Correction: Fatty acids' double role in the prebiotic formation of a hydrophobic dipeptide
TL;DR: This work has shown that fatty acids have a double role in the prebiotic formation of a hydrophobic dipeptide and this role may be related to the role played by phosphorous and nitrogen in the phytochemical reaction.
Abstract: Correction for ‘Fatty acids' double role in the prebiotic formation of a hydrophobic dipeptide’ by Sara Murillo-Sanchez et al., Chem. Sci., 2016, DOI: 10.1039/c5sc04796j.
Citations
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16 Jul 2020
TL;DR: A review of the emerging field of chemical reactivity at aqueous interfaces can be found in this paper, where the basic theories intended to explain interface catalysis are presented. And the results of advanced ab initio molecular-dynamics simulations are discussed.
Abstract: This Review aims to critically analyse the emerging field of chemical reactivity at aqueous interfaces. The subject has evolved rapidly since the discovery of the so-called ‘on-water catalysis’, alluding to the dramatic acceleration of reactions at the surface of water or at its interface with hydrophobic media. We review critical experimental studies in the fields of atmospheric and synthetic organic chemistry, as well as related research exploring the origins of life, to showcase the importance of this phenomenon. The physico-chemical aspects of these processes, such as the structure, dynamics and thermodynamics of adsorption and solvation processes at aqueous interfaces, are also discussed. We also present the basic theories intended to explain interface catalysis, followed by the results of advanced ab initio molecular-dynamics simulations. Although some topics addressed here have already been the focus of previous reviews, we aim at highlighting their interconnection across diverse disciplines, providing a common perspective that would help us to identify the most fundamental issues still incompletely understood in this fast-moving field. Enhanced chemical reactivity on-water has major implications in many fields, ranging from atmospheric to prebiotic chemistry. This Review analyses recent experimental and theoretical studies in this fast-moving research area and brings together some key findings across diverse fields.
103 citations
TL;DR: A review of some recent advances that suggest that canonical metabolites are predisposed chemical structures suggests unprecedented scope for exploration of the origins of life and an exciting new perspective on a four-billion-year-old problem.
98 citations
01 Oct 2018
TL;DR: In this article, the authors illustrate the general concepts applied in such systems and illustrate them with selected examples, ranging from enzyme mimics, the preparation of conductive polymers and transition-metal-catalysed organic syntheses on the industrial scale to the chemistry of prebiotic systems.
Abstract: Although aqueous solutions are considered to be sustainable, environmentally friendly reaction media, their use is often limited by poor reactant solubility. This limitation can be overcome by converting aqueous solutions into soft, dispersed interface-rich systems such as polyelectrolyte solutions, micellar solutions, oil-in-water microemulsions or vesicle dispersions. All consist of homogeneously distributed dynamic structures that, in a fashion reminiscent of enzymes, provide local environments that are different from the bulk solution. The presence of soft, dispersed interface-rich structures leads to not only selective reaction accelerations but also changes in reaction pathways, whereby chemical reactions are guided towards desired products. Once again, the analogy to enzyme-catalysed transformations is enticing. In this Review, we illustrate the general concepts applied in such systems and illustrate them with selected examples, ranging from enzyme mimics, the preparation of conductive polymers and transition-metal-catalysed organic syntheses on the industrial scale to the chemistry of prebiotic systems. Aqueous media containing homogeneously distributed soft dynamic structures can promote a wide range of synthetic and degradative chemical reactions. This promotion is illustrated by selected examples from academia and industry, as well as from the field of prebiotic chemistry.
78 citations
TL;DR: It is found that amino acids, the building blocks of proteins, bind to fatty acid membranes and stabilize them against salts, and enhanced stabilization persists after dilution as would occur when a dehydrated pool refills with water—a likely setting for the emergence of cells.
Abstract: The membranes of the first protocells on the early Earth were likely self-assembled from fatty acids. A major challenge in understanding how protocells could have arisen and withstood changes in their environment is that fatty acid membranes are unstable in solutions containing high concentrations of salt (such as would have been prevalent in early oceans) or divalent cations (which would have been required for RNA catalysis). To test whether the inclusion of amino acids addresses this problem, we coupled direct techniques of cryoelectron microscopy and fluorescence microscopy with techniques of NMR spectroscopy, centrifuge filtration assays, and turbidity measurements. We find that a set of unmodified, prebiotic amino acids binds to prebiotic fatty acid membranes and that a subset stabilizes membranes in the presence of salt and Mg2+ Furthermore, we find that final concentrations of the amino acids need not be high to cause these effects; membrane stabilization persists after dilution as would have occurred during the rehydration of dried or partially dried pools. In addition to providing a means to stabilize protocell membranes, our results address the challenge of explaining how proteins could have become colocalized with membranes. Amino acids are the building blocks of proteins, and our results are consistent with a positive feedback loop in which amino acids bound to self-assembled fatty acid membranes, resulting in membrane stabilization and leading to more binding in turn. High local concentrations of molecular building blocks at the surface of fatty acid membranes may have aided the eventual formation of proteins.
68 citations
TL;DR: A concrete proposal for the set of molecular control mechanisms that must be coupled to bring about autonomous functional systems, at the interface between chemistry and biology, is provided.
Abstract: In recent years, an extension of the Darwinian framework is being considered for the study of prebiotic chemical evolution, shifting the attention from homogeneous populations of naked molecular species to populations of heterogeneous, compartmentalized and functionally integrated assemblies of molecules. Several implications of this shift of perspective are analysed in this critical review, both in terms of the individual units, which require an adequate characterization as self-maintaining systems with an internal organization, and also in relation to their collective and long-term evolutionary dynamics, based on competition, collaboration and selection processes among those complex individuals. On these lines, a concrete proposal for the set of molecular control mechanisms that must be coupled to bring about autonomous functional systems, at the interface between chemistry and biology, is provided.
