It is becoming increasingly apparent that a generalized thermodynamic approach to chemical reacti... more It is becoming increasingly apparent that a generalized thermodynamic approach to chemical reactivity, in place since the pioneering contributions of Boltzmann and Gibbs a century ago, is unable to adequately explain, let alone predict, the entire space of chemical potentiality, and that more extensive exploration of the kinetic domain may be required. The relatively recent discovery of kinetically-governed processes, such as those observed in dissipative self-assembly, reveals the existence of a largely undiscovered kinetic domain for which we propose the general term dynamic kinetic chemistry. Our analysis suggests that all biological systems and associated sub-systems belong to this distinct kinetic domain, thereby enabling the placement of biological systems within a coherent physical/chemical framework. Such a classification appears to assist in bridging the problematic animate– inanimate conceptual gap as well as offering new insights into the origin of life (OOL) process. Add...
Thermodynamic stability, as expressed by the Second Law, generally constitutes the driving force ... more Thermodynamic stability, as expressed by the Second Law, generally constitutes the driving force for chemical assembly processes. Yet, somehow, within the living world most self-organisation processes appear to challenge this fundamental rule. Even though the Second Law remains an inescapable constraint, under energy-fuelled, far-from-equilibrium conditions, populations of chemical systems capable of exponential growth can manifest another kind of stability, dynamic kinetic stability (DKS). It is this stability kind based on time/persistence, rather than on free energy, that offers a basis for understanding the evolutionary process. Furthermore, a threshold distance from equilibrium, leading to irreversibility in the reproduction cycle, is needed to switch the directive for evolution from thermodynamic to DKS. The present report develops these lines of thought and argues against the validity of a thermodynamic approach in which the maximisation of the rate of energy dissipation/entr...
The origin-of-life problem remains one of the major scientific riddles of all time and the diffic... more The origin-of-life problem remains one of the major scientific riddles of all time and the difficulties in attempts to synthesize simple protolife reflect yet one additional facet of this long-standing problem. In this review we argue that a strategy for the synthesis of protolife requires the characterization of the physicochemical state of life’s primordial beginnings, not just its material composition. It is through the concept of dynamic kinetic stability (DKS) that key elements of that state can be specified. A protolife system potentially able to evolve toward biological complexity would need to be both driven by exponential replicative growth as well as to be in a dynamic, non-equilibrium and energy-fueled (DKS) state. With the recent discovery that DKS systems are experimentally accessible and show remarkably different physical and chemical characteristics to regular chemical systems, the door to the possible synthesis of simple protolife now appears to be open.
Origins of life and evolution of the biosphere : the journal of the International Society for the Study of the Origin of Life, Jan 23, 2016
In this paper we propose a logical connection between the physical and biological worlds, one res... more In this paper we propose a logical connection between the physical and biological worlds, one resting on a broader understanding of the stability concept. We propose that stability manifests two facets - time and energy, and that stability's time facet, expressed as persistence, is more general than its energy facet. That insight leads to the logical formulation of the Persistence Principle, which describes the general direction of material change in the universe, and which can be stated most simply as: nature seeks persistent forms. Significantly, the principle is found to express itself in two mathematically distinct ways: in the replicative world through Malthusian exponential growth, and in the 'regular' physical/chemical world through Boltzmann's probabilistic considerations. By encompassing both 'regular' and replicative worlds, the principle appears to be able to help reconcile two of the major scientific theories of the 19th century - the Second Law o...
Journal of the Chemical Society, Perkin Transactions 2, 1978
... By Yishai Karton and Addy Pross," Department of Chemistry, Ben Gurion University, Beer S... more ... By Yishai Karton and Addy Pross," Department of Chemistry, Ben Gurion University, Beer Sheva, Israel ... 0 20 LO 60 80 % Acetone (v/v) FIGURE 3 Effect of added acetone on the selectivities of (A) diphenylmethyl chloride ; (B) benzyl chloride; (C) octyl bro-mide in 50% aqueous ...
Journal of the Chemical Society, Perkin Transactions 2, 1977
The effect of solvent polarity on the selectivity of a series of substituted diphenylmethyl deriv... more The effect of solvent polarity on the selectivity of a series of substituted diphenylmethyl derivatives is investigated. The key result is that all substrates studied exhibit higher selectivity in solvents of higher polarity. Three possible explanations for this effect are proposed. (a) Greater stabilization of solvolytic intermediates in more polar solvents results in these species showing greater selectivity. (b) Increased solvent ionizing power results in greater dissociation to free ions which are intrinsically more selective. (c) The effect of an increase in solvent polarity on the nucleophilicity of ethanol and water may result in enhanced ethanol nucleophilicity. No clear differentiation between these three alternatives appears possible at the present time.
