Theoretical Modeling of Redox Potentials of Biomolecules
Abstract
:1. Introduction
2. Theoretical-Computational Approaches
2.1. Evaluation of the Free Energy by Means of Phase Space Sampling
2.2. Implicit Solvent Approaches
2.3. Quantum-Classical (QM-CL) Approaches
2.3.1. QM/MM Strategies: On-the-Fly Treatment of the QM Region
- In the subtractive scheme, the inner part is treated at both QM and CL levels, whereas the outer part is treated at the CL level only. The system energy is then estimated by summation of the inner-part QM energy and the outer-part energy subtracted by the inner-part CL energy (see, for example, the IMOMO model [44]).In this simple scheme, the coupling between the inner- and outer-parts is treated at the CL level, i.e., typically modeling the electrostatic terms as Coulomb interactions between QM- and CL-fixed atomic charges.
- In the additive scheme, the energy of the outer part of the system is still evaluated at CL level, but the inner part is described by using two energy terms: the QM energy of the inner part and an explicit coupling term providing the interaction between the two subparts.QM/MM methods differ by these coupling terms, which involve the description of the mutual polarization between the two subparts of the system. Briefly, such a polarization can be described as mechanical embedding, electrostatic embedding, and polarized embedding [45].These three approaches differ in how the mutual effects are treated: in the mechanical embedding scheme, the atomic charges are assigned to the QM subpart, and the interactions between the two regions are simply described by the charge–charge electrostatics. In the electrostatic embedding, the effect of the environment on the inner region is included by performing the QM calculations in the presence of the MM charges of the outer region. The polarized embedding attempts to include also the polarization of the MM charges of the outer region.The reader is referred to the extended review by Bakowies and Thiel [45], where a detailed description of these methods is reported.
2.3.2. QM/MM Strategies: A-Posteriori Treatment of the QM Region
2.4. Methods Based on a Full Quantum-Mechanical Hamiltonian
2.5. Statistical Inaccuracies
3. Applications
3.1. Redox Potential of Proteins
3.1.1. Redox Potential of Copper Proteins
3.1.2. Redox Potentials of Iron–Sulfur Proteins
3.1.3. The NAD/FAD Redox Potential
3.1.4. Redox potentials of Cytochromes
3.1.5. Redox Potentials of Small Molecules in Enzymes
- Redox potentials of OEC in PSIIThe oxygen-evolving complex (OEC; see Figure 6) in the PSII has been one of the most studied redox active sites to describe the mechanism of water oxidation catalyzed by the PSII. The use of DFT calculations and quantum-chemical-cluster methods [62] have been useful in the structural characterization of the intermediate states of the active site as well as in the estimation of the relative energies of the water oxidation-reaction steps [123,124].
- Nitric-oxide reductaseNitric-oxide reductase (NOR; see Figure 7) is an enzyme that catalyzes the reduction of nitric oxide to nitrous oxide [125]. To gain insight in the catalytic steps describing such a reaction, the quantum-chemical-cluster approach [62] was applied. Such a method suggested a cis:b3 mechanism with respect to the trans mechanism, which was found to be energetically unfavorable. In addition, the authors described the energetics of several steps involved in this reaction and found the mechanism to be -dependent, in agreement with experimental data.
3.2. Redox Potential of Nucleic Acids
3.2.1. The Redox Potential of Single Nucleotides/Nucleosides
3.2.2. The Redox Potential of Complex Nucleic Acids (oligomers/ssDNA/dsDNA)
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Chen, C.G.; Nardi, A.N.; Amadei, A.; D’Abramo, M. Theoretical Modeling of Redox Potentials of Biomolecules. Molecules 2022, 27, 1077. https://doi.org/10.3390/molecules27031077
Chen CG, Nardi AN, Amadei A, D’Abramo M. Theoretical Modeling of Redox Potentials of Biomolecules. Molecules. 2022; 27(3):1077. https://doi.org/10.3390/molecules27031077
Chicago/Turabian StyleChen, Cheng Giuseppe, Alessandro Nicola Nardi, Andrea Amadei, and Marco D’Abramo. 2022. "Theoretical Modeling of Redox Potentials of Biomolecules" Molecules 27, no. 3: 1077. https://doi.org/10.3390/molecules27031077