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Merged Heme and Non-Heme Manganese Cofactors for a Dual Antioxidant Surveillance in Photosynthetic Organisms
ACS Catalysis ( IF 13.1 ) Pub Date : 2017-02-13 00:00:00 , DOI: 10.1021/acscatal.7b00004
Andrea Squarcina Antonio Sorarù Francesco Rigodanza Mauro Carraro Giovanna Brancatelli Tommaso Carofiglio Silvano Geremia Véronique Larosa Tomas Morosinotto Marcella Bonchio

The coupling of a polycationic Mn(III)-porphyrin, with a dinuclear Mn2(II,II)L2 core (HL = 2-{[[di(2-pyridyl)methyl](methyl)amino]methyl}phenol), results in a dual Superoxide Dismutase (SOD) and Catalase (CAT) functional analogue, Mn2L2Pn+, enabling a detoxification cascade of the superoxide anion and hydrogen peroxide into benign H2O and O2. The SOD/CAT artificial manifolds, joined in one asset, exhibit a peak catalytic performance under physiological conditions, with log kcat(O2• –) ≥ 7 and kcat(H2O2)/KM = 1890. The dual-enzyme (dizyme) concept allows for a built-in self-protection against the irreversible bleaching of the porphyrin unit (>75% protection), readily induced by H2O2 (200 μM, 20 equiv, in buffer solution, pH 7.8). We show herein that incubation of the photosynthetic green algae, Chlamydomonas reinhardtii, with the synthetic dizyme (as low as 0.1 μM), prevents H2O2 accumulation under high-light illumination conditions, thus providing antioxidant surveillance and photoprotection.

中文翻译:

合并的血红素和非血红素锰辅助因子在光合生物中的双重抗氧化监测

聚阳离子Mn(III)-卟啉与双核Mn 2(II,II)L 2核的偶联(HL = 2-{[[[[((2-(吡啶基)甲基)] [甲基]氨基]甲基}苯酚) ,产生双重超氧化物歧化酶(SOD)和过氧化氢酶(CAT)功能类似物Mn 2 L 2 P n +,使超氧阴离子和过氧化氢解毒级联为良性H 2 O和O 2。SOD / CAT人工歧管结合在一起,在生理条件下显示出最高的催化性能,log k cat(O 2 •–)≥7和k cat(H 2O 2)/ K M =1890。双酶(二酶)概念可实现针对H 2 O 2(200容易诱导的卟啉单元不可逆漂白的内置自我保护作用(> 75%的保护作用)。μM,20当量,在pH 7.8的缓冲溶液中)。我们在本文中显示,光合作用的藻类(莱茵衣藻)与合成的二酶(低至0.1μM)一起孵育可防止H 2 O 2在强光照射条件下积累,从而提供了抗氧化剂监测和光保护作用。
更新日期:2017-02-13
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