Synthesis, structure and interactions with DNA of novel tetranuclear, [Mn-4(II/II/II/IV)] mixed valence complexes
(2008) In Journal of Inorganic Biochemistry 102(4). p.618-628- Abstract
- Reaction of Mn(II) with phenoxyalkanoic acids and di-2-pyridyl ketone oxime (Hpko) leads to neutral tetranuclear complexes of the general formula Mn-4(O)(pko)(4)(phenoxyalkanoato)(4) (phenoxyalkanoic acids: H-mcpa = 2-methyl-4-chloro-phenoxy-acetic acid, H-2,4,5-T = 2,4.5-trichloro-phenoxy-acetic acid or H3,4-D = 3,4-dichloro-phenoxy-acetic acid). The compounds were synthesized by adding di2-pyridyl ketone oxime to MnCl2 in the presence of the sodium salts of the alkanoic acids in methanol. The crystal structure of Mn-4(II/II/ II/IV)(O)(pko)4(()2,4,5-T)(4) . 2.5CH(3)OH . 0.25H(2)O 1 shows that the complex consists of a [Mn-4( mu(4)-O)](8+) core with a Mn(IV) and 3 Mn(II) ions in octahedral environment and a mu(4)-O atom bridging the four... (More)
- Reaction of Mn(II) with phenoxyalkanoic acids and di-2-pyridyl ketone oxime (Hpko) leads to neutral tetranuclear complexes of the general formula Mn-4(O)(pko)(4)(phenoxyalkanoato)(4) (phenoxyalkanoic acids: H-mcpa = 2-methyl-4-chloro-phenoxy-acetic acid, H-2,4,5-T = 2,4.5-trichloro-phenoxy-acetic acid or H3,4-D = 3,4-dichloro-phenoxy-acetic acid). The compounds were synthesized by adding di2-pyridyl ketone oxime to MnCl2 in the presence of the sodium salts of the alkanoic acids in methanol. The crystal structure of Mn-4(II/II/ II/IV)(O)(pko)4(()2,4,5-T)(4) . 2.5CH(3)OH . 0.25H(2)O 1 shows that the complex consists of a [Mn-4( mu(4)-O)](8+) core with a Mn(IV) and 3 Mn(II) ions in octahedral environment and a mu(4)-O atom bridging the four manganese ions. Spectroscopic studies of the interaction of these tetranuclear clusters with DNA showed that these compounds bind to dsDNA. The binding strength of the Mn-4(II/II/II/ IV)(O)(pko)(4)(2,4,5-T)(4) complex for calf thymus DNA is equal to 1.1 X 10(4) M-1. Among the deoxyribonucleotides they bind preferentially to deoxyguanylic acid (dGMP). Competitive studies with ethidium bromide (EthBr) showed that the Mn-4(II/II/II/ IV)(O)(pko)(4)(2,4,.5-T)(4) complex exhibited the ability to displace the DNA-bound EthBr indicating that the complex binds to DNA via intercalation in strong competition with EthBr for the intercalative binding site. Additionally, DNA electrophoretic mobility experiments showed that all three complexes, at low cluster concentration, are obviously capable of binding to pDNA causing its cleavage (relaxation) at physiological pH and temperature. At higher cluster concentration, catenated dimer forms of pDNA was formed. (Less)
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- author
- Dimitrakopoulou, Anastasia ; Dendrinou-Samara, Catherine ; Pantazaki, Anastasia A ; Alexiou, Maria ; Nordlander, Ebbe LU and Kessissglou, Dimitris P
- organization
- publishing date
- 2008
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- phenoxyalkanoic acids, manganese complexes, mixed valence, DNA, interaction
- in
- Journal of Inorganic Biochemistry
- volume
- 102
- issue
- 4
- pages
- 618 - 628
- publisher
- Elsevier
- external identifiers
-
- wos:000255131500003
- scopus:40649125555
- pmid:18055016
- ISSN
- 1873-3344
- DOI
- 10.1016/j.jinorgbio.2007.10.005
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
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- 6ec9595f-bcf7-4065-9bd5-199a3f0d9edf (old id 1206359)
- date added to LUP
- 2016-04-01 13:26:09
- date last changed
- 2022-03-13 23:57:25
@article{6ec9595f-bcf7-4065-9bd5-199a3f0d9edf,
abstract = {{Reaction of Mn(II) with phenoxyalkanoic acids and di-2-pyridyl ketone oxime (Hpko) leads to neutral tetranuclear complexes of the general formula Mn-4(O)(pko)(4)(phenoxyalkanoato)(4) (phenoxyalkanoic acids: H-mcpa = 2-methyl-4-chloro-phenoxy-acetic acid, H-2,4,5-T = 2,4.5-trichloro-phenoxy-acetic acid or H3,4-D = 3,4-dichloro-phenoxy-acetic acid). The compounds were synthesized by adding di2-pyridyl ketone oxime to MnCl2 in the presence of the sodium salts of the alkanoic acids in methanol. The crystal structure of Mn-4(II/II/ II/IV)(O)(pko)4(()2,4,5-T)(4) . 2.5CH(3)OH . 0.25H(2)O 1 shows that the complex consists of a [Mn-4( mu(4)-O)](8+) core with a Mn(IV) and 3 Mn(II) ions in octahedral environment and a mu(4)-O atom bridging the four manganese ions. Spectroscopic studies of the interaction of these tetranuclear clusters with DNA showed that these compounds bind to dsDNA. The binding strength of the Mn-4(II/II/II/ IV)(O)(pko)(4)(2,4,5-T)(4) complex for calf thymus DNA is equal to 1.1 X 10(4) M-1. Among the deoxyribonucleotides they bind preferentially to deoxyguanylic acid (dGMP). Competitive studies with ethidium bromide (EthBr) showed that the Mn-4(II/II/II/ IV)(O)(pko)(4)(2,4,.5-T)(4) complex exhibited the ability to displace the DNA-bound EthBr indicating that the complex binds to DNA via intercalation in strong competition with EthBr for the intercalative binding site. Additionally, DNA electrophoretic mobility experiments showed that all three complexes, at low cluster concentration, are obviously capable of binding to pDNA causing its cleavage (relaxation) at physiological pH and temperature. At higher cluster concentration, catenated dimer forms of pDNA was formed.}},
author = {{Dimitrakopoulou, Anastasia and Dendrinou-Samara, Catherine and Pantazaki, Anastasia A and Alexiou, Maria and Nordlander, Ebbe and Kessissglou, Dimitris P}},
issn = {{1873-3344}},
keywords = {{phenoxyalkanoic acids; manganese complexes; mixed valence; DNA; interaction}},
language = {{eng}},
number = {{4}},
pages = {{618--628}},
publisher = {{Elsevier}},
series = {{Journal of Inorganic Biochemistry}},
title = {{Synthesis, structure and interactions with DNA of novel tetranuclear, [Mn-4(II/II/II/IV)] mixed valence complexes}},
url = {{http://dx.doi.org/10.1016/j.jinorgbio.2007.10.005}},
doi = {{10.1016/j.jinorgbio.2007.10.005}},
volume = {{102}},
year = {{2008}},
}