control over a man-made fuel driven system and induce a change in a macromolecular superstructure, as ubiquitously found in natural non-equilibrium systems. </p>

scholarly journals Organocatalytic Control over a Fuel-Driven Transient Esterification Network

2020 ◽  
Author(s):  
Michelle van der Helm ◽  
Chang-Lin Wang ◽  
Mariano Macchione ◽  
Eduardo Mendes ◽  
Rienk Eelkema
Keyword(s):  
Chemical Change ◽  
Polymer System ◽  
Reaction Networks ◽  
Polymer Conformation ◽  
Controlled Processes ◽  
Full Control ◽  
Ester Formation ◽  
Driven System ◽  
Ester Yield ◽  
Non Equilibrium

<p>Signal transduction in living systems is the conversion of information into a chemical change and the principal process by which cells communicate. This process enables phenomena such as time-keeping and signal amplification. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. While these catalytically controlled processes are an integral part of biocatalytic pathways, man-made analogs are rare. Here, we incorporate catalysis in an artificial fuel driven out-of-equilibrium CRN. The study entails the design of an organocatalytically controlled fuel driven esterification CRN, where the forward (ester formation) and backward reaction (ester hydrolysis) are controlled by varying the ratio of two different organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. The fuel-driven strategy is subsequently used in the design of a responsive polymer system, where transient polymer conformation and aggregation can be controlled through variation of fuel and catalysts levels. Altogether, we show how organocatalysis is an important tool to exert control over a man-made fuel driven system and induce a change in a macromolecular superstructure, as ubiquitously found in natural non-equilibrium systems. </p>

scholarly journals Parasitic Behavior in Competing Chemically Fueled Reaction Cycles

2021 ◽  
Author(s):  
Patrick S. Schwarz ◽  
Sudarshana Laha ◽  
Jacqueline Janssen ◽  
Tabea Huss ◽  
Job Boekhoven ◽  
...  
Keyword(s):  
Dynamic Behavior ◽  
Model Systems ◽  
Reaction Networks ◽  
Reaction Cycles ◽  
Non Equilibrium

Non-equilibrium, fuel-driven reaction cycles serve as model systems of the intricate reaction networks of life. Rich and dynamic behavior is observed when reaction cycles regulate assembly processes, such as phase...

scholarly journals Behavior of Floquet Topological Quantum States in Optically Driven Semiconductors

2019 ◽  
Author(s):  
Andreas Lubatsch ◽  
Regine Frank
Keyword(s):  
Mean Field Theory ◽  
Mean Field ◽  
Three Dimensional ◽  
Quantum States ◽  
Topological Quantum ◽  
Driven System ◽  
Generalized Hubbard Model ◽  
Physical Impact ◽  
Physical Consequences ◽  
Non Equilibrium

Spatially uniform optical excitations can induce Floquet topological band structures within insulators which can develop similar or equal characteristics as are known from three-dimensional topological insulators. We derive in this article theoretically the development of Floquet topological quantum states for electromagnetically driven semiconductor bulk matter and we present results for the lifetime of these states and their occupation in the non-equilibrium. The direct physical impact of the mathematical precision of the Floquet-Keldysh theory is evident when we solve the driven system of a generalized Hubbard model with our framework of dynamical mean field theory (DMFT) in the non-equilibrium for a case of ZnO. The physical consequences of the topological non-equilibrium effects in our results for correlated systems are explained with their impact on optoelectronic applications.

scholarly journals Behavior of Floquet Topological Quantum States in Optically Driven Semiconductors

Symmetry ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1246 ◽  
Author(s):  
Andreas Lubatsch ◽  
Regine Frank
Keyword(s):  
Mean Field Theory ◽  
Mean Field ◽  
Three Dimensional ◽  
Quantum States ◽  
Topological Quantum ◽  
Driven System ◽  
Generalized Hubbard Model ◽  
Physical Impact ◽  
Physical Consequences ◽  
Non Equilibrium

