Ecological Clues to the Nature of Consciousness

Total Page:16

File Type:pdf, Size:1020Kb

Ecological Clues to the Nature of Consciousness entropy Concept Paper Ecological Clues to the Nature of Consciousness Robert E. Ulanowicz 1,2 1 Department of Biology, University of Florida, Gainesville, FL 32611-8525, USA; [email protected]; Tel.: +1-(352)-392-6917 2 Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, Solomons, MD 20688-0038, USA Received: 20 April 2020; Accepted: 26 May 2020; Published: 30 May 2020 Abstract: Some dynamics associated with consciousness are shared by other complex macroscopic living systems. For example, autocatalysis, an active agency in ecosystems, imparts to them a centripetality, the ability to attract resources that identifies the system as an agency apart from its surroundings. It is likely that autocatalysis in the central nervous system likewise gives rise to the phenomenon of selfhood, id or ego. Similarly, a coherence domain, as constituted in terms of complex bi-level coordination in ecosystems, stands as an analogy to the simultaneous access the mind has to assorted information available over different channels. The result is the feeling that various features of one’s surroundings are present to the individual all at once. Research on these phenomena in other fields may suggest empirical approaches to the study of consciousness in humans and other higher animals. Keywords: autocatalysis; centripetality; coherence domain; consciousness; ecosystem dynamics; simultaneity 1. Introduction Panpsychism is the view that all features of the natural world share elements of consciousness or mind. One need not accept this belief in its entirety to acknowledge that behaviors contributing to consciousness might be evident in natural systems seemingly removed from the brain or human mental activity, thereby contributing insights into the nature of consciousness and how it might have arisen. While physics certainly can contribute to understanding many biotic phenomena, it is limited in that its laws can treat only collections of indistinguishable objects [1]. This restriction to homogeneous variables makes it difficult to apply the fundamental laws to behaviors among radically different biological kinds [2,3]. Ecology, in contrast with physics, embraces heterogeneity in its very foundations with its emphasis on the relationships among many differing types. Some even assert that proto-ecosystem behaviors had to precede the appearance of the first organisms—that physical cycling among regions that are dominated by antagonistic reactions (e.g., oxidation/reduction) provided the crucible that fostered the first proto-organisms [4]. It is thus plausible to consider whether some features of ecosystem dynamics might resemble those of the complex phenomenon known as consciousness. There is almost universal agreement that the experience of consciousness is one of the most difficult problems facing science. Theories of consciousness are common [5,6], relying on a host of subsidiary theories and phenomena. The major challenge is to connect consciousness to theories that are amenable to quantification, and empirical investigation [7]. One such endeavor is the Global Workspace Theory, where information is considered to be held in a global workspace and distributed to brain modules associated with specific tasks [8]. Another is Integrated Information Theory [9], which is an attempt to quantify the information that is actually fed back into the neuronal system to change it. The following essay is an attempt simply to highlight two ecosystem repertoires that might contribute to these efforts to illumine the very complex phenomenon of consciousness. Entropy 2020, 22, 611; doi:10.3390/e22060611 www.mdpi.com/journal/entropy EntropyEntropy2020 2020, 22, 2,2 611, x FOR PEER REVIEW 22 of of 10 10 The first such behavior is autocatalysis, in which major reactants and products catalyze one anotherThe in first a closed such behavior fashion. isSuch autocatalysis, autocatalytic in dynamics which major are reactantscapable of and engendering products catalyzea progressive one anothertendency in to a closeddraw ever fashion. more Such resources autocatalytic into its dynamicsactive orbit. are (See capable example of engendering below.) This a phenomenon progressive tendencywas noted to drawin chemistry ever more decades resources ago intoby Bertrand its active Russell orbit. (See [10] example, who called below.) it “chem