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Thermodynamic Dissipation Theory of the Origin and Evolution of Life: Salient characteristics of RNA and DNA and other fundamental molecules suggest an origin of life driven by UV-C light

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... The fact that a very small amount of free energy available in sunlight is not instantly dissipated by ecosystems, and instead is stored for different amounts of time, has no bearing on the point under discussion concerning whether or not pigments, life, and ecosystems arose as a result of the thermodynamic imperative of photon dissipation. Storage of free energy for later use is, of course, necessary for maintaining the different trophic levels of an ecosystem, and this hierarchy can be shown to improve global photon dissipation (Michaelian, 2016). ...
... He ignores the other components involved in photon dissipation in vegetation mentioned in our original article and abstract: (1) the shift towards the infrared of the emitted spectrum (wavelength dependence of the emissivity), (2) photon emission into a greater solid angle due to similar day and night temperatures as a result of the increase in atmospheric water vapor attributable to vegetation, (3) the coupling of life to other photon-dissipating processes such as the water cycle, and (4) the covering of all of Earth's surface with pigments and water. His conclusions are therefore incorrect and thus do not provide a legitimate reason for doubting our assertion that we have presented evidence that supports the thermodynamic dissipation theory of the origin of life (Michaelian, 2009(Michaelian, , 2011(Michaelian, , 2016(Michaelian, , 2017(Michaelian, , 2021. ...
... Since our first articles published on the topic beginning in 2005 (Michaelian, 2005(Michaelian, , 2011, we have continued to uncover more evidence supporting a connection between photon dissipation and the origin and evolution of life. This includes the fact (1) that many of the fundamental molecules of life strongly absorb UV-C light in exactly the wavelength region that was arriving at Earth's surface during the Archean (Michaelian, 2012a, b;Michaelian and Simeonov, 2015;Michaelian, 2016); (2) that many of the fundamental molecules of life possess conical intersections for rapid radiation-less dissipation of the photon-induced electronic excitation energy (Michaelian, 2017(Michaelian, , 2021; (3) that efficient photochemical routes to production of the fundamental molecules from simple and common precursors, such as HCN, cyanogen, and CO 2 in water, under UV-C light have been found and that these routes have the hallmarks of dissipative structuring (Michaelian, 2017;Michaelian and Rodriguez, 2019;Michaelian, 2021;Hernández and Michaelian, 2022); (4) that we have discovered a DNA and RNA enzyme-less denaturing mechanism involving UV-C photon dissipation (Michaelian and Santillan, 2019); (5) that the homochirality of life can be explained from the morning/afternoon ocean surface temperature asymmetry and UV-C photon circular polarization at the ocean surface and the temperature dependence of UV-C-induced denaturing (Michaelian, 2018); (6) that the strong chemical affinity of the UV-C absorbing amino acids (the aromatics), and others, to their codons and anticodons can be explained based on the thermodynamic selection of greater photon dissipation afforded to the complex (Mejía Morales and Michaelian, 2020); (7) that dissipative structuring of the fundamental molecules under UV-C light provides a simple explanation for their existence in space as well as on other astronomical bodies (Michaelian and Simeonov, 2017); and (8) that plants appear to optimize evapotranspiration (the water cycle) over photosynthesis (see Michaelian, 2012a, b, and references therein). ...
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Lars Björn doubts our assertion that the driving force behind the origin and evolution of life has been the thermodynamic imperative of increasing the entropy production of the biosphere through increasing global solar photon dissipation. Björn bases his critique on the fact that the albedo of non-biological material can sometimes be lower than that of biological material and concludes that such examples counter our assertion. Our reply to Björn, however, is that albedo (reflection) is only one factor involved in the entropy production through photon dissipation occurring in the interaction of light with material. The other contributions to entropy production, which were listed in our article, are (1) the shift towards the infrared of the emitted spectrum (including a wavelength-dependent emissivity), (2) the diffuse reflection and emission of light into a greater outgoing solid angle, and (3) the heat of photon dissipation inducing evapotranspiration in the pigmented leaf, thereby coupling to the abiotic dissipative processes of the water cycle, which, besides shifting the emitted spectrum even further towards the infrared, promotes pigment production over the entire Earth surface. His analysis, therefore, does not provide a legitimate reason for doubting our assertion that life and evolution are driven by photon dissipation. We remain emphatic in our assertion that the fundamental molecules of life were originally dissipatively structured UV-C pigments arising in response to the thermodynamic imperative of dissipating the prevailing Archean solar spectrum. In the following, we respond to Björn's comment using the same section headings.
