TY - JOUR
T1 - Stability in solution and chemoprotection by octadecavanadates(IV/V) in E. coli cultures
AU - Postal, Kahoana
AU - Santana, Francielli S.
AU - Hughes, David L.
AU - Rüdiger, André L.
AU - Ribeiro, Ronny R.
AU - Sá, Eduardo L.
AU - De Souza, Emanuel M.
AU - Soares, Jaísa F.
AU - Nunes, Giovana G.
PY - 2021/6
Y1 - 2021/6
N2 - Two mixed-valence octadecavanadates, (NH
4)
2(Me
4N)
5[V
IV
12V
V
6O
42I]·Me
4NI·5H
2O (V
18I) and [{K
6(OH
2)
12V
IV
11V
V
7O
41(PO
4)·4H
2O}
n] (V
18P), were synthesized and characterized by single-crystal X-ray diffraction analysis and FTIR, Raman,
51V NMR, EPR and UV/Vis/NIR spectroscopies. The chemoprotective activity of V
18I and V
18P towards the alkylating agent diethyl sulfate was assessed in E. coli cultures. The complex V
18I was nontoxic in concentrations up to 5.0 mmol L
−1, while V
18P presented moderate toxicity in the concentration range 0.10 - 10 mmol L
−1. Conversely, a ca. 35% enhancement in culture growth as compared to cells treated only with diethyl sulfate was observed upon addition of V
18I (0.10 to 2.5 mmol L
−1), while the combination of diethyl sulfate with V
18P increased the cytotoxicity presented by diethyl sulfate alone.
51V NMR and EPR speciation studies showed that V
18I is stable in solution, while V
18P suffers partial breakage to give low nuclearity oxidometalates of vanadium(V) and (IV). According to the results, the chemoprotective effect depends strongly on the direct reactivity of the polyoxidovanadates (POV) towards the alkylating agent. The reaction of diethyl sulfate with V
18I apparently produces a new, rearranged POV instead of poorly-reactive breakage products, while V
18P shows the formation and subsequent consumption of low-nuclearity species. The correlation of this chemistry with that of other mixed-valence polyoxidovanadates, [H
6V
IV
2V
V
12O
38PO
4]
5- (V
14) and [V
IV
8V
V
7O
36Cl]
6- (V
15), suggests a relationship between stability in solution and chemoprotective performance.
AB - Two mixed-valence octadecavanadates, (NH
4)
2(Me
4N)
5[V
IV
12V
V
6O
42I]·Me
4NI·5H
2O (V
18I) and [{K
6(OH
2)
12V
IV
11V
V
7O
41(PO
4)·4H
2O}
n] (V
18P), were synthesized and characterized by single-crystal X-ray diffraction analysis and FTIR, Raman,
51V NMR, EPR and UV/Vis/NIR spectroscopies. The chemoprotective activity of V
18I and V
18P towards the alkylating agent diethyl sulfate was assessed in E. coli cultures. The complex V
18I was nontoxic in concentrations up to 5.0 mmol L
−1, while V
18P presented moderate toxicity in the concentration range 0.10 - 10 mmol L
−1. Conversely, a ca. 35% enhancement in culture growth as compared to cells treated only with diethyl sulfate was observed upon addition of V
18I (0.10 to 2.5 mmol L
−1), while the combination of diethyl sulfate with V
18P increased the cytotoxicity presented by diethyl sulfate alone.
51V NMR and EPR speciation studies showed that V
18I is stable in solution, while V
18P suffers partial breakage to give low nuclearity oxidometalates of vanadium(V) and (IV). According to the results, the chemoprotective effect depends strongly on the direct reactivity of the polyoxidovanadates (POV) towards the alkylating agent. The reaction of diethyl sulfate with V
18I apparently produces a new, rearranged POV instead of poorly-reactive breakage products, while V
18P shows the formation and subsequent consumption of low-nuclearity species. The correlation of this chemistry with that of other mixed-valence polyoxidovanadates, [H
6V
IV
2V
V
12O
38PO
4]
5- (V
14) and [V
IV
8V
V
7O
36Cl]
6- (V
15), suggests a relationship between stability in solution and chemoprotective performance.
KW - Alkylation
KW - Chemoprotection
KW - Diethyl sulfate
KW - Polyoxidovanadates
KW - Speciation
UR - http://www.scopus.com/inward/record.url?scp=85103613015&partnerID=8YFLogxK
U2 - 10.1016/j.jinorgbio.2021.111438
DO - 10.1016/j.jinorgbio.2021.111438
M3 - Article
SN - 0162-0134
VL - 219
JO - Journal of Inorganic Biochemistry
JF - Journal of Inorganic Biochemistry
M1 - 111438
ER -