This phenomenonical imperialism” was notedand he in pointed chemistry to it decades as the drive ago byr behind Bertrand all Russellof evolution. [10], who Ulanowicz called it [11] “chemical instead imperialism”used Isaac Newton’s and he pointedterm, “centripetality” to it as the driver to describe behind allsuch of accumulation. evolution. Ulanowicz Despite [the11] fact instead that usedthis phenomenon Isaac Newton’s is readily term, “centripetality”visible in all living to describe systems, such it accumulation. appears on no Despite one’s thelist factof the that fundamental this phenomenon properties is readily of life. visible For inexample, all living Varela systems, et al. it [12] appears, in their on nodetailed one’s listpioneering of the fundamental description of properties autopoesis of life.(as engendered For example, by Varelaautocatalysis) et al. [12],, do in theirnot detailedtouch upon pioneering the phenomenon. description ofYet, autopoesis the phenomenon (as engendered implicitly by autocatalysis), defines the dosystem not touch as a self, upon the the focus phenomenon. of its component Yet, the activities. phenomenon implicitly defines the system as a self, the focusThe of its second component property activities. concerns the simultaneity with which various sources of information are accessibleThe second to a virtual property center concerns that may the simultaneitybe defined by with centripetality. which various That sources is, at any of informationmoment, an areindividual’s accessible attention to a virtual may center be focused that may on bea particular defined by thing centripetality. or activity, That but is,that at agent any moment, remains anconscious individual’s of a host attention of other may sources be focused of information on a particular—neuronal, thing visual or activity,, olfactory, but taste that agentor sensory remains—all conscioustranspiring of at a hostthe same of other time sources on the periphery of information—neuronal, of the mind. The theoretical visual, olfactory, origins taste of such or sensory—all simultaneity transpiringmight be traced at the sameback timeto physics, on the peripheryand in particular of the mind. to the The notion theoretical of a origins“coherence of such domain”. simultaneity Such mightcoherence be traced is exhibited back to physics, by persisting and in particular aggregations to the notionof hundreds of a “coherence or more domain”. water molecules Such coherence in the isplasmas exhibited of living by persisting systems aggregations [13]. Below, how of hundreds the same or coherent more water behavior molecules might in be the extrapolated plasmas of to living work systemsin the process [13]. Below, of ecosystem how the development same coherent is behaviordiscussed might [14]. be extrapolated to work in the process of ecosystem development is discussed [14]. 2. Towards a Conception of Self 2. Towards a Conception of Self Autocatalysis is a dynamic that appears in consciousness literature (e.g., [15–17]. Broadly defined,Autocatalysis an autocatalytic is a dynamic set is a that collection appears of in entities, consciousness each of which literature benefits (e.g., [and15– 17is ].benefitted Broadly defined,by other anentities autocatalytic within the set same is a collection set so as ofto entities,maintain each the ofconfiguration which benefits of the and wh isole. benefitted To illumine by other some entities of the withinproperties the same of setautocatalysis, so as to maintain one themay configuration begin by ofconsidering the whole. Tosimple illumine autocatalytic some of the cycles. properties An ofautocatalytic autocatalysis, cycle one mean may begins any bycycle considering of processes simple for autocatalyticwhich each constituent cycles. An autocatalytic process benefits cycle the means next anyone cyclein the of sequence processes [18] for. whichIn Figure each 1, constituentfor example, process if process benefits A facilitates the next another one in the process, sequence B, and [18 ].B Inbenefit Figures 1C,, forwhich example, in its turn if process augments A facilitates A, then another the activity process, of A B, indirectly and B benefits promotes C, which itself. in The its same turn augmentsgoes, of course, A, then for the B activityand C. of A indirectly promotes itself. The same goes, of course, for B and C. Figure 1. Schematic of a hypothetical three-component autocatalytic cycle. Figure 1. Schematic of a hypothetical