... Non-equilibrium thermodynamic theory, in particular Classical Irreversible Thermodynamics (CIT), developed by Théophile de Donder, Lars Onsager, Ilya Prigogine, Paul Glansdorff, Grégoire Nicolis, Agnessa Babloyantz, and others from the "Brussels school" has proven to be a very useful formalism for understanding living systems and their dynamics, including; the origin of life [9][10][11][12][13][14][15][16][17][18], the cell [19], cell differentiation [20], ecosystems [21,22], the biosphere [19,[23][24][25][26] and even the synthesis of organic molecules detected in space [27]. ...
... This, along with auto-and cross-catalytic proliferation, provides a mechanism for evolution which may be termed dissipative selection, or more generally, thermodynamic selection. Dissipative structuring, dissipative proliferation, and dissipative selection, are the necessary and sufficient elements for a non-equilibrium thermodynamic framework from within which the origin and evolution of life can be explained in purely physical and chemical terms [10,11,13]. ...
... The thermodynamic dissipation theory for the origin of life [11,13] as summarized above, employed as the framework here, defines life as; the dissipative structuring, proliferation, and evolution of molecular pigments and their support structures from common precursor carbon-based molecules under the impressed short wavelength solar photon potential for performing the explicit thermodynamic function of dissipating this light into long wavelength infrared light (heat). The external photon potential supplied continuously by the environment, and its dissipation into heat by the spontaneously assembled dissipative structures, are both integral components necessary for understanding life. ...
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We have suggested that the abiogenisis of life around the beginning of the Archean may have been an example of microscopic dissipative structuring of UVC pigments (the fundamental molecules of life) under the prevailing surface UV solar spectrum. In a previous article in this series, we have describe the non-equilibrium thermodynamics and the photochemical mechanisms which may have been involved in the dissipative structuring of the purines adenine and hypoxanthine from the common precursor molecules of HCN and water under UVC light. In this article we extend our analysis to include the production of the other two important purines, guanine and xanthine, from these same precursors. The photochemical reactions are presumed to occur within a fatty acid vesicle floating on a hot ocean surface exposed to the prevailing UV light. Reaction-diffusion equations are resolved under different environmental conditions. Significant amounts of adenine (∼10−5 M) and guanine (∼10−6 M) are obtained within only a few months at 80 °C under plausible initial concentrations of HCN and cyanogen (a photochemical product of HCN).
... Non-equilibrium thermodynamic theory, in particular Classical Irreversible Thermodynamics (CIT), developed by Théophile de Donder, Lars Onsager, Ilya Prigogine, Paul Glansdorff, Grégoire Nicolis, Agnessa Babloyantz, and others from the "Brussels school" has proven to be a very useful formalism for understanding living systems and their dynamics, including; the origin of life [9][10][11][12][13][14][15][16][17][18], the cell [19], cell differentiation [20], ecosystems [21,22], the biosphere [19,[23][24][25][26] and even the synthesis of organic molecules detected in space [27]. ...
... This, along with auto-and cross-catalytic proliferation, provides a mechanism for evolution which may be termed dissipative selection, or more generally, thermodynamic selection. Dissipative structuring, dissipative proliferation, and dissipative selection, are the necessary and sufficient elements for a non-equilibrium thermodynamic framework from within which the origin and evolution of life can be explained in purely physical and chemical terms [10,11,13]. ...
... The thermodynamic dissipation theory for the origin of life [11,13] as summarized above, employed as the framework here, defines life as; the dissipative structuring, proliferation, and evolution of molecular pigments and their support structures from common precursor carbon-based molecules under the impressed short wavelength solar photon potential for performing the explicit thermodynamic function of dissipating this light into long wavelength infrared light (heat). The external photon potential supplied continuously by the environment, and its dissipation into heat by the spontaneously assembled dissipative structures, are both integral components necessary for understanding life. ...