It is becoming increasingly apparent that a generalized thermodynamic approach to chemical reacti... more It is becoming increasingly apparent that a generalized thermodynamic approach to chemical reactivity, in place since the pioneering contributions of Boltzmann and Gibbs a century ago, is unable to adequately explain, let alone predict, the entire space of chemical potentiality, and that more extensive exploration of the kinetic domain may be required. The relatively recent discovery of kinetically-governed processes, such as those observed in dissipative self-assembly, reveals the existence of a largely undiscovered kinetic domain for which we propose the general term dynamic kinetic chemistry. Our analysis suggests that all biological systems and associated sub-systems belong to this distinct kinetic domain, thereby enabling the placement of biological systems within a coherent physical/chemical framework. Such a classification appears to assist in bridging the problematic animate– inanimate conceptual gap as well as offering new insights into the origin of life (OOL) process. Add...
Thermodynamic stability, as expressed by the Second Law, generally constitutes the driving force ... more Thermodynamic stability, as expressed by the Second Law, generally constitutes the driving force for chemical assembly processes. Yet, somehow, within the living world most self-organisation processes appear to challenge this fundamental rule. Even though the Second Law remains an inescapable constraint, under energy-fuelled, far-from-equilibrium conditions, populations of chemical systems capable of exponential growth can manifest another kind of stability, dynamic kinetic stability (DKS). It is this stability kind based on time/persistence, rather than on free energy, that offers a basis for understanding the evolutionary process. Furthermore, a threshold distance from equilibrium, leading to irreversibility in the reproduction cycle, is needed to switch the directive for evolution from thermodynamic to DKS. The present report develops these lines of thought and argues against the validity of a thermodynamic approach in which the maximisation of the rate of energy dissipation/entr...
The origin-of-life problem remains one of the major scientific riddles of all time and the diffic... more The origin-of-life problem remains one of the major scientific riddles of all time and the difficulties in attempts to synthesize simple protolife reflect yet one additional facet of this long-standing problem. In this review we argue that a strategy for the synthesis of protolife requires the characterization of the physicochemical state of life’s primordial beginnings, not just its material composition. It is through the concept of dynamic kinetic stability (DKS) that key elements of that state can be specified. A protolife system potentially able to evolve toward biological complexity would need to be both driven by exponential replicative growth as well as to be in a dynamic, non-equilibrium and energy-fueled (DKS) state. With the recent discovery that DKS systems are experimentally accessible and show remarkably different physical and chemical characteristics to regular chemical systems, the door to the possible synthesis of simple protolife now appears to be open.
Origins of life and evolution of the biosphere : the journal of the International Society for the Study of the Origin of Life, Jan 23, 2016
In this paper we propose a logical connection between the physical and biological worlds, one res... more In this paper we propose a logical connection between the physical and biological worlds, one resting on a broader understanding of the stability concept. We propose that stability manifests two facets - time and energy, and that stability's time facet, expressed as persistence, is more general than its energy facet. That insight leads to the logical formulation of the Persistence Principle, which describes the general direction of material change in the universe, and which can be stated most simply as: nature seeks persistent forms. Significantly, the principle is found to express itself in two mathematically distinct ways: in the replicative world through Malthusian exponential growth, and in the 'regular' physical/chemical world through Boltzmann's probabilistic considerations. By encompassing both 'regular' and replicative worlds, the principle appears to be able to help reconcile two of the major scientific theories of the 19th century - the Second Law o...
Journal of the Chemical Society, Perkin Transactions 2, 1978
... By Yishai Karton and Addy Pross," Department of Chemistry, Ben Gurion University, Beer S... more ... By Yishai Karton and Addy Pross," Department of Chemistry, Ben Gurion University, Beer Sheva, Israel ... 0 20 LO 60 80 % Acetone (v/v) FIGURE 3 Effect of added acetone on the selectivities of (A) diphenylmethyl chloride ; (B) benzyl chloride; (C) octyl bro-mide in 50% aqueous ...
Journal of the Chemical Society, Perkin Transactions 2, 1977
The effect of solvent polarity on the selectivity of a series of substituted diphenylmethyl deriv... more The effect of solvent polarity on the selectivity of a series of substituted diphenylmethyl derivatives is investigated. The key result is that all substrates studied exhibit higher selectivity in solvents of higher polarity. Three possible explanations for this effect are proposed. (a) Greater stabilization of solvolytic intermediates in more polar solvents results in these species showing greater selectivity. (b) Increased solvent ionizing power results in greater dissociation to free ions which are intrinsically more selective. (c) The effect of an increase in solvent polarity on the nucleophilicity of ethanol and water may result in enhanced ethanol nucleophilicity. No clear differentiation between these three alternatives appears possible at the present time.
Uploads
Papers