three-component autocatalytic cycle. As an ecological example of autocatalysis, one may consider the aquatic community that develops As an ecological example of autocatalysis, one may consider the aquatic community that around a family of aquatic weeds known as Bladderworts (genus Utricularia)[19]. Scattered along the develops around a family of aquatic weeds known as Bladderworts (genus Utricularia) [19]. Scattered feather-like stems and leaves of these plants are small visible bladders that normally maintain within along the feather-like stems and leaves of these plants are small visible bladders that normally themselves a lower osmotic pressure than their surroundings (Figure2a). At the end of each bladder maintain
Recommended publications
  • Chemical Oscillations 1
    GENERAL I ARTICLE Chemical Oscillations 1. Basic Principles and Examples Monika Sharma and Pra'Veen Kumar A chemical reaction is usually thought of as coming to­ gether of reactant molecules to form products. The concen­ trations of initial components (reactants) decrease, and concentrations of products increase until they reach a well defined state: the equilibrium. This process is accompa­ nied by a decrease of the system free energy (compared at constant pressure and temperature), until it reaches a mini­ Monika Shanna is a JRF mum in the equilibrium. Thus, it follows from the nature of at the Protein Science and the law ofmass-action that every simple reaction approaches Engineering Unit, its equilibrium asymptotically, and the evolution of any Institute of Microbial Technology (IMTECH), physico-chemical system leads invariably to the steady Chandigarh. state ofmaximum disorder in the universe. Normally, chemi­ cal systems approach equilibrium in a smooth, frequently exponential relaxation. Under special circumstances, how­ ever, coherent behavior such as sustained oscillations are observed and the oscillations of chemical origin have been present as long as life itseH. Such reactions can be studied Praveen Kumar is using mathematical models, the Lotka-Volterra model be­ pursuing his PhD in ing the earliest and the simplest one. chemical dynamics at Panjab University, 1. Introduction Chandigarh. Every living system contains hundreds of chemical oscillators. Some examples are systems such as circadian clocks and rhyth­ mic activity
    [Show full text]
  • Universal Motifs and the Diversity of Autocatalytic Systems
    Universal motifs and the diversity of autocatalytic systems Alex Blokhuisa,b,c,d,1, David Lacostea, and Philippe Ngheb,1 aGulliver Laboratory, UMR CNRS 7083, Paris Sciences et Lettres University, Paris F-75231, France; bLaboratoire de Biochimie, UMR CNRS 8231, Chimie Biologie et Innovation, Ecole Superieure´ de Physique et de Chimie Industrielles de la ville de Paris, PSL University, Paris F-75231, France; cGroningen Institute for Evolutionary Life Sciences, University of Groningen, 9747 AG Groningen, The Netherlands; and dCentre for Systems Chemistry, Stratingh Institute, University of Groningen, 9747 AG Groningen, The Netherlands Edited by Peter Schuster, University of Vienna, Vienna, Austria, and approved September 1, 2020 (received for review June 30, 2020) Autocatalysis is essential for the origin of life and chemical evo- From this definition, we derive conditions to determine lution. However, the lack of a unified framework so far prevents whether a subnetwork embedded in a larger chemical network a systematic study of autocatalysis. Here, we derive, from basic can be catalytic or autocatalytic. These conditions provide a principles, general stoichiometric conditions for catalysis and auto- mathematical basis to identify minimal motifs, called autocat- catalysis in chemical reaction networks. This allows for a classifica- alytic cores. We found that cores have five fundamental cat- tion of minimal autocatalytic motifs called cores. While all known egories of motifs. They allow classification of all previously autocatalytic systems indeed contain minimal motifs, the classifica- described forms of autocatalysis, and also reveal hitherto uniden- tion also reveals hitherto unidentified motifs. We further examine tified autocatalytic schemes. We then study the kinetic condi- conditions for kinetic viability of such networks, which depends tions, which we call viability conditions, under which autocat- on the autocatalytic motifs they contain and is notably increased alytic networks can appear and be maintained on long timescales.
