Comparison of Nonheme Manganese- and Iron-Containing Flavone Synthase Mimics

Lakk-Bogáth, Dóra; Pantalon Juraj, Natalija; Meena, Bashdar I.; Perić, Berislav; Kirin, Srećko I.; Kaizer, József (2021) Comparison of Nonheme Manganese- and Iron-Containing Flavone Synthase Mimics. Molecules, 26 (11). ISSN 1420-3049

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Official URL: https://www.mdpi.com/1420-3049/26/11/3220

Abstract

Heme and nonheme-type flavone synthase enzymes, FS I and FS II are responsible for the synthesis of flavones, which play an important role in various biological processes, and have a wide range of biomedicinal properties including antitumor, antimalarial, and antioxidant activities. To get more insight into the mechanism of this curious enzyme reaction, nonheme structural and functional models were carried out by the use of mononuclear iron, [FeII(CDA-BPA*)]2+ (6) [CDABPA = N, N, N’, N’-tetrakis-(2-pyridylmethyl)- cyclohexanediamine], [FeII(CDA-BQA*)]2+ (5) [CDABQA = N, N, N’, N’-tetrakis-(2-quinolilmethyl)- cyclohexanediamine], [FeII(Bn-TPEN)(CH3CN)]2+ (3) [Bn-TPEN = N-benzyl-N, N’, N’-tris(2- pyridylmethyl)-1, 2-diaminoethane], [FeIV(O)(Bn- TPEN)]2+ (9), and manganese, [MnII(N4Py*)(CH3CN)]2+ (2) [N4Py* = N, N-bis(2-pyridylmethyl)-1, 2-di(2-pyridyl) ethylamine)], [MnII(Bn-TPEN)(CH3CN)]2+ (4) complexes as catalysts, where the possible reactive intermediates, high-valent FeIV(O) and MnIV(O) are known and well characterised. The results of the catalytic and stoichiometric reactions showed that the ligand framework and the nature of the metal cofactor significantly influenced the reactivity of the catalyst and its intermediate. Comparing the reactions of [FeIV(O)(Bn-TPEN)]2+ (9) and [MnIV(O)(Bn- TPEN)]2+ (10) towards flavanone under the same conditions, a 3.5-fold difference in reaction rate was observed in favor of iron, and this value is three orders of magnitude higher than was observed for the previously published [FeIV(O)(N2Py2Q*)]2+ [N, N-bis(2-quinolylmethyl)-1, 2-di(2- pyridyl)ethylamine] species.

Item Type:

Article

Uncontrolled Keywords:

flavone synthase ; iron(IV)-oxo ; manganese(IV)-oxo ; oxidation ; kinetic studies

Subjects:

NATURAL SCIENCES > Chemistry

Divisions:

Division of Materials Chemistry

Projects:

Project title	Project leader	Project code	Project type
Minimalni umjetni enzimi: Proširenje primjene posredne indukcije na nove supstrate i nove asimetrične reakcije	Kirin, Srećko	IP-2014-09-1461	HRZZ
Inovativna rješenja u katalitičkim proizvodnim procesima za potrebe farmaceutske industrije	Kirin, Srećko	KK.01.1.1.04.0013	EK

Depositing User:

Natalija Pantalon Juraj

Date Deposited:

05 Jul 2021 13:29

URI:

http://fulir.irb.hr/id/eprint/6478

DOI:

10.3390/molecules26113220