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A Heterobimetallic ...
A Heterobimetallic FeIIIMnII Complex of an Unsymmetrical Dinucleating Ligand : A Structural and Functional Model Complex for the Active Site of Purple Acid Phosphatase of Sweet Potato
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- Das, Biswanath (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Daver, Henrik (författare)
- Stockholms universitet,Institutionen för organisk kemi
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- Singh, Amrendra (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Singh, Reena (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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Haukka, Matti (författare)
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Demeshko, Serhiy (författare)
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Meyer, Franc (författare)
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Lisensky, George (författare)
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- Jarenmark, Martin (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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- Himo, Fahmi (författare)
- Stockholms universitet,Institutionen för organisk kemi
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- Nordlander, Ebbe (författare)
- Lund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH
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(creator_code:org_t)
- 2014-03-26
- 2014
- Engelska.
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; 2014:13, s. 2204-2212
- Relaterad länk:
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http://dx.doi.org/10...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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https://lup.lub.lu.s...
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Abstract
Ämnesord
Stäng
- The heterodinuclear mixed-valence complex [FeMn(ICIMP)(OAc)(2)Cl] (1) {H2ICIMP = 2-(N-carboxylmethyl)-[N-(N-methylimidazolyl-2-methyl)aminomethyl]-[6-(N-isopropylmethyl)-[N-(N-methylimidazolyl-2-methyl)]aminomethyl-4-methylphenol], an unsymmetrical N4O2 donor ligand} has been synthesized and fully characterized by several spectroscopic techniques as well as by X-ray crystallography. The crystal structure of the complex reveals that both metal centers in 1 are six-coordinate with the chloride ion occupying the sixth coordination site of the Mn-II ion. The phenoxide moiety of the ICIMP ligand and both acetate ligands bridge the two metal ions of the complex. Mossbauer spectroscopy shows that the iron ion in 1 is high-spin Fe-III. Two quasi-reversible redox reactions for the complex, attributed to the (FeMnII)-Mn-III/(FeMnII)-Mn-II (at -0.67 V versus Fc/Fc(+)) and (FeMnII)-Mn-III/(FeMnIII)-Mn-III (at 0.84 V), were observed by means of cyclic voltammetry. Complex 1, with an Fe-III-Mn-II distance of 3.58 angstrom, may serve as a model for the mixed-valence oxidation state of purple acid phosphatase from sweet potato. The capability of the complex to effect organophosphate hydrolysis (phosphatase activity) has been investigated at different pH levels (5.5-11) by using bis(2,4-dinitrophenyl)phosphate (BDNPP) as the substrate. Density functional theory calculations indicate that the substrate coordinates to the Mn-II ion. In the transition state, a hydroxide ion that bridges the two metal ions becomes terminally coordinated to the Fe-III ion and acts as a nucleophile, attacking the phosphorus center of BDNPP with the concomitant dissociation of the leaving group.
Ämnesord
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
- NATURVETENSKAP -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)
Nyckelord
- Metalloenzymes
- Mixed-valent compounds
- Moessbauer spectroscopy
- Density functional calculations
- Transition states
- Hydrolysis
- organisk kemi
- Organic Chemistry
- Metalloenzymes
- Mixed-valent compounds
- Moessbauer spectroscopy
- Density
- functional calculations
- Transition states
- Hydrolysis
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Till lärosätets databas
- Av författaren/redakt...
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Das, Biswanath
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Daver, Henrik
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Singh, Amrendra
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Singh, Reena
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Haukka, Matti
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Demeshko, Serhiy
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visa fler...
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Meyer, Franc
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Lisensky, George
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Jarenmark, Marti ...
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Himo, Fahmi
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Nordlander, Ebbe
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- Om ämnet
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- NATURVETENSKAP
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NATURVETENSKAP
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och Kemi
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och Organisk kemi
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NATURVETENSKAP
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och Fysik
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och Atom och molekyl ...
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European Journal ...
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Stockholms universitet
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Lunds universitet