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The electron transport chain (ETC) is a crucial metabolic pathway that facilitates energy conversion in prokaryotic and eukaryotic cells. In eukaryotes, the ETC comprises four membrane-associated protein complexes in the inner mitochondrial membrane. In prokaryotes, the ETC in the plasma membrane can vary in composition, with fewer or different complexes depending on the organism and environmental conditions. These complexes transfer electrons from electron donors, such as NADH and FADH2, to...
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Chemiosmosis and ATP Synthesis01:22

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The electron transport chain is a critical component of cellular respiration, occurring in the inner mitochondrial membrane. It facilitates the transfer of high-energy electrons from reduced cofactors NADH and FADH₂ to molecular oxygen, the final electron acceptor. This transfer of electrons through a series of protein complexes is tightly coupled to the translocation of protons across the membrane, generating a proton gradient essential for ATP synthesis.Electron Flow and Proton...
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Electron Transport Chain: Complex III and IV01:43

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During the electron transport chain, electrons from NADH and FADH2 are first transferred to complexes I and II, respectively. These two complexes then transfer the electrons to ubiquinol, which carries them further to complex III. Complex III passes the electrons across the intermembrane space to Cyt c, which carries them further to complex IV. Complex IV donates electrons to oxygen and reduces it to water. As electrons pass through complexes I, III, and IV, the energy released aids the pumping...
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Electron Transport Chains01:28

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The final stage of cellular respiration is oxidative phosphorylation that consists of two steps: the electron transport chain and chemiosmosis. The electron transport chain is a set of proteins found in the inner mitochondrial membrane in eukaryotic cells. Its primary function is to establish a proton gradient that can be used during chemiosmosis to produce ATP and generate electron carriers, such as NAD+ and FAD, that are used in glycolysis and the citric acid cycle.
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Tutorial on computing nonadiabatic proton-coupled electron transfer rate constants.

Phillips Hutchison1, Kai Cui2, Jiayun Zhong2

  • 1Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544, USA.

The Journal of Chemical Physics
|September 5, 2025
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Summary
This summary is machine-generated.

Proton-coupled electron transfer (PCET) is fundamental across sciences. This tutorial details computing PCET rate constants, including quantum effects like proton tunneling, using the pyPCET package for diverse systems.

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Area of Science:

  • Multidisciplinary science
  • Physical chemistry
  • Biophysics

Background:

  • Proton-coupled electron transfer (PCET) is a fundamental process in chemistry, biology, and physics.
  • A general theoretical framework for PCET has been developed, incorporating quantum mechanical effects of electrons and protons, hydrogen tunneling, environmental reorganization, and donor-acceptor fluctuations.
  • Analytical rate constants have been derived for various regimes, with a focus on the vibronically nonadiabatic regime.

Purpose of the Study:

  • To provide a tutorial on computing input quantities for PCET rate constants in the vibronically nonadiabatic regime.
  • To detail the calculation of inner-sphere and outer-sphere reorganization energies, diabatic proton potentials, electronic coupling, reaction free energy, and proton donor-acceptor distance distribution.
  • To guide the determination of electron-proton nonadiabaticity for vibronic coupling.

Main Methods:

  • Focus on the golden rule rate constant expression applicable to the vibronically nonadiabatic regime.
  • Detailed instructions for computing essential input parameters for PCET systems.
  • Application of methods to diverse systems including enzymatic, homogeneous molecular electrochemical, photochemical molecular, and heterogeneous electrochemical PCET.

Main Results:

  • Provides a comprehensive guide for calculating PCET rate constants.
  • Demonstrates the application of the theoretical formulation through detailed examples.
  • Introduces the publicly available Python package, pyPCET, for computing nonadiabatic PCET rate constants.

Conclusions:

  • The tutorial equips researchers with the necessary tools and knowledge to compute PCET rate constants.
  • The pyPCET package facilitates the application of advanced theoretical methods to various PCET systems.
  • This work enhances the understanding and computational accessibility of complex PCET processes across scientific disciplines.