Chapters authored
Useful Work and Gibbs Energy
Part of the book: Thermodynamics
Murburn Model of Photosynthesis: Effect of Additives like Chloride and Bicarbonate
Oxygenic photosynthesis essentially involves photo-lysis (splitting of water to release oxygen), photo-reduction (formation of NADPH), and photo-phosphorylation (synthesis of ATP) reactions. These reactions use photoactive pigments such as chlorophylls and carotenoids. Z-scheme and Kok-Joliot cycle, the acclaimed and deterministic model of photosynthesis, are founded on the classical enzyme reaction mechanisms that depend solely on affinity-based interactions of enzymes with the substrates at defined active sites, for explaining electron/moiety transfers. In contrast, the new murburn model is built on stochastic collisions between diffusible reactive species (DRS) and other milieu components (including enzymes, substrates and ions). This novel perspective explains fast kinetics and action spectrum, and affords a spontaneously probable/evolvable biochemical system. The murburn perspective proposes that the photo-excitation of pigments in the chloroplast leads to effective charge separation and DRS-formation. DRS are stabilized/utilized by a pool of redox-active components via disordered/parallel bimolecular interactions at the thylakoid membrane interface. Herein, we provide details of how murburn model is a thermodynamically, kinetically, and mechanistically viable mechanism for the formation of ATP, NADPH and oxygen. The murburn model also provides more viable explanations for several classical experimental observations in photosynthesis (Emerson enhancement effect, Jagendorf/Racker experiments, etc.) and the non-specific effects of diverse additives (such as chloride and bicarbonate).
Part of the book: Chlorophylls
Comprehensive Analyses of the Enhancement of Oxygenesis in Photosynthesis by Bicarbonate and Effects of Diverse Additives: Z-scheme Explanation versus Murburn Model
The Z-scheme electron transport chain (ETC) explanation for photosynthesis starts with the serial/sequential transfer of electrons sourced from water molecules bound at Photosystem II via a deterministic array of redox centers (of various stationary/mobile proteins), before “sinking” via the reduction of NADP+ bound at flavin-enzyme reductase. Several research groups’ finding that additives (like bicarbonate) enhance the light reaction had divided the research community because it violated the Z-scheme. The untenable aspects of the Z-scheme perception were demonstrated earlier and a murburn bioenergetics (a stochastic/parallel paradigm of ion-radical equilibriums) model was proposed to explain photophosphorylation and Emerson effect. Herein, we further support the murburn model with accurate thermodynamic calculations, which show that the cost of one-electron abstraction from bicarbonate [491 kJ/mol] is lower than water [527 kJ/mol]. Further, copious thioredoxin enables the capture of photoactivated electrons in milieu, which aid in the reduction of nicotinamide nucleotides. The diffusible reactive species (DRS) generated in milieu sponsor phosphorylations and oxygenic reactions. With structural analysis of Photosystems and interacting molecules, we chart out the equations of reactions that explain the loss of labeled O-atom traces in delocalized oxygenesis. Thus, this essay discredits the Z-scheme and explains key outstanding observations in the field.
Part of the book: Plant Physiology Annual Volume 2023