The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments
Abstract
:1. Introduction
2. Results
2.1. Ex Vivo, In Vitro Oxidative Challenge of Red Blood Cells by Hydroperoxides
2.2. Redox Equilibria of the Bio-Thiols and Measurement of the Standard Electrochemical Potential (E0)
E0(RefS) + RT/nF ln([OXRefS]/[REDRef]2)
2.3. Calculation of the Redox Potential of the Thiol Group of Hemoglobin’s Beta-93 Cysteine
E0(Hb) + RT/nF ln [HbSSG]/[HbSH]
2.3.1. First-Tier Calculation
2.3.2. Second-Tier Calculation
2.4. Coping with Oxidative Stress and Redox Potentials of the Thiols in the Red Blood Cells
2.4.1. Placement of Glutathionyl-Hemoglobin among the Redox Bio-Thiols
2.4.2. Towards a Mechanistic Understanding of the RBC Response to Oxidative Burst
E0(Hb) + RT/nF ln [HbSSG]/[HbSH]
3. Discussion
4. Materials and Methods
5. Conclusions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
Appendix A
Time min | GSH [mM] | GSSG [mM] | HbSSG [mM] | GS_tot [mM] | HbSSG % |
---|---|---|---|---|---|
0 | 1.24 | 0.014 | 0.0006 | 1.27 | 0.01% |
10 | 0.06 | 0.557 | 0.0738 | 1.25 | 1.44% |
20 | 0.09 | 0.529 | 0.0625 | 1.21 | 1.22% |
30 | 0.34 | 0.443 | 0.0513 | 1.28 | 1.00% |
40 | 0.59 | 0.314 | 0.0400 | 1.25 | 0.78% |
50 | 0.86 | 0.171 | 0.0313 | 1.23 | 0.61% |
60 | 1.13 | 0.057 | 0.0213 | 1.26 | 0.41% |
70 | 1.20 | 0.029 | 0.0138 | 1.27 | 0.27% |
80 | 1.23 | 0.014 | 0.0088 | 1.27 | 0.17% |
90 | 1.26 | 0.007 | 0.0038 | 1.28 | 0.07% |
100 | 1.27 | 0.007 | 0.0013 | 1.29 | 0.02% |
110 | 1.26 | 0.007 | 0.0013 | 1.27 | 0.02% |
120 | 1.26 | 0.007 | 0.0025 | 1.27 | 0.05% |
Appendix B
Appendix C
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Thiol | E0′ 1 | E0′ 2 | E0(7.4) 3 | Ref. |
---|---|---|---|---|
hemoglobin (human) | - | - | −121 | This work |
glutathione | −205 | −205 ± 3 | −264 | [54] |
homocysteine | −196 | −218 ± 3 | - | [54] |
cysteine | −247 | −246 ± 3 | - | [54] |
γGluCySH | - | −265 ± 3 | - | [54] |
penicillamine | −267 | −266 ± 3 | - | [54] |
N-acetylcysteine | - | −268 ± 3 | - | [54] |
HSCyGly | - | −272 ± 3 | - | [54] |
cysteine methyl ester | - | −282 ± 3 | - | [54] |
N-acetylpenicillamine | - | −295 ± 4 | - | [54] |
cysteamine | −203 | −372 ± 7 | - | [54] |
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Rubino, F.M. The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments. Molecules 2021, 26, 2528. https://doi.org/10.3390/molecules26092528
Rubino FM. The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments. Molecules. 2021; 26(9):2528. https://doi.org/10.3390/molecules26092528
Chicago/Turabian StyleRubino, Federico Maria. 2021. "The Redox Potential of the β-93-Cysteine Thiol Group in Human Hemoglobin Estimated from In Vitro Oxidant Challenge Experiments" Molecules 26, no. 9: 2528. https://doi.org/10.3390/molecules26092528