Article
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The non-equilibrium thermodynamics and the photochemical reaction mechanisms are described which may have been involved in the dissipative structuring, proliferation and complexation of the fundamental molecules of life from simpler and more common precursors under the UVC photon flux prevalent at the Earth’s surface at the origin of life. Dissipative structuring of the fundamental molecules is evidenced by their strong and broad wavelength absorption bands in the UVC and rapid radiationless deexcitation. Proliferation arises from the auto- and cross-catalytic nature of the intermediate products. Inherent non-linearity gives rise to numerous stationary states permitting the system to evolve, on amplification of a fluctuation, towards concentration profiles providing generally greater photon dissipation through a thermodynamic selection of dissipative efficacy. An example is given of photochemical dissipative abiogenesis of adenine from the precursor HCN in water solvent within a fatty acid vesicle floating on a hot ocean surface and driven far from equilibrium by the incident UVC light. The kinetic equations for the photochemical reactions with diffusion are resolved under different environmental conditions and the results analyzed within the framework of non-linear Classical Irreversible Thermodynamic theory.
... During the late Hadean and early Archean, sunlight surpassed all other forms of free energy (hydrothermal vents, lightening, chemical potentials, shock waves, etc.) by at least three orders of magnitude [20]. The most important dissipative structures existing on Earth's surface today are the organic pigments in water solvent [21] and these are responsible for approximately 63% of the total entropy production resulting from Earth's interaction with its solar environment [22]. The coupling of the heat of dissipation of the solar photons in organic pigments to other macroscopic irreversible processes such as ocean and wind currents and the water cycle, accounts for the majority of the rest of the entropy production on Earth [23]. ...
... Corroborating evidence for the exposure of life to this UVC photon potential, and indeed life's thermodynamic preoccupation with its dissipation, can be found in the fundamental molecules of life (those common to all three domains of life). Most of these absorb and dissipate this light into heat with great efficiency (see Figure 1) [21,26]. We have therefore suggested that the fundamental molecules originated in the later Hadean or early Archean as microscopic dissipative structures to perform this thermodynamic function [7][8][9][10]26]. ...
... The fundamental molecules of life (those molecules common to all three domains of life) and their associations in complexes are examples of microscopic self-organized dissipative structures which formed under the Archean UVC photon potential [7][8][9][10]26,27]. Evidence for this can be found in the strong absorption cross sections of the fundamental molecules, with absorption maxima lying exactly within the predicted UVC window of Earth's atmosphere during the Archean [24] (Figure 1), and in the existence of inherent conical intersections giving these molecules an extraordinarily rapid non-radiative electronic excited state decay into heat [10,21,30]. ...
Article
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Ultraviolet light incident on organic material can initiate its spontaneous dissipative structuring into chromophores which can catalyze their own replication. This may have been the case for one of the most ancient of all chromophores dissipating the Archean UVC photon flux, the nucleic acids. Oligos of nucleic acids with affinity to particular amino acids which foment UVC photon dissipation would most efficiently catalyze their own reproduction and thus would have been selected through non-equilibrium thermodynamic imperatives which favor dissipation. Indeed, we show here that those amino acids with characteristics most relevant to fomenting UVC photon dissipation are precisely those with greatest chemical affinity to their codons or anticodons. This could provide a thermodynamic basis for the specificity in the amino acid-nucleic acid interaction and an explanation for the accumulation of information in nucleic acids since this information is relevant to the optimization of dissipation of the externally imposed thermodynamic potentials. The accumulation of information in this manner provides a link between evolution and entropy production.
... Photons from within this region of the solar spectrum have enough free energy to reconfigure covalent bonds of carbon based organic molecules, but not enough energy to disassociate these. From this perspective, molecular synthesis can be understood as microscopic dissipative structuring of pigments [6, 9,13] and proliferation can be understood as autocatalytic photochemical replication of these [5], both driven by the dissipation of the Archean solar longwavelength UVC photon flux; a process still relevant today for organic pigment synthesis and proliferation, albeit at visible wavelengths of lower photon energy, thus requiring routes of much greater biochemical complexity [6,7,8]. Indeed, many of the fundamental molecules of life including nucleotides, amino acids, enzymes, vitamins, cofactors, stacked protoporphyrins, and conjugated fatty acids, all absorb and dissipate photons strongly within the 220 to 290 nm long wavelength UVC region [10], precisely that wavelength region where Sagan [14] and later Cnossen et al. [15] established the probable existence of an Archean atmospheric window. ...
