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Showing 1 to 20 of 30 for “"Non-Heme Iron"”.
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Oxyanion reduction in a non-heme iron system
… to access both tautomeric forms of the ligand in iron(II) complexes. Moreover, the ability of each arm of the ligand to tautomerize independently was observed in an iron(II)-hydroxo complex that included both tautomeric forms. The secondary coordination sphere also displayed a propensity to engage …
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Small molecule activation and reduction using non-heme iron complexes
… stabilizing reactive species, such as a terminal iron(III)-oxo species. Using this ligand framework, our lab previously reported the syntheses of a series of metal complexes featuring pseudohalide ligands. In each of these complexes, hydrogen bonding interactions between the bound substrate and …
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Two versatile cofactors, flavin adenine dinucleotide and non-heme iron, involved in DNA repair and natural product halogenation
… cofactors, flavin adenine dinucleotide (FAD) and non-heme iron, together with molecular oxygen as an oxidizing agent, perform a wide array of reactions. Hydroxylation in DNA repair is one example. AidB is an adaptive response protein that is up-regulated in the presence of alkylating agents. AidB …
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Non-heme iron C-H oxidation: tolerance of nitrogen-containing motifs with application to amino-acid and peptide oxidation
Direct oxidation of C-H bonds using non-heme iron catalysis has proven to be a highly useful transformation since its development in recent years. The ability to directly install oxygen into a hydrocarbon framework negates the need for pre-oxidized materials, and allows for quick and efficient …
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I. Biomimetic oxidations using non-heme iron catalysis. II. Palladium- and hypervalent iodine-catalyzed tandem wacker-dehydrogenation of terminal olefins
ABSTRACT I. BIOMIMETIC OXIDATIONS USING NON-HEME IRON CATALYSIS Nature’s oxidation catalysts promote a remarkable variety of highly selective oxidation reactions of alkanes, olefins, and arenes. Inspired by this diversity of reactivity, the chemical community has long sought to replicate enzymatic …
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Reactions of dioxygen and nitric oxide with iron(II) compounds : models for chemistry occuring in the active sites of non-heme iron enzymes
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1995.
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The Effect of Soy Products in The Diet on Retention of Non-Heme Iron From Radiolabeled Test Meals Fed to Marginally Iron-Deficient Young Rats
… or soy products and containing about 25 ppm iron were fed to weanling rats for 13 days. Rats were fasted overnight and fed a ('59)Fe-radiolabeled casein test meal the morning of day 14. On day 21 less ('59)Fe was retained by rats fed various diets based on selected soy products than by rats …
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Crystallographic studies on enzymatic halogenation of natural products
… the flavin-dependent halogenases and the non-heme iron dependent halogenases. Structures of the flavin-dependent tryptophan 7-halogenase RebH from Lechevalieria aerocolonigenes, involved in rebeccamycin biosynthesis, were solved by molecular replacement. These structures show distant …
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Computational Investigation of the Catalytic and Structural Roles of Metals in Metalloenzymes
… to understand the role of metals and protein environment in dynamically promoting the reactivity and selectivity of metalloenzymes is of fundamental importance. In this thesis, we study the catalytic and structural roles of metals in metalloenzymes using quantum mechanics (QM), classical …
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Experimental and theoretical studies of the photosystem II reaction center: Implications for bicarbonate binding and function
… near the putative bicarbonate binding sites, the non-heme iron and the Q$\sb{\rm B}$ binding niche, were mutated in a unicellular green alga Chlamydomonas reinhardtii. The effects of mutations on bicarbonate binding and on other aspects of PSII photochemistry were investigated.
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C—H oxidation reactions: development and application
… as well as applications of a biomimetic non-heme iron catalyst towards generating diverse oxidation products and exploring biological pathways. Linear allylic amines are a common motif found in many organic molecules; however, their synthesis involves a lengthy, multi-step sequence that …
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Interplay of Transition Metals and Noncovalent Interactions in C–H Activation Catalysis
… poor selectivity, biological systems, such as non-heme iron enzymes, carry out selective C–H activation efficiently under ambient conditions. These enzymes catalyze a variety of reactions including C–H halogenation, hydroxylation, epoxidation, and ring closures, several of which are mediated …
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Accumulation Of Subcortical Iron As A Modifier Of Volumetric And Cognitive Decline In Healthy Aging: Two Longitudinal Studies
<p>Accumulation of non-heme iron in the brain has been theorized as a cellular mechanism underlying global neural and cognitive decline in normal aging and neurodegenerative disease. Relatively few studies of brain iron in normal aging exist and extant studies are almost exclusively …
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Investigation of phosphonate biosynthesis: I. Structure of dehydrophos II. Mechanism of hydroxyethylphosphonate dioxygenase
… Characterization of HEPD has shown it to be a non-heme iron dependent dioxygenase that is dependent on only ferrous iron and molecular oxygen for activity. Studies with substrate isotopologues and substrate analogues have given insight into the mechanism and suggest a hydroperoxylation …
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Mechanistic studies of electron transfer, complex formation, C-H bond activation, and product binding in soluble methane monooxygenase
… a hydroxylase (MMOH) that contains a dinuclear non-heme iron active site, a reductase (MMOR) that facilitates electron transfer from NADH to the diiron site of MMOH, and a coupling protein (MMOB). MMOR uses a non-covalently bound FAD cofactor and a [2Fe-2S] cluster to mediate electron transfer. …
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Mechanistic investigations of enzymes in phosphonate metabolism
… dioxygenase (HEPD) is a non-heme iron enzyme that catalyzes the cleavage of the carbon-carbon bond of 2-hydroxyethylphosphonate (2- HEP) during the biosynthesis of the herbicide phosphinothricin. Mechanistic studies were undertaken to elucidate the mechanism of catalysis …
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Diverse functions of the two segmentally duplicated 9-lipoxygenases ZmLOX4 and ZmLOX5 of maize
Plant lipoxygenases (LOX) are non-heme iron containing dioxygenases that catalyze the hydroperoxidation of polyunsaturated fatty acids resulting in the synthesis of a large number of functionally diverse oxylipins. Although the physiological functions of jasmonate-producing 13-LOXs in dicots have …
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The role of outer-sphere residues and substrate-binding at the 3-mercaptopropionic acid dioxygenase (3mdo) active site: a combined spectroscopic and computational investigation
Thiol Dioxygenases (TDOs) are non-heme iron enzymes that catalyze the O2-dependent oxidation of thiol-bearing amino acid derivatives to their corresponding sulfinic acid. Recently, considerable work has been focused on this class of enzymes, as sulfur metabolite imbalances have been correlated with …
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Metal complexes of non-heme ligands: biological applications
… trypsin, chymotrypsin and 20S proteasome) by non–heme iron complexes, and glutathionylation of non–heme cobalt complexes mimicking the N5 coordination environment like that of biologically important cofactor cobalamin or B<sub>12</sub> (Cbl) are reported. Different non–heme ligand sets or …
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Interdomain Repression in the Enhancer Binding Protein NorR
… domain in the absence of NO. NO binds to the non-heme iron centre of the GAF domain, stimulating ATP hydrolysis by the AAA+ domain and establishing an interaction between the activator and σ54 that leads to the remodelling of the closed promoter complex. However, the route by which NorR …
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