Izvestiya of Saratov University.

Chemistry. Biology. Ecology

ISSN 1816-9775 (Print)
ISSN 2541-8971 (Online)


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Shablovsky Y. О. Тhermodynamical modelling for equilibriumless processes in biochemical systems. Izvestiya of Saratov University. Chemistry. Biology. Ecology, 2026, vol. 26, iss. 1, pp. 47-53. DOI: 10.18500/1816-9775-2026-26-1-47-53, EDN: IPPEYY

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Russian
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Article
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544.341
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IPPEYY

Тhermodynamical modelling for equilibriumless processes in biochemical systems

Autors: 
Shablovsky Yaroslav О., Pavel Sukhoi State Technical University of Gomel
Abstract: 

The dynamics of a biochemical system is obviously subjected to universal laws of thermodynamics, but analytical forms of the criteria and constraints having been deduced up to date and findable in the literature are to some extent arguable. The paper examines the thermodynamic constraints on chemical reaction pathways and is aimed at fi nding the ways to boost equilibrium-limited reactions under mild conditions by means of blurring the equilibrium or circumventing it. In particular, herein we deal with the thermodynamic analysis of reactions that proceed with exhibiting either the multiplicity of equilibrium states (partial equilibria) or the total absence of an equilibrium. The multiplicity of equilibrium states refers to oscillatory reactions. Thermochemical regularities of such reactions are revealed, and it is shown that they are not determined by positive or negative feedback. The total absence of an equilibrium is inherent in conjugate reactions, i.e. in couples of chemical reactions, one of which (namely, the induced reaction) is impossible in the absence of the other one (namely, the inducing reaction) because of being thermodynamically prohibited. To tackle the challenge of providing thermodynamic control of such reactions we focus on exergetic restrictions and hence deduce general conditions for inducing a heterogeneous homophase reaction.

Reference: 
  1. Alberty R. A. Equilibrium compositions of solutions of biochemical species and heats of biochemical reactions // Proceedings of the National Academy of Sciences. 1991. Vol. 88, №8. Р. 3268–3271. https://doi.org/10.1073/pnas.88.8.3268
  2. Quan H., Beard D. A. Thermodynamics of stoichiometric biochemical networks in living systems far from equilibrium // Biophysical Chemistry. 2005. Vol. 114, №2-3. Р. 213–220. https://doi.org/10.1016/j.bpc.2004.12.001
  3. Shinnar R., Feng C. A. Structure of complex catalytic reactions: Thermodynamic constraints in kinetic modeling and catalyst evaluation // Industrial & Engineering Chemistry Fundamentals. 1985. Vol. 24, №1. Р. 153–170. https://doi.org/10.1021/i100018a005
  4. Armor J. N. Overcoming equilibrium limitations in chemical processes // Applied Catalysis A: General. 2001. Vol. 222, №1-2. P. 91–99. https://doi.org/10.1016/S0926-860X(01)00833-X
  5. Hung J., Song Y., Riisager A. Interfacial thermoconvection and relay catalysis enable equilibrium shifting and rapid glucose-to-fructose isomerization // Angewandte Chemie (International Edition). 2024. Vol. 63, №50. Р. e202411544-1–e202411544-10. https://doi.org/10.1002/anie.202411544
  6. Nagiev T. The theory of conjugate reactions in the context of modern ideas // Advances in Chemical Engineering and Science. 2020. Vol. 10, №1. Р. 52–68. https://doi.org/10.4236/aces.2020.101004
  7. Keizer J. Thermodynamic coupling in chemical reactions // Journal of Theoretical Biology. 1975. Vol. 49, №2. P. 323–335. https://doi.org/10.1016/S0022-5193(75)80037-3
  8. Voit E. O. Biochemical systems theory: A review // ISRN Biomathematics. 2013. Vol. 2013, №1. Р. 1–53. https://doi.org/10.1155/2013/897658
  9. Штыков С. Н. Организованные среды как альтернатива традиционным растворителям в химическом анализе // Известия Саратовского университета. Новая серия. Серия: Химия. Биология. Экология. 2005. Т. 5, вып. 1. С. 47–52.
  10. Michaelides E. Exergy in biological systems // Exergy analysis for energy conversion systems. Cambridge : Cambridge University Press, 2021. Р. 201–250. https://doi.org/10.1017/9781108635684.006
  11. Шилов Н. А. О сопряжённых реакциях окисления. М. : Типография Мамонтова, 1905. 304 с.
  12. Нагиев Т. М. Сопряжённые реакции окисления перекисью водорода // Успехи химии. 1985. Т. 54, №10. Р. 1654–1673. https://doi.org/10.1070/RC1985v054n10ABEH003152
  13. Брук Л. Г., Тёмкин О. Н. Сопряжённые реакции: новые возможности старой идеи // Кинетика и катализ. 2016. Т. 57, №3. С. 275–295. https://doi.org/10.7868/S0453881116030023
  14. Nicolis G., Portnow J. Chemical oscillations // Chemical Reviews. 1973. Vol. 73, №4. Р. 365–384. https://doi.org/10.1021/cr60284a003
  15. Поваров В. Г. О некоторых издержках современного моделирования колебательных химических процессов // Вестник Санкт-Петербургского университета. Серия 4: Химия. 2007. №3. С. 75–87.
  16. Ryzowicz C. J., Bertram R., Karamched B. R. Oscillations in delayed positive feedback systems // Phys. Chem. Chem. Phys. 2024. Vol. 26, №38. Р. 24861–24869. https://doi.org/10.1039/d4cp01867b
  17. Yutaka H., Takada M., Hara S. Biochemical oscillations in delayed negative cyclic feedback: Existence and profiles // Automatica. 2013. Vol. 49, №9. P. 2581–2590. https://doi.org/10.1016/j.automatica.2013.04.020
  18. Bharath A., Herzel H., Thattai M. Positive feedback promotes oscillations in negative feedback loops // PLoS ONE. 2014. Vol. 9, №8. Р. e104761-1–e104761-11. https://doi.org/10.1371/journal.pone.0104761
  19. Marsland R., Wenping C., Horowitz J. The thermodynamic uncertainty relation in biochemical oscillations // Journal of The Royal Society Interface. 2019. Vol. 16, №154. Р. 20190098-1–20190098-12. https://doi.org/10.1098/rsif.2019.0098
  20. Kurin-Csörgei K., Epstein I., Orbán M. Systematic design of chemical oscillators using complexation and precipitation equilibria // Nature. 2005. Vol. 433, iss. 7022. Р. 139–142. https://doi.org/10.1038/nature03214
  21. Крупенин В. Л. Автоколебательные процессы в сильно нелинейных системах в присутствии случайных возмущений // Вестник научно-технического развития. 2008. Т. 14, №10. С. 54–59.
Received: 
01.12.2025
Accepted: 
04.02.2026
Published: 
31.03.2026
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