    [Show full text]
  • Universal Motifs and the Diversity of Autocatalytic Systems
    Universal motifs and the diversity of autocatalytic systems Alex Blokhuisa,b,c,d,1, David Lacostea, and Philippe Ngheb,1 aGulliver Laboratory, UMR CNRS 7083, Paris Sciences et Lettres University, Paris F-75231, France; bLaboratoire de Biochimie, UMR CNRS 8231, Chimie Biologie et Innovation, Ecole Superieure´ de Physique et de Chimie Industrielles de la ville de Paris, PSL University, Paris F-75231, France; cGroningen Institute for Evolutionary Life Sciences, University of Groningen, 9747 AG Groningen, The Netherlands; and dCentre for Systems Chemistry, Stratingh Institute, University of Groningen, 9747 AG Groningen, The Netherlands Edited by Peter Schuster, University of Vienna, Vienna, Austria, and approved September 1, 2020 (received for review June 30, 2020) Autocatalysis is essential for the origin of life and chemical evo- From this definition, we derive conditions to determine lution. However, the lack of a unified framework so far prevents whether a subnetwork embedded in a larger chemical network a systematic study of autocatalysis. Here, we derive, from basic can be catalytic or autocatalytic. These conditions provide a principles, general stoichiometric conditions for catalysis and auto- mathematical basis to identify minimal motifs, called autocat- catalysis in chemical reaction networks. This allows for a classifica- alytic cores. We found that cores have five fundamental cat- tion of minimal autocatalytic motifs called cores. While all known egories of motifs. They allow classification of all previously autocatalytic systems indeed contain minimal motifs, the classifica- described forms of autocatalysis, and also reveal hitherto uniden- tion also reveals hitherto unidentified motifs. We further examine tified autocatalytic schemes. We then study the kinetic condi- conditions for kinetic viability of such networks, which depends tions, which we call viability conditions, under which autocat- on the autocatalytic motifs they contain and is notably increased alytic networks can appear and be maintained on long timescales.
    [Show full text]
  • Design Principles of Autocatalytic Cycles Constrain Enzyme Kinetics and Force Low Substrate Saturation at Flux Branch Points
    bioRxiv preprint doi: https://doi.org/10.1101/074641; this version posted January 2, 2017. The copyright holder for this preprint (which was not certified by peer review) is the author/funder, who has granted bioRxiv a license to display the preprint in perpetuity. It is made available under aCC-BY-ND 4.0 International license. Design principles of autocatalytic cycles constrain enzyme kinetics and force low substrate saturation at flux branch points Uri Barenholz1, Dan Davidi1, Ed Reznik2,3, Yinon Bar-On1, Niv Antonovsky1, Elad Noor4, and Ron Milo1 1Department of Plant and Environmental Sciences, The Weizmann Institute of Science 2Computational Biology Program, Memorial Sloan Kettering Cancer Center 3Center for Molecular Oncology, Memorial Sloan Kettering Cancer Center 4Institue of Molecular Systems Biology, ETH Zurich Abstract A set of chemical reactions that require a metabolite to synthesize more of that metabolite is an autocatalytic cycle. Here we show that most of the reactions in the core of central carbon metabolism are part of compact autocatalytic cycles. Such metabolic designs must meet specific conditions to support stable fluxes, hence avoiding depletion of intermediate metabolites. As such, they are subjected to constraints that may seem counter-intuitive: the enzymes of branch reactions out of the cycle must be overexpressed and the affinity of these enzymes to their substrates must be relatively weak. We use recent quantitative proteomics and fluxomics measurements to show that the above conditions hold for functioning cycles in central carbon metabolism of E.coli. This work demonstrates that the topology of a metabolic network can shape kinetic parameters of enzymes and lead to seemingly wasteful enzyme usage.
    [Show full text]
  • Autocatalysis As the Natural Philosophy Underlying Complexity Andbiological Evolution
    Interdisciplinary Description of Complex Systems 9(1), 1-22, 2011 AUTOCATALYSIS AS THE NATURAL PHILOSOPHY UNDERLYING COMPLEXITY AND BIOLOGICAL EVOLUTION Güngör Gündüz* Department of Chemical Engineering, Middle East Technical University Ankara, Turkey Regular article Received: 28. March 2011. Accepted: 27. June 2011. ABSTRACT The importance and different aspects of autocatalysis in evolution was analyzed. The behaviour of autocatalytic reactions mainly the Lotka-Volterra and the Schlögl equations were discussed in terms of phase change, entropy, and their oscillation frequency. The increase of complexity as the general direction of evolution was examined on some patterns in terms of both their entropy and information content. In addition, the relation between stability and functionality, stability and cohesion were discussed. It was concluded that evolution drifts in the direction of increasing complexity as a kind of natural philosophy to counteract the increase of entropy in the universe. KEY WORDS autocatalysis, entropy, evolution, complexity, information, oscillation frequency, cohesion CLASSIFICATION JEL: C02, Z19 PACS: 01.70.+w, 89.75.-k *Corresponding author, η: [email protected]; (90) 312 210 26 16; Kimya Mühendisliği Bölümü, Orta Doğu Teknik Üniversitesi, Ankara 06531, Turkey G. Gündüz INTRODUCTION The theory of biological evolution did not only have a spectacular impact on human knowledge of biological systems, but also founded a close relationship between many disciplines of science such as, chemistry, physics, geology, and philosophy; yet sociology, psychology, economy, and similar other fields use evolutionary concepts to evaluate long term changes. In early 19th century physical and chemical principles had not yet been strongly introduced into biology, and Darwin could make his reasoning on some philosophical and observational facts.
