498
T. Marinoet al.
This behavior is different from that observed in the LUMO comparison between
Ca-MDH and Ce-MDH in a previous work [55] and confirms the better Lewis acid
nature of lanthanide ions.
4 Conclusions
In the present work, we have performed a theoretical investigation at QM level
and using the hybrid B3LYP functional with the dispersion contribution, for giving
details about the different coordination chemistry of the two considered lanthanide
ions (Ce
3+ and Eu
3+ ) in their ES complexes. The catalytic behavior of Ce-MDH
as compared to Ca-MDH has been also examined. The emerged differences and
similarities have been correlated to the periodic properties as atomic radius and
relativistic effects (in the case of lanthanide ions).
In particular, results show that:
• PESs calculated for Ce-MDH by taking into account three diverse dielectric constant values do not suffer evident changes.
• Metal ion can play a crucial role in the activation of the methanol substrate (first step
of the investigated catalytic mechanism) more than in the PQQ cofactor reduction.
• Cerium ion is a better Lewis acid than calcium and europium ones.
• Cerium more than europium acts as a better biomimetic agent for calciumcontaining methanol dehydrogenase.
• Frontier orbital and NBO analysis of the enzyme–substrate complex for Ce- and
Eu-MDH support the better catalytic activity of the cerium-containing enzyme.
References
1. Good NM, Vu HN, Suriano CJ, Subuyuj GA, Skovran E, Martinez-Gomez NC (2016) Pyrroloquinoline quinone ethanol dehydrogenase in Methylobacterium extorquens AM1 extends
lanthanide-dependent metabolism to multicarbon substrates. J Bacteriol 198:3109–3118.
https://doi.org/10.1128/JB.00478-16
2. Panichev AM (2015) Rare Earth Elements: Review of medical and biological properties and
their abundance in the rock materials and mineralized spring waters in the context of animal
and human geophagia reason evaluation Achiev. Life Sci 9:95–103. https://doi.org/10.1016/j.
als.2015.12.001
3. Brittain HG, Richardson FS, Martin RB (1976) Terbium(III) emission as a probe of calcium(II)
binding sites in proteins. J Am Chem Soc 98:8255–8260. https://doi.org/10.1021/ja00441a060
4. Martin RB, Richardson F (1979) Lanthanides as probes for calcium in biological systems. Q
Rev Biophys 12:181–209. https://doi.org/10.1017/S0033583500002754
5. Chistoserdova L (1996) Metabolism of formaldehyde in M. extorquens AM1. Molecular genetic
analysis and mutant characterization. In: Lidstrom ME, Tabita FR (eds) Microbial growth on
C1 compounds. Kluwer Academic Publishers, Dordrecht, pp 16–24
6. Harms N, Ras J, Koning S, Reijinders WNM, Stouthamer AH, van Spanning RJM (1996)
Genetics of C1 metabolism regulation in Paracoccus denitrificans. In: Lidstrom ME, Tabita
T. Marinoet al.
This behavior is different from that observed in the LUMO comparison between
Ca-MDH and Ce-MDH in a previous work [55] and confirms the better Lewis acid
nature of lanthanide ions.
4 Conclusions
In the present work, we have performed a theoretical investigation at QM level
and using the hybrid B3LYP functional with the dispersion contribution, for giving
details about the different coordination chemistry of the two considered lanthanide
ions (Ce
3+ and Eu
3+ ) in their ES complexes. The catalytic behavior of Ce-MDH
as compared to Ca-MDH has been also examined. The emerged differences and
similarities have been correlated to the periodic properties as atomic radius and
relativistic effects (in the case of lanthanide ions).
In particular, results show that:
• PESs calculated for Ce-MDH by taking into account three diverse dielectric constant values do not suffer evident changes.
• Metal ion can play a crucial role in the activation of the methanol substrate (first step
of the investigated catalytic mechanism) more than in the PQQ cofactor reduction.
• Cerium ion is a better Lewis acid than calcium and europium ones.
• Cerium more than europium acts as a better biomimetic agent for calciumcontaining methanol dehydrogenase.
• Frontier orbital and NBO analysis of the enzyme–substrate complex for Ce- and
Eu-MDH support the better catalytic activity of the cerium-containing enzyme.
References
1. Good NM, Vu HN, Suriano CJ, Subuyuj GA, Skovran E, Martinez-Gomez NC (2016) Pyrroloquinoline quinone ethanol dehydrogenase in Methylobacterium extorquens AM1 extends
lanthanide-dependent metabolism to multicarbon substrates. J Bacteriol 198:3109–3118.
https://doi.org/10.1128/JB.00478-16
2. Panichev AM (2015) Rare Earth Elements: Review of medical and biological properties and
their abundance in the rock materials and mineralized spring waters in the context of animal
and human geophagia reason evaluation Achiev. Life Sci 9:95–103. https://doi.org/10.1016/j.
als.2015.12.001
3. Brittain HG, Richardson FS, Martin RB (1976) Terbium(III) emission as a probe of calcium(II)
binding sites in proteins. J Am Chem Soc 98:8255–8260. https://doi.org/10.1021/ja00441a060
4. Martin RB, Richardson F (1979) Lanthanides as probes for calcium in biological systems. Q
Rev Biophys 12:181–209. https://doi.org/10.1017/S0033583500002754
5. Chistoserdova L (1996) Metabolism of formaldehyde in M. extorquens AM1. Molecular genetic
analysis and mutant characterization. In: Lidstrom ME, Tabita FR (eds) Microbial growth on
C1 compounds. Kluwer Academic Publishers, Dordrecht, pp 16–24
6. Harms N, Ras J, Koning S, Reijinders WNM, Stouthamer AH, van Spanning RJM (1996)
Genetics of C1 metabolism regulation in Paracoccus denitrificans. In: Lidstrom ME, Tabita