Abstract
A new flavin, 2,4,7-trimethyl-10-benzylquino[8,7,-g]pteridine-9,11 (7H,10H)-dione (PyFI) has been synthesised which has within the molecule a flavin as a catalytic site and a fused pyridine as an additional metal-chelation site. Unlike conventional oxidised flavins lacking affinity with most metal ions, PyFI could associate with a variety of metal ions in acetonitrile. PyFI forms 1:1 complexes with ZnII, CdII, and CoII ions, the association constants being (1.4-4.4) × 105 M -1. These are the largest association constants reported for oxidised flavin-d-metal complexes. The oxidation of 1-benzyl-1,4-dihydronicotinamide (BNAH) by PyFI in acetonitrile, which did not take place in the absence of metal ion, was efficiently catalysed by several metal ions: [MgII, Zn II, CdII, and SbIII]. Furthermore, the reaction with BNAH in the presence of MgII, ZnII, and Cd II resulted in the formation of the flavosemiquinone which could be detected by absorption and e.s.r. spectroscopy. The e.s.r. spectral pattern is identical to that prepared by mixing equimolar amounts of oxidised and reduced PyFI. These results suggest that PyFI becomes even more electron-deficient than flavin owing to a PyFI → metal charge transfer while the semiquinone is stabilised through the interaction with these metal ions. These flavin-metal interactions serve as a model system possibly relevant to the action of metalloflavoenzymes. Such reactions cannot be provided by using conventional flavins.
| Original language | English |
|---|---|
| Pages (from-to) | 1825-1831 |
| Number of pages | 7 |
| Journal | Journal of the Chemical Society, Perkin Transactions 1 |
| Publication status | Published - 1986 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
Coenzyme models. Part 43. New metal-stabilised radicals of a flavin with a fused pyridine moiety which serves also as a metal chelation site in the oxidised state. / Shinkai, Seiji; Nakao, Hideki; Honda, Noriaki; Manabe, Osamu; Müller, Franz.
In: Journal of the Chemical Society, Perkin Transactions 1, 1986, p. 1825-1831.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Coenzyme models. Part 43. New metal-stabilised radicals of a flavin with a fused pyridine moiety which serves also as a metal chelation site in the oxidised state
AU - Shinkai, Seiji
AU - Nakao, Hideki
AU - Honda, Noriaki
AU - Manabe, Osamu
AU - Müller, Franz
PY - 1986
Y1 - 1986
N2 - A new flavin, 2,4,7-trimethyl-10-benzylquino[8,7,-g]pteridine-9,11 (7H,10H)-dione (PyFI) has been synthesised which has within the molecule a flavin as a catalytic site and a fused pyridine as an additional metal-chelation site. Unlike conventional oxidised flavins lacking affinity with most metal ions, PyFI could associate with a variety of metal ions in acetonitrile. PyFI forms 1:1 complexes with ZnII, CdII, and CoII ions, the association constants being (1.4-4.4) × 105 M -1. These are the largest association constants reported for oxidised flavin-d-metal complexes. The oxidation of 1-benzyl-1,4-dihydronicotinamide (BNAH) by PyFI in acetonitrile, which did not take place in the absence of metal ion, was efficiently catalysed by several metal ions: [MgII, Zn II, CdII, and SbIII]. Furthermore, the reaction with BNAH in the presence of MgII, ZnII, and Cd II resulted in the formation of the flavosemiquinone which could be detected by absorption and e.s.r. spectroscopy. The e.s.r. spectral pattern is identical to that prepared by mixing equimolar amounts of oxidised and reduced PyFI. These results suggest that PyFI becomes even more electron-deficient than flavin owing to a PyFI → metal charge transfer while the semiquinone is stabilised through the interaction with these metal ions. These flavin-metal interactions serve as a model system possibly relevant to the action of metalloflavoenzymes. Such reactions cannot be provided by using conventional flavins.
AB - A new flavin, 2,4,7-trimethyl-10-benzylquino[8,7,-g]pteridine-9,11 (7H,10H)-dione (PyFI) has been synthesised which has within the molecule a flavin as a catalytic site and a fused pyridine as an additional metal-chelation site. Unlike conventional oxidised flavins lacking affinity with most metal ions, PyFI could associate with a variety of metal ions in acetonitrile. PyFI forms 1:1 complexes with ZnII, CdII, and CoII ions, the association constants being (1.4-4.4) × 105 M -1. These are the largest association constants reported for oxidised flavin-d-metal complexes. The oxidation of 1-benzyl-1,4-dihydronicotinamide (BNAH) by PyFI in acetonitrile, which did not take place in the absence of metal ion, was efficiently catalysed by several metal ions: [MgII, Zn II, CdII, and SbIII]. Furthermore, the reaction with BNAH in the presence of MgII, ZnII, and Cd II resulted in the formation of the flavosemiquinone which could be detected by absorption and e.s.r. spectroscopy. The e.s.r. spectral pattern is identical to that prepared by mixing equimolar amounts of oxidised and reduced PyFI. These results suggest that PyFI becomes even more electron-deficient than flavin owing to a PyFI → metal charge transfer while the semiquinone is stabilised through the interaction with these metal ions. These flavin-metal interactions serve as a model system possibly relevant to the action of metalloflavoenzymes. Such reactions cannot be provided by using conventional flavins.
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M3 - Article
AN - SCOPUS:37049070936
SP - 1825
EP - 1831
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
SN - 1472-7781
ER -