    [Show full text]
  • Entropy Generation in MHD Casson Fluid Flow with Variable Heat Conductance and Thermal Conductivity Over Non-Linear Bi-Direction
    www.nature.com/scientificreports OPEN Entropy generation in MHD Casson fuid fow with variable heat conductance and thermal conductivity over non‑linear bi‑directional stretching surface Muhammad Sohail1, Zahir Shah 2*, Asifa Tassaddiq 3, Poom Kumam 4,5* & Prosun Roy6 This consideration highlights the belongings of momentum, entropy generation, species and thermal dissemination on boundary layer fow (BLF) of Casson liquid over a linearly elongating surface considering radiation and Joule heating efects signifcant. Transportation of thermal and species are ofered by using the temperature‑dependent models of thermal conductivity and mass difusion coefcient. Arising problem appear in the form of nonlinear partial diferential equations (NPDEs) against the conservation laws of mass, momentum, thermal and species transportation. Appropriate renovation transfgures the demonstrated problem into ordinary diferential equations. Numerical solutions of renovated boundary layer ordinary diferential equations (ODEs) are attained by a profcient and reliable technique namely optimal homotopy analysis method (OHAM). A graphical and tabular interpretation is given for convergence of analytic solutions through error table and fow behavior of convoluted physical parameters on calculated solutions are presented and explicated in this examination. Reliability and efectiveness of the anticipated algorithm is established by comparing the results of present contemplation as a limiting case of available work, and it is found to be in excellent settlement. Decline in fuid velocity and enhancement in thermal and species transportation is recorded against the fuctuating values of Hartman number. Also reverse comportment of Prandtl number and radiation parameter is portrayed. Moreover, it is conveyed that supplementing values of the magnetic parameter condenses the fuid velocity and upsurges the thermal and concentration distributions.
    [Show full text]
  • SFI Online Lecture Autocatalysis Nathaniel Virgo
    Reaction networks and autocatalysis Nathaniel Virgo Autocatalysis • Chemical self production: • the ability of a set of chemical species to make more of that same set, by undergoing a series of chemical reactions Life makes life Chemical reactions Chemical reactions A A A A A A Chemical reactions Chemical reactions Chemical reactions Chemical reactions Chemical reactions B Chemical reactions Chemical reactions Chemical reactions Chemical reactions 2A → B Chemical reactions 2A → B reactants product Chemical reactions 2A → B reactants product reactions generally happen faster the higher the concentration of reactants Catalysis 2A →C B e.g. 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network 2A + C → C2A C2A → CB CB → B + C C net reaction 2A + C → B + C Catalysis as a reaction network A A 2A + C → C2A CAA C2A → CB CB → B + C C CB B net reaction 2A + C → B + C Catalysis as a reaction network A A 2A + C → C2A CAA C2A → CB CB → B + C C CB B Catalytic cycle net reaction 2A + C → B + C Catalyst broad definition: something that gets returned after a sequence of reactions Autocatalyst broad definition: something that acts as a catalyst for its own production Autocatalytic reaction networks Reaction network: multiple chemical reactions that interact.