57 citations
References
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16 Jul 2020
TL;DR: A review of the emerging field of chemical reactivity at aqueous interfaces can be found in this paper, where the basic theories intended to explain interface catalysis are presented. And the results of advanced ab initio molecular-dynamics simulations are discussed.
Abstract: This Review aims to critically analyse the emerging field of chemical reactivity at aqueous interfaces. The subject has evolved rapidly since the discovery of the so-called ‘on-water catalysis’, alluding to the dramatic acceleration of reactions at the surface of water or at its interface with hydrophobic media. We review critical experimental studies in the fields of atmospheric and synthetic organic chemistry, as well as related research exploring the origins of life, to showcase the importance of this phenomenon. The physico-chemical aspects of these processes, such as the structure, dynamics and thermodynamics of adsorption and solvation processes at aqueous interfaces, are also discussed. We also present the basic theories intended to explain interface catalysis, followed by the results of advanced ab initio molecular-dynamics simulations. Although some topics addressed here have already been the focus of previous reviews, we aim at highlighting their interconnection across diverse disciplines, providing a common perspective that would help us to identify the most fundamental issues still incompletely understood in this fast-moving field. Enhanced chemical reactivity on-water has major implications in many fields, ranging from atmospheric to prebiotic chemistry. This Review analyses recent experimental and theoretical studies in this fast-moving research area and brings together some key findings across diverse fields.
103 citations
TL;DR: A review of some recent advances that suggest that canonical metabolites are predisposed chemical structures suggests unprecedented scope for exploration of the origins of life and an exciting new perspective on a four-billion-year-old problem.
98 citations
01 Oct 2018
TL;DR: In this article, the authors illustrate the general concepts applied in such systems and illustrate them with selected examples, ranging from enzyme mimics, the preparation of conductive polymers and transition-metal-catalysed organic syntheses on the industrial scale to the chemistry of prebiotic systems.
Abstract: Although aqueous solutions are considered to be sustainable, environmentally friendly reaction media, their use is often limited by poor reactant solubility. This limitation can be overcome by converting aqueous solutions into soft, dispersed interface-rich systems such as polyelectrolyte solutions, micellar solutions, oil-in-water microemulsions or vesicle dispersions. All consist of homogeneously distributed dynamic structures that, in a fashion reminiscent of enzymes, provide local environments that are different from the bulk solution. The presence of soft, dispersed interface-rich structures leads to not only selective reaction accelerations but also changes in reaction pathways, whereby chemical reactions are guided towards desired products. Once again, the analogy to enzyme-catalysed transformations is enticing. In this Review, we illustrate the general concepts applied in such systems and illustrate them with selected examples, ranging from enzyme mimics, the preparation of conductive polymers and transition-metal-catalysed organic syntheses on the industrial scale to the chemistry of prebiotic systems. Aqueous media containing homogeneously distributed soft dynamic structures can promote a wide range of synthetic and degradative chemical reactions. This promotion is illustrated by selected examples from academia and industry, as well as from the field of prebiotic chemistry.
78 citations
TL;DR: It is found that amino acids, the building blocks of proteins, bind to fatty acid membranes and stabilize them against salts, and enhanced stabilization persists after dilution as would occur when a dehydrated pool refills with water—a likely setting for the emergence of cells.
Abstract: The membranes of the first protocells on the early Earth were likely self-assembled from fatty acids. A major challenge in understanding how protocells could have arisen and withstood changes in their environment is that fatty acid membranes are unstable in solutions containing high concentrations of salt (such as would have been prevalent in early oceans) or divalent cations (which would have been required for RNA catalysis). To test whether the inclusion of amino acids addresses this problem, we coupled direct techniques of cryoelectron microscopy and fluorescence microscopy with techniques of NMR spectroscopy, centrifuge filtration assays, and turbidity measurements. We find that a set of unmodified, prebiotic amino acids binds to prebiotic fatty acid membranes and that a subset stabilizes membranes in the presence of salt and Mg2+ Furthermore, we find that final concentrations of the amino acids need not be high to cause these effects; membrane stabilization persists after dilution as would have occurred during the rehydration of dried or partially dried pools. In addition to providing a means to stabilize protocell membranes, our results address the challenge of explaining how proteins could have become colocalized with membranes. Amino acids are the building blocks of proteins, and our results are consistent with a positive feedback loop in which amino acids bound to self-assembled fatty acid membranes, resulting in membrane stabilization and leading to more binding in turn. High local concentrations of molecular building blocks at the surface of fatty acid membranes may have aided the eventual formation of proteins.
68 citations
TL;DR: A concrete proposal for the set of molecular control mechanisms that must be coupled to bring about autonomous functional systems, at the interface between chemistry and biology, is provided.
Abstract: In recent years, an extension of the Darwinian framework is being considered for the study of prebiotic chemical evolution, shifting the attention from homogeneous populations of naked molecular species to populations of heterogeneous, compartmentalized and functionally integrated assemblies of molecules. Several implications of this shift of perspective are analysed in this critical review, both in terms of the individual units, which require an adequate characterization as self-maintaining systems with an internal organization, and also in relation to their collective and long-term evolutionary dynamics, based on competition, collaboration and selection processes among those complex individuals. On these lines, a concrete proposal for the set of molecular control mechanisms that must be coupled to bring about autonomous functional systems, at the interface between chemistry and biology, is provided.
57 citations