Iskanje po katalogu digitalne knjižnice

Opis: The self-organization of open reaction systems is closely related to specific mechanisms that allow the export of internally generated entropy from systems to their environment. According to the second law of thermodynamics, systems with effective entropy export to the environment are better internally organized. Therefore, they are in thermodynamic states with low entropy. In this context, we study how self-organization in enzymatic reactions depends on their kinetic reaction mechanisms. Enzymatic reactions in an open system are considered to operate in a non-equilibrium steady state, which is achieved by satisfying the principle of maximum entropy production (MEPP). The latter is a general theoretical framework for our theoretical analysis. Detailed theoretical studies and comparisons of the linear irreversible kinetic schemes of an enzyme reaction in two and three states are performed. In both cases, in the optimal and statistically most probable thermodynamic steady state, a diffusion-limited flux is predicted by MEPP. Several thermodynamic quantities and enzymatic kinetic parameters, such as the entropy production rate, the Shannon information entropy, reaction stability, sensitivity, and specificity constants, are predicted. Our results show that the optimal enzyme performance may strongly depend on the number of reaction steps when linear reaction mechanisms are considered. Simple reaction mechanisms with a smaller number of intermediate reaction steps could be better organized internally and could allow fast and stable catalysis. These could be features of the evolutionary mechanisms of highly specialized enzymes.
Ključne besede: enzymes, kinetic data analysis, steady state, self-organization, maximum entropy production
Objavljeno v DKUM: 08.05.2024; Ogledov: 234; Prenosov: 9
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Opis: The discrete element method (DEM) is an alternative computational tool for augmenting laboratory experiments because of its advantages in detailing macro- and micro-mechanical information. However, it should be noted that the DEM does not usually consider the convergence for each time step, because of the necessity for a huge calculation time. In that case, it indicates that the uniqueness of the solution is not guaranteed, except in the case of a very small strain rate, even though the behavior looks qualitatively reasonable. At first, the influence of strain rate among numerically imaginary input parameters for a non-cohesive material was investigated for monotonic, biaxial shear tests. Then, new findings were obtained from the DEM simulations. Strain rate has a significant influence on the shear behavior, especially after the peak strength of dense specimens. A quasi-static steady state exists, not a static steady state. The “strong” fabric ratio is closely related to the stress ratio. The maximum slip coordination number occurs around the phase-transformation ratio and the shear band appears around the peak strength.
Ključne besede: discrete element method, DEM, induced anisotropy, quasi-static steady state, strain rate, uniqueness
Objavljeno v DKUM: 14.06.2018; Ogledov: 1144; Prenosov: 220
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