    [Show full text]
  • The Dissipative Photochemical Origin of Life: UVC Abiogenesis of Adenine
    entropy Article The Dissipative Photochemical Origin of Life: UVC Abiogenesis of Adenine Karo Michaelian Department of Nuclear Physics and Applications of Radiation, Instituto de Física, Universidad Nacional Autónoma de México, Circuito Interior de la Investigación Científica, Cuidad Universitaria, Mexico City, C.P. 04510, Mexico; karo@fisica.unam.mx Abstract: The non-equilibrium thermodynamics and the photochemical reaction mechanisms are described which may have been involved in the dissipative structuring, proliferation and complex- ation 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. Keywords: origin of life; dissipative structuring; prebiotic chemistry; abiogenesis; adenine; organic molecules; non-equilibrium thermodynamics; photochemical reactions Citation: Michaelian, K. The Dissipative Photochemical Origin of MSC: 92-10; 92C05; 92C15; 92C40; 92C45; 80Axx; 82Cxx Life: UVC Abiogenesis of Adenine.
    [Show full text]
  • Rates of Chemical Reactions: Their Measurement and Mathematical Expressions - Beltrame P
    FUNDAMENTALS OF CHEMISTRY – Vol. II - Rates of Chemical Reactions: Their Measurement and Mathematical Expressions - Beltrame P. RATES OF CHEMICAL REACTIONS: THEIR MEASUREMENT AND MATHEMATICAL EXPRESSIONS Beltrame P Università di Milano, Italy Keywords: activation energy, adsorption isotherm, Arrhenius equation, autocatalysis, chemical adsorption, chemical kinetics, consecutive reactions, continuous reactions, differential reactor, discontinuous reactions, enzymatic catalysis, fast reactions, frequency factor, half-life, heterogeneous catalysis, homogeneous catalysis, integral reactor, integrated rate equation, Langmuir-Hinshelwood mechanism, Michaelis constant, opposing reactions, parallel reactions, perturbation and relaxation method, phase-transfer catalysis, phase-transfer cation, power–law rate equation, reaction order, reaction rate, relaxation time, residence time, stirred tank reactor, stopped flow, time factor, tubular reactor, turnover frequency (TOF) Contents l. Reaction Rate, Kinetic Equation, Catalysis 1.1. Definitions 1.2. Simple Reactions 1.3. Complex Reactions 1.3.1. Opposing Reactions 1.3.2. Parallel Reactions 1.3.3. Consecutive Reactions 1.4. Catalytic Reactions 1.4.1. Homogeneous Catalysis 1.4.2. Enzymatic Catalysis 1.4.3. Heterogeneous Catalysis 2. Dependence of the Rate on Temperature 3. Measurement of Rates 3.1. Measurement by Discontinuous Methods 3.2. Measurement by Continuous Methods Glossary BibliographyUNESCO – EOLSS Biographical Sketch Summary SAMPLE CHAPTERS Following a definition of the typical expressions of chemical kinetics, simple reactions at constant temperature and their rate equations are considered. Then complex reactions (opposing, parallel, or consecutive) and the main types of reaction promoted by catalysis (homogeneous, enzymatic, and heterogeneous) are dealt with. It is explained briefly how the rate of reaction depends on temperature. Methods for measuring the rates are indicated for both slow and fast reactions, considering the use of batch or continuous reactors.
    [Show full text]
  • Autocatalysis in Chemical Networks
    1 Autocatalysis in chemical networks: unifications and extensions 1, 2 1 2 2 Alex Blokhuis, David Lacoste, and Philippe Nghe 1) 3 Gulliver Laboratory, UMR CNRS 7083, PSL University, 10 rue Vauquelin, Paris F-75231, 4 France 2) 5 Laboratoire de Biochimie, Chimie Biologie et Innovation, ESPCI Paris, PSL University,10 rue Vauquelin, 6 Paris F-75231, France 7 (Dated: May 16, 2020) 8 Autocatalysis is an essential property for theories of abiogenesis and chemical evolution. However, the 9 different formalisms proposed so far seemingly address different forms of autocatalysis and it remains unclear 10 whether all of them have been captured. Furthermore, the lack of unified framework thus far prevents 11 a systematic study of autocatalysis. Here, we derive general stoichiometric conditions for catalysis and 12 autocatalysis in chemical reaction networks from basic principles in chemistry. This allows for a classification 13 of minimal autocatalytic motifs, which includes all known autocatalytic systems and motifs that had not 14 been reported previously. We further examine conditions for kinetic viability of such networks, which 15 depends on the autocatalytic motifs they contain. Finally, we show how this framework extends the range 16 of conceivable autocatalytic systems, by applying our stoichiometric and kinetic analysis to autocatalysis 17 emerging from coupled compartments. The unified approach to autocatalysis presented in this work lays a 18 foundation towards the building of a systems-level theory of chemical evolution. 19 PACS numbers: 05.40.-a 82.65.+r 82.20.-w 20 INTRODUCTION 53 different descriptions of autocatalysis and is based on 27–30 54 reaction network stoichiometry .