... Photons from within this region of the solar spectrum have enough free energy to reconfigure covalent bonds of carbon based organic molecules, but not enough energy to disassociate these. From this perspective, molecular synthesis can be understood as microscopic dissipative structuring of pigments [6, 9,13] and proliferation can be understood as autocatalytic photochemical replication of these [5], both driven by the dissipation of the Archean solar longwavelength UVC photon flux; a process still relevant today for organic pigment synthesis and proliferation, albeit at visible wavelengths of lower photon energy, thus requiring routes of much greater biochemical complexity [6,7,8]. Indeed, many of the fundamental molecules of life including nucleotides, amino acids, enzymes, vitamins, cofactors, stacked protoporphyrins, and conjugated fatty acids, all absorb and dissipate photons strongly within the 220 to 290 nm long wavelength UVC region [10], precisely that wavelength region where Sagan [14] and later Cnossen et al. [15] established the probable existence of an Archean atmospheric window. ...
... Many also have chemical affinity to the secondary or tertiary structures of RNA and DNA [20]. The UVC absorbing amino acids, including the aromatic tryptophan, tyrosine, phenylalanine, as well as the photon-induced charge transfer amino acids histidine, cysteine and lysine, have particularly strong chemical affinity to their 4 DNA codons or anti-codons [21], suggesting not only a stereochemical era [21][22][23][24], but also a UVC dissipative era for incipient life [2,3,4,6,9,10]. ...
... Non-equilibrium thermodynamics indicates that the origin, persistence, and evolution of any irreversible process require the dissipation of a generalized thermodynamic potential. We have conjectured [1,2,3,4,5,6,7,8,9,10,11,12,13] that the early synthesis, complexation, proliferation and evolution of the fundamental molecules of life (those common to all three domains; bacteria, eukarya, and archea) were driven by the dissipation of the long-wavelength (220-290 nm) part of the UVC solar photon spectrum prevailing for at least 1,000 million years at Earth's surface throughout the Archean [14,15]. Photons from within this region of the solar spectrum have enough free energy to reconfigure covalent bonds of carbon based organic molecules, but not enough energy to disassociate these. ...
... Photons from within this region of the solar spectrum have enough free energy to reconfigure covalent bonds of carbon based organic molecules, but not enough energy to disassociate these. From this perspective, molecular synthesis can be understood as microscopic dissipative structuring of pigments [6,9,13] and proliferation can be understood as autocatalytic photochemical replication of these [5], both driven by the dissipation of the Archean solar long-wavelength UVC photon flux; a process still relevant today for organic pigment synthesis and proliferation, albeit at visible wavelengths of lower photon energy, thus requiring routes of much greater biochemical complexity [6,7,8]. ...
... Photons from within this region of the solar spectrum have enough free energy to reconfigure covalent bonds of carbon based organic molecules, but not enough energy to disassociate these. From this perspective, molecular synthesis can be understood as microscopic dissipative structuring of pigments [6,9,13] and proliferation can be understood as autocatalytic photochemical replication of these [5], both driven by the dissipation of the Archean solar long-wavelength UVC photon flux; a process still relevant today for organic pigment synthesis and proliferation, albeit at visible wavelengths of lower photon energy, thus requiring routes of much greater biochemical complexity [6,7,8]. ...
Article
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Non-equilibrium thermodynamics is a relevant framework from within which to address formidable difficulties encountered in explaining the origin of life; from molecular synthesis and complexation, enzyme-less proliferation, to evolution (including the acquisition of homochirality and information). From within this framework we have proposed that the origin of life was the origin of the dissipative structuring of organic pigments which became the fundamental molecules of life (e.g. RNA and DNA) proliferated through autocatalytic photochemical reactions under the thermodynamic imperative of dissipating the imposed UVC solar photon flux available at the Archean surface. Here we present experimental evidence demonstrating that the absorption and dissipation of UVC light by synthetic DNA of 25 base pairs (and also natural salmon sperm DNA) over a range of temperatures, including below their melting temperature, leads to denaturing. Since denaturing is a non-trivial step on route to enzyme-less replication, our data suggests the possibility of a dissipative route to DNA replication at the origin of life. Such a dissipation-replication relation provides a simple mechanism for the early accumulation of both 2 homochirality and information. Possible mechanisms of UVC photon-induced denaturing of DNA are discussed.
