The pK $_{\textrm{a}}$ value of the proximal water molecule trans to a high-valent Mn $^{\textrm{{V}}}$ O porphyrin: towards the control of reactivity by pH. Saint-Germes, L., Bar, L., Dejeu, J., Spinelli, N., Defrancq, E., & Pratviel, G. Dalton Transactions, 46(36):12088–12094, 2017. Paper doi abstract bibtex In water, the protonation state of the proximal water molecule of a high-valent manganese-oxo porphyrin could be controlled by pH. While in interaction with DNA the porphyrin was able to cleave DNA, only when the proximal water molecule was in the form of a hydroxyl group. , The high-valent manganese-oxo species of Mn-TMPyP4 porphyrin interacts in the minor grooves of AT-rich regions of DNA and mediates hydroxylation of C–H bonds of deoxyribose leading to DNA break. The reaction was observed at different pHs. It is shown that the hydroxylation was not efficient at low pH (pH 6) while it worked well at higher pH (pH 8). Deprotonation of the coordinated water molecule, trans to the manganese-oxo entity, into a hydroxide anion drives high-valent manganese-oxo porphyrin toward hydroxylation at pH \textgreater 7.
@article{saint-germes_pk_2017,
title = {The {pK} $_{\textrm{a}}$ value of the proximal water molecule trans to a high-valent {Mn} $^{\textrm{{V}}}$ {O} porphyrin: towards the control of reactivity by {pH}},
volume = {46},
issn = {1477-9226, 1477-9234},
shorttitle = {The {pK} $_{\textrm{a}}$ value of the proximal water molecule trans to a high-valent {Mn} $^{\textrm{{V}}}$ {O} porphyrin},
url = {http://xlink.rsc.org/?DOI=C7DT01829K},
doi = {10.1039/C7DT01829K},
abstract = {In water, the protonation state of the proximal water molecule of a high-valent manganese-oxo porphyrin could be controlled by pH. While in interaction with DNA the porphyrin was able to cleave DNA, only when the proximal water molecule was in the form of a hydroxyl group.
,
The high-valent manganese-oxo species of Mn-TMPyP4 porphyrin interacts in the minor grooves of AT-rich regions of DNA and mediates hydroxylation of C–H bonds of deoxyribose leading to DNA break. The reaction was observed at different pHs. It is shown that the hydroxylation was not efficient at low pH (pH 6) while it worked well at higher pH (pH 8). Deprotonation of the coordinated water molecule,
trans
to the manganese-oxo entity, into a hydroxide anion drives high-valent manganese-oxo porphyrin toward hydroxylation at pH {\textgreater} 7.},
language = {en},
number = {36},
urldate = {2021-06-16},
journal = {Dalton Transactions},
author = {Saint-Germes, Laurie and Bar, Laure and Dejeu, Jérôme and Spinelli, Nicolas and Defrancq, Eric and Pratviel, Geneviève},
year = {2017},
pages = {12088--12094},
}
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