    [Show full text]
  • Autocatalytic Cycles in a Copper-Catalyzed Azide–Alkyne Cycloaddition Reaction
    Article Cite This: J. Am. Chem. Soc. 2018, 140, 10221−10232 pubs.acs.org/JACS Autocatalytic Cycles in a Copper-Catalyzed Azide−Alkyne Cycloaddition Reaction † ⊥ † † † Sergey N. Semenov, , Lee Belding, Brian J. Cafferty, Maral P.S. Mousavi, † † † ∥ † ‡ § Anastasiia M. Finogenova, Ricardo S. Cruz, Ekaterina V. Skorb, , and George M. Whitesides*, , , † Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States ‡ Kavli Institute for Bionano Inspired Science and Technology, School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, Massachusetts 02138, United States § Wyss Institute for Biologically Inspired Engineering, Harvard University, 60 Oxford Street, Cambridge, Massachusetts 02138, United States *S Supporting Information ABSTRACT: This work describes the autocatalytic copper- catalyzed azide−alkyne cycloaddition (CuAAC) reaction between tripropargylamine and 2-azidoethanol in the presence of Cu(II) salts. The product of this reaction, tris- (hydroxyethyltriazolylmethyl)amine (N(C3N3)3), accelerates the cycloaddition reaction (and thus its own production) by two mechanisms: (i) by coordinating Cu(II) and promoting its reduction to Cu(I) and (ii) by enhancing the catalytic reactivity of Cu(I) in the cycloaddition step. Because of the cooperation of these two processes, a rate enhancement of >400× is observed over the course of the reaction. The kinetic profile of the autocatalysis can be controlled by using different azides and alkynes or ligands (e.g., ammonia) for Cu(II). When carried out in a layer of 1% agarose gel, and initiated by ascorbic acid, this autocatalytic reaction generates an autocatalytic front. This system is prototypical of autocatalytic reactions where the formation of a product, which acts as a ligand for a catalytic metal ion, enhances the production and activity of the catalyst.
    [Show full text]
  • Autocatalysis in a Hierarchically Organized Inorganic Chemical Network
    Autocatalysis in a Hierarchically Organized Inorganic Chemical Network Cole Mathis1, Haralampos Miras1 and Leroy Cronin1 1School of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK. [email protected] Abstract The Mo-Blue wheel system presents an interesting chemical One of the salient features of living systems is presence of system because it contains three clear hierarchical levels of Downloaded from http://direct.mit.edu/isal/proceedings-pdf/isal2019/31/652/1903529/isal_a_00235.pdf by guest on 27 September 2021 autocatalytic chemical reaction networks. Here we present a organization: small intermediates (Mo1-Mo6), small templates stochastic model of an inorganic autocatalyst, which is derived (Mo36) and larger structures (Mo154). The existence of these directly from empirical results. Using the model, we can clearly delineated levels of organization enables us to explore explore the emergence of autocatalysis and its consequences on the consequences of autocatalysis on the levels above and the larger, hierarchical, chemical network. This model provides below the proposed autocatalytic entity. a useful tool to study the emergence and organization of autocatalytic chemical networks and the effect autocatalysis To explore the consequences of this proposed mechanism we has on the global system dynamics. developed a model of the Mo-Blue dynamics. Our model is implemented using a kinetic Monte Carlo algorithm A characteristic feature of living systems is the existence of (Gillespie, 1977). This technique represents all reactions as autocatalytic cycles, which enables the exponential growth of either uni-molecular degradation reactions (A → B + C) or individuals and thus evolutionary dynamics (Cronin & Walker bimolecular (A + B→ C). Structures and intermediates form 2016, Kauffman 1992).
    [Show full text]