... From the perspective of the "Thermodynamic Dissipation Theory of the Origin of Life" [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28], descriptions of molecular synthesis alone, however, are insufficient to capture life's vitality, which includes proliferation, dynamics, and evolution. The vitality of life requires instead a constant dissipation of an imposed thermodynamic potential. ...
Article
Full-text available
We have proposed that the abiogenesis of life around the beginning of the Archean may have been an example of “spontaneous” microscopic dissipative structuring of UV-C pigments under the prevailing surface ultraviolet solar spectrum. The thermodynamic function of these Archean pigments (the “fundamental molecules of life”), as for the visible pigments of today, was to dissipate the incident solar light into heat. We have previously described the non-equilibrium thermodynamics and the photochemical mechanisms which may have been involved in the dissipative structuring of the purines adenine and hypoxanthine from the common precursor molecules of hydrogen cyanide and water under this UV light. In this article, we extend our analysis to include the production of the other two important purines, guanine and xanthine. The photochemical reactions are presumed to occur within a fatty acid vesicle floating on a hot (∼80 ∘C) neutral pH ocean surface exposed to the prevailing UV-C light. Reaction–diffusion equations are resolved under different environmental conditions. Significant amounts of adenine (∼10−5 M) and guanine (∼10−6 M) are obtained within 60 Archean days, starting from realistic concentrations of the precursors hydrogen cyanide and cyanogen (∼10−5 M).
... Connected with these reaction conditions are three different sets of basic requirements that are schematically illustrated in Fig. 11. [257]. In this latter, the biotic-abiotic co-evolution of the biosphere was envisaged as being based on the observation that the photon dissipation efficacy of Earth in its solar environment has increased ever since the formation of Earth in the Hadean and that this evolution has incurred the dissipative structuring of pigments: "…Their proliferation to far beyond equilibrium concentrations can be understood in terms of non-linear, non-equilibrium thermodynamic principles directing autocatalytic photochemical reactions in which these pigments catalyze the dissipation of the same thermodynamic potential (the solar photon flux) that produced them." ...
Article
An interdisciplinary review of the chemical literature that points to a unifying scenario for the origin of life, referred to as the Primordial Multifunctional organic Entity (PriME) scenario, is provided herein. In the PriME scenario it is suggested that the Insoluble Organic Matter (IOM) in carbonaceous chondrites, as well as interplanetary dust particles from meteorites and comets may have played an important role in the three most critical processes involved in the origin of life, namely 1) metabolism, via a) the provision and accumulation of molecules that are the building blocks of life, b) catalysis (e.g., by templation), and c) protection of developing life molecules against radiation by excited state deactivation; 2) compartmentalization, via adsorption of compounds on the exposed organic surfaces in fractured meteorites, and 3) replication, via deaggregation, desorption and related physical phenomena. This scenario is based on the hitherto overlooked structural and physicochemical similarities between the IOM and the dark, insoluble, multifunctional melanin polymers found in bacteria and fungi and associated with the ability of these microorganisms to survive extreme conditions, including ionizing radiation. The underlying conceptual link between these two materials is strengthened by the fact that primary precursors of bacterial and fungal melanins (collectively referred to herein as allomelanins) are hydroxylated aromatic compounds like homogentisic acid and 1,8-dihydroxynaphthalene, and that similar hydroxylated aromatic compounds, including hydroxynaphthalenes, figure prominently among possible components of the organic materials on dust grains and ices in the interstellar matter, and may be involved in the formation of IOM in meteorites. Inspired by this rationale, a vis-à-vis review of the properties of IOM from various chondrites and non-nitrogenous allomelanin pigments from bacteria and fungi is provided herein. The unrecognized similarities between these materials may pave the way for a novel scenario at the origin of life, in which IOM-related complex organic polymers delivered to the early Earth are proposed to serve as PriME and were preserved and transformed in those primitive forms of life that shared the ability to synthesize melanin polymers playing an important role in the critical processes underlying the establishment of terrestrial eukaryotes.
