Synthetic Analogues of Cysteinate-Ligated Non-Heme Iron and Non-Corrinoid Cobalt Enzymes
نویسندگان
چکیده
منابع مشابه
A functional model for the cysteinate-ligated non-heme iron enzyme superoxide reductase (SOR).
Superoxide reductases (SORs) are cysteine-ligated, non-heme iron enzymes that reduce toxic superoxide radicals (O2-). The functional role of the trans cysteinate, as well as the mechanism by which SOR reduces O2-, is unknown. Herein is described a rare example of a functional metalloenzyme analogue, which catalytically reduces superoxide in a proton-dependent mechanism, via a trans thiolate-lig...
متن کاملSynthetic Models for the Cysteinate-Ligated Non-Heme Iron Enzyme Superoxide Reductase: Observation and Structural Characterization by XAS of an Fe-OOH Intermediate
Superoxide reductases (SORs) belong to a new class of metalloenzymes that degrade superoxide by reducing it to hydrogen peroxide. These enzymes contain a catalytic iron site that cycles between the FeII and FeIII states during catalysis. A key step in the reduction of superoxide has been suggested to involve HO2 binding to FeII, followed by innersphere electron transfer to afford an FeIII-OO(H)...
متن کاملSynthetic models for the cysteinate-ligated non-heme iron enzyme superoxide reductase: observation and structural characterization by XAS of an Fe(III)-OOH intermediate.
Superoxide reductases (SORs) belong to a new class of metalloenzymes that degrade superoxide by reducing it to hydrogen peroxide. These enzymes contain a catalytic iron site that cycles between the Fe(II) and Fe(III) states during catalysis. A key step in the reduction of superoxide has been suggested to involve HO(2) binding to Fe(II), followed by innersphere electron transfer to afford an Fe(...
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Non-heme iron enzymes catalyze a wide range of O(2) reactions, paralleling those of heme systems. Non-heme iron active sites are, however, much more difficult to study because they do not exhibit the intense spectral features characteristic of the porphyrin ligand. A spectroscopic methodology was developed that provides significant mechanistic insight into the reactivity of non-heme ferrous act...
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Nogalamycin, an aromatic polyketide displaying high cytotoxicity, has a unique structure, with one of the carbohydrate units covalently attached to the aglycone via an additional carbon-carbon bond. The underlying chemistry, which implies a particularly challenging reaction requiring activation of an aliphatic carbon atom, has remained enigmatic. Here, we show that the unusual C5''-C2 carbocycl...
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ژورنال
عنوان ژورنال: Chemical Reviews
سال: 2004
ISSN: 0009-2665,1520-6890
DOI: 10.1021/cr020619e