Spatially uniform optical excitations can induce Floquet topological band structures within insulators which can develop similar or equal characteristics as are known from three-dimensional topological insulators. We derive in this article theoretically the development of Floquet topological quantum states for electromagnetically driven semiconductor bulk matter and we present results for the lifetime of these states and their occupation in the non-equilibrium. The direct physical impact of the mathematical precision of the Floquet-Keldysh theory is evident when we solve the driven system of a generalized Hubbard model with our framework of dynamical mean field theory (DMFT) in the non-equilibrium for a case of ZnO. The physical consequences of the topological non-equilibrium effects in our results for correlated systems are explained with their impact on optoelectronic applications.

scholarly journals Chemical Basis of Biological Homochirality during the Abiotic Evolution Stages on Earth

Symmetry ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 814 ◽  
Author(s):  
Josep M. Ribó ◽  
David Hochberg
Keyword(s):  
Symmetry Breaking ◽  
Chemical Evolution ◽  
Mirror Symmetry ◽  
Reaction Network ◽  
Reaction Networks ◽  
Stationary States ◽  
Cell Systems ◽  
Basic Model ◽  
Stochastic Distribution ◽  
Non Equilibrium

Spontaneous mirror symmetry breaking (SMSB), a phenomenon leading to non-equilibrium stationary states (NESS) that exhibits biases away from the racemic composition is discussed here in the framework of dissipative reaction networks. Such networks may lead to a metastable racemic non-equilibrium stationary state that transforms into one of two degenerate but stable enantiomeric NESSs. In such a bifurcation scenario, the type of the reaction network, as well the boundary conditions, are similar to those characterizing the currently accepted stages of emergence of replicators and autocatalytic systems. Simple asymmetric inductions by physical chiral forces during previous stages of chemical evolution, for example in astrophysical scenarios, must involve unavoidable racemization processes during the time scales associated with the different stages of chemical evolution. However, residual enantiomeric excesses of such asymmetric inductions suffice to drive the SMSB stochastic distribution of chiral signs into a deterministic distribution. According to these features, we propose that a basic model of the chiral machinery of proto-life would emerge during the formation of proto-cell systems by the convergence of the former enantioselective scenarios.

scholarly journals Reaction Networks as Systems for Resource Allocation: A Variational Principle for Their Non-Equilibrium Steady States

PLoS ONE ◽  
2012 ◽  
Vol 7 (7) ◽  
pp. e39849 ◽  
Author(s):  
Andrea De Martino ◽  
Daniele De Martino ◽  
Roberto Mulet ◽  
Guido Uguzzoni
Keyword(s):  
Resource Allocation ◽  
Variational Principle ◽  
Steady States ◽  
Reaction Networks ◽  
Non Equilibrium

Chemical Change in Deforming Materials

1993 ◽  
Author(s):  
Brian Bayly
Keyword(s):  
Stress State ◽  
Elementary Mathematics ◽  
Chemical Potential ◽  
Chemical Change ◽  
Technical Literature ◽  
Chemical Changes ◽  
Viscous Deformation ◽  
Macroscopic Level ◽  
Fundamental Understanding ◽  
Non Equilibrium

This book is the first to detail the chemical changes that occur in deforming materials subjected to unequal compressions. While thermodynamics provides, at the macroscopic level, an excellent means of understanding and predicting the behavior of materials in equilibrium and non-equilibrium states, much less is understood about nonhydrostatic stress and interdiffusion at the chemical level. Little is known, for example, about the chemistry of a state resulting from a cylinder of deforming material being more strongly compressed along its length than radially, a state of non-equilibrium that remains no matter how ideal the cylinder's condition in other respects. M. Brian Bayly here provides the outline of a comprehensive approach to gaining a simplified and unified understanding of such phenomena. The author's perspective differs from those commonly found in the technical literature in that he emphasizes two little-used equations that allow for a description and clarification of viscous deformation at the chemical level. Written at a level that will be accessible to many non-specialists, this book requires only a fundamental understanding of elementary mathematics, the nonhydrostatic stress state, and chemical potential. Geochemists, petrologists, structural geologists, and materials scientists will find Chemical Change in Deforming Materials interesting and useful.

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