... Life, although incorporating equilibrium structures, is fundamentally a nonequilibrium process and therefore its existence is dependent on the dissipation of one or more thermodynamic potentials in its environment. Boltzmann recognized this almost 125 years ago [1] and suggested that the most important thermodynamic potential that life dissipates is the solar photon potential [2]. Present day life has evolved to dissipate other thermodynamic potentials accessible on Earth's surface, for example, chemical potentials available in biological material or at hydrothermal vents. ...
Conference Paper
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It has been conjectured that the origin of the fundamental molecules of life, their proliferation over the surface of Earth, and their complexation through time, are examples of photochemical dissipative structuring, dissipative proliferation, and dissipative selection, respectively, arising out of the nonequilibrium conditions created on Earth’s surface by the solar photon spectrum. Here I describe the nonequilibrium thermodynamics and the photochemical mechanisms involved in the synthesis and evolution of the fundamental molecules of life from simpler more common precursor molecules under the long wavelength UVC and UVB solar photons prevailing at Earth’s surface during the Archean. Dissipative structuring through photochemical mechanisms leads to carbon based UVC pigments with peaked conical intersections which endow them with a large photon disipative capacity (broad wavelength absorption and rapid radiationless dexcitation). Dissipative proliferation occurs when the photochemical dissipative structuring becomes autocatalytic. Dissipative selection arises when fluctuations lead the system to new stationary states (corresponding to different molecular concentration profiles) of greater dissipative capacity as predicted by the universal evolution criterion of Classical Irreversible Thermodynamic theory established by Onsager, Glansdorff, and Prigogine. An example of the UV photochemical dissipative structuring, proliferation, and selection of the nucleobase adenine from an aqueous solution of HCN under UVC light is given.
... From a thermodynamic perspective, the fate of the electronic excitation energy is also a very relevant aspect of the absorption event since it is directly linked to the amount of entropy produced by the dissipative microscopic structure (i.e., the polyatomic molecule). Nonradiative, vibrational relaxation pathways of the excited state lead to more efficient energy dissipation and higher entropy production when compared to the fluorescent or phosphorescent radiative decay channels (Michaelian 2011(Michaelian , 2012(Michaelian , 2016. MAAs have the ability to protect the cell by absorbing UVR and dissipating the energy as heat without generating ROS (Conde et al. 2004). ...
Chapter
Mycosporine-like amino acids (MAAs) are the most common group of transparent ultraviolet radiation absorbing intracellular secondary metabolites synthesized by cyanobacteria as part of an overall strategy to diminish the direct and indirect damaging effects of environmental ultraviolet radiation (UVR). MAAs are a family of more than 30 compounds and characterized by a cyclohexenone or cyclohexenimine chromophore core conjugated with amino acids or imino alcohol substituents, having absorption maxima ranging from 268 to 362 nm. These are attached to the core through imine linkages, leading to a combination of resonance tautomers which facilitates absorption of UV light. These UV screening compounds are highly photostable photoprotectant and also serve as potent antioxidants. Considerable interest has been centered on MAAs because experimental evidence indicated that in cyanobacteria the major functions of MAAs are to act as photo-protective UV filters and/or to act as antioxidants. In the present chapter we also describe the structure and physicochemical properties of MAAs, including the recently discovered MAAs and the modern methods used for their isolation and identification. Multiple environmental signals influence MAAs biosynthesis and regulation of induction of these UV screening compounds is a part of complex stress response pathway. This chapter Rajneesh et al. 98 provides insight into the genes of cyanobacteria involved in MAA biosynthesis and thus widens the field of research for molecular, bioinformatics and phylogenetic analysis of these evolutionary and industrially important compounds. Study of these sunscreens has also led to the discovery of new classes of compounds, new metabolic pathways, a deeper understanding of microbial photobiology and the potential for dermatological or biomedical applications.
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