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Journal of inorganic biochemistry v.182, 2018년, pp.29 - 36   SCI SCIE
본 등재정보는 저널의 등재정보를 참고하여 보여주는 베타서비스로 정확한 논문의 등재여부는 등재기관에 확인하시기 바랍니다.

Tuning the MnII 2/MnIII 2 redox cycle of a phenoxo-bridged diMn catalase mimic with terminal carboxylate donors

Solís, Verónica (IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina ) ; Palopoli, Claudia (IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina ) ; Daier, Verónica (IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina ) ; Rivière, Eric (Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS, Université ) ; Collin, Fabrice (Paris Sud, Université ) ; Moreno, Diego M. (Paris Saclay, 91405 Orsay Cedex, France ) ; Hureau, Christelle (UPS, INPT, Universit&eac ) ; Signorella, Sandra ;
  • 초록  

    Abstract A new phenoxo-bridged diMn III complex, Na[Mn 2 L(OH) 2 (H 2 O) 2 ]·5H 2 O ( 1 ), obtained with the ligand L 5− = 5̴ 5‑methyl‑2‑hydroxo‑1,3‑xylene‑α,α‑diamine‑ N , N , N ′, N ′‑tetraacetato, has been prepared and characterized. Mass spectrometry, conductivity, UV–visible, EPR and 1 H NMR spectroscopic studies showed that the complex exists in solution as a monoanionic diMn III complex. Complex 1 catalyzes H 2 O 2 disproportionation with second-order rate constant k cat = 3 305(9) M −1 min −1 and without a time-lag phase. Based on spectroscopic results, the catalase activity of complex 1 in methanol involves a Mn III 2 /Mn II 2 redox cycle, which distinguishes this catalyst from other phenoxo-bridged diMn complexes that cycle between Mn II Mn III /Mn III Mn IV species. Addition of base stabilizes the catalyst, restrains demetallation during catalysis and causes moderate enhancement of catalase activity. The terminal carboxylate donors of 1 not only contribute as internal bases to assist deprotonation of H 2 O 2 but also favor the formation of active homovalent diMn species, just as observed for the enzyme. Highlights A new phenoxo-bridged-Mn 2 III catalase mimic has been obtained. H 2 O 2 disproportionation occurs through a cycle involving Mn III 2 and Mn II 2 states. The Mn 2 II form reacts with H 2 O 2 in the slow step, as do the enzyme. Terminal carboxylate groups in the catalyst assist H 2 O 2 deprotonation. Four carboxylate groups favor the formation of active homovalent diMn species. Graphical abstract The phenoxo-bridged complex Na[Mn 2 L(OH) 2 (H 2 O) 2 ], where L 5− = 5̴ 5‑methyl‑2‑hydroxo‑1,3‑xylene‑α,α‑diamine‑ N , N , N ′, N ′‑tetraacetato, catalyzes H 2 O 2 disproportionation involving a Mn III 2 /Mn II 2 redox cycle, a behavior that distinguishes this catalyst from other phenoxo-bridged diMn complexes with terminal pyridyl or pyridyl/carboxylato donors that cycle between Mn II Mn III /Mn III Mn IV species. [DISPLAY OMISSION]


  • 주제어

    Catalase mimic .   Manganese .   Kinetics .   Polycarboxylate ligand.  

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