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Neutralization of Reactive Oxygen Species at Dinuclear Cu(II)-Cores: Tuning the Antioxidant Manifold in Water by Ligand Design
ACS Catalysis ( IF 12.9 ) Pub Date : 2020-05-14 , DOI: 10.1021/acscatal.0c01955
Andrea Squarcina , Alice Santoro , Neal Hickey 1 , Rita De Zorzi 1 , Mauro Carraro , Silvano Geremia 1 , Marco Bortolus , Marilena Di Valentin , Marcella Bonchio
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Dinuclear Cu2(II,II)-cores stabilized by the N3O donorset of HL1 = (2-{[[di(2-pyridyl)methyl](methyl)amino]methyl}phenol), HL2 = 2-({[di(2-pyridyl)methyl]amino}methyl)phenol), and HL3 = 2-({[di(2-pyridyl)methyl]amino}methyl)-4-nitrophenol display a unique superoxide dismutase (SOD) combined with catalase (CAT)-like activity in water, at neutral pH. The Cu2L12 < Cu2L22 < Cu2L32 structure–reactivity trend puts a spotlight on the electron-deficient core of Cu2L32 that exhibits the highest SOD (log kcat(O2•–) = 7.55) and CAT-like (kH2O2 = 0.66 M–1 s–1) performance. Time-lapse ESI-MS and EPR experiments indicate that a dimeric core is essential for oxygenic turnover upon H2O2 decomposition.

中文翻译:

在双核Cu(II)核上中和活性氧的中性:通过配体设计调整水中的抗氧化剂歧管

通过HL 1 =(2-{[[[[(二(2-吡啶基)甲基](甲基)氨基]甲基}苯酚)的N 3 O供体组稳定的双核Cu 2(II,II)-核,HL 2 = 2- ({[(二(2-吡啶基)甲基]氨基}甲基)苯酚)和HL 3 = 2-({[(二(吡啶基甲基)甲基]氨基}甲基)-4-硝基苯酚显示独特的超氧化物歧化酶(SOD )与中性pH下的过氧化氢酶(CAT)样活性结合。所述的Cu 2大号1 2 <2大号2 2 <2大号3 2结构反应性趋势看跌聚光灯上的缺电子的芯的Cu2 L 3 2表现出最高的SOD(log k cat(O 2 •–)= 7.55)和类CAT( k H 2 O 2 = 0.66 M –1 s –1)。延时ESI-MS和EPR实验表明,二聚体核心对于H 2 O 2分解时的氧气转换至关重要。
更新日期:2020-07-02
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