Enzymatic hydrolysis by transition-metal-dependent nucleophilic aromatic substitution

Date

2016-12-01

Author

Kalyoncu, Sibel
Heaner, David P.
Kurt, Zöhre
Bethel, Casey M.
Ukachukwu, Chiamaka U.
Chakravarthy, Srinivas
Spain, Jim C.
Lieberman, Raquel L.

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

172
views

0
downloads

Nitroaromatic compounds are typically toxic and resistant to degradation. Bradyrhizobium species strain JS329 metabolizes 5-nitroanthranilic acid (5NAA), which is a molecule secreted by Streptomyces scabies, the plant pathogen responsible for potato scab. The first biodegradation enzyme is 5NAA-aminohydrolase (5NAA-A), a metalloprotease family member that converts 5NAA to 5-nitrosalicylic acid. We characterized 5NAA-A biochemically and obtained snapshots of its mechanism. 5NAA-A, an octamer that can use several divalent transition metals for catalysis in vitro, employs a nucleophilic aromatic substitution mechanism. Unexpectedly, the metal in 5NAA-A is labile but is readily loaded in the presence of substrate. 5NAA-A is specific for 5NAA and cannot hydrolyze other tested derivatives, which are likewise poor inhibitors. The 5NAA-A structure and mechanism expand our understanding of the chemical ecology of an agriculturally important plant and pathogen, and will inform bioremediation and biocatalytic approaches to mitigate the environmental and ecological impact of nitroanilines and other challenging substrates.

Subject Keywords

Diversity, Resolution, Resistance, Deacetylase, Biosynthesis, Biodegradation, Mechanisms, Degradation, Evolutionary, 5-nitroanthranilic acid

URI

https://hdl.handle.net/11511/42673

Journal

NATURE CHEMICAL BIOLOGY

DOI

https://doi.org/10.1038/nchenbio.2191

Collections

Department of Environmental Engineering, Article

Suggestions

OpenMETU
Core

Fate and degradation kinetics of nonylphenol compounds in aerobic batch digesters Omeroglu, Seçil; Sanin, Faika Dilek (2014-11-01) Nonylphenol (NP) compounds are toxic and persistent chemicals that are not fully degraded either in natural or engineered systems. Current knowledge indicates that these compounds concentrate in sewage sludge. Therefore, investigating the degradation patterns and types of metabolites formed during sludge treatment are important for land application of sewage sludge. Unfortunately, the information on the fate of nonylphenol compounds in sludge treatment is very limited. This study aims to investigate the bio...
Enantioselective michael addition of 1-nitropropane to nitroolefins with 2-aminodmap and quinine based bifunctional organocatalysts Kanberoğlu, Esra; Tanyeli, Cihangir; Department of Chemistry (2015) 1,3-dinitro compounds are key materials in the synthesis of a variety of important fine chemicals. Moreover, they are reduced to 1,3-diamines which are starting materials of biologically active compounds, agrochemicals and pharmaceuticals. In this study, ((2S,3S)-1,3-dinitropentan-2-yl)benzene was synthesized via the Michael addition of 1-nitropropane to trans-β-nitrostyrene in the presence of chiral bifunctional 2-aminoDMAP and quinine based organocatalysts. In the first part of study, reaction conditions ...
Biomimetic preparation of HA precursors at 37 degrees C in urea- and enzyme urease-containing synthetic body fluids Bayraktar, D; Tas, AC (1999-12-01) An important inorganic phase of synthetic bone applications, calcium hydroxyapatite (HA, Ca-10(PO4)(6)(OH)(2)), was prepared as a single-phase and sub-micron bioceramic powder. Carbonated HA precursors were synthesized from calcium nitrate tetrahydrate and diammonium hydrogen phosphate salts dissolved in "synthetic body fluid" (SBF) solutions, containing urea (H2NCONH2) and enzyme urease, under the biomimetic conditions of 37 degrees C and pH 7.4, by using a novel chemical precipitation technique.
Dimethyl Ether Synthesis over Novel Silicotungstic Acid Incorporated Nanostructured Catalysts Ciftci, Aysegul; VARIŞLI, DİLEK; Doğu, Timur (2010-01-01) Dimethyl ether (DME), which is an excellent green diesel-fuel alternate with excellent clean burning properties, is synthesized by dehydration of methanol over novel solid acid catalysts, which are synthesized following a direct hydrothermal route and using silicotungstic acid (STA) as the active compound. These mesoporous silicate structured catalysts have surface area values of 108-393 m(2)/g, depending upon their W/Si ratio. These catalysts showed very high methanol dehydration activity and also very hig...
Attenuation of polychlorinated biphenyls (PCBs) under anaerobic conditions Kaya, Devrim; Sanin, Faika Dilek; İmamoğlu, İpek; Department of Environmental Engineering (2012) Polychlorinated biphenyls (PCBs) are toxic and persistent anthropogenic contaminants. Concern on their adverse health effects has led to their regulation in air, water and/or soil in addition to sludge. Hence, removal of PCBs in various matrices, including transformer oils (TO) is a priority. This study aims to investigate PCB-118 and Aroclor 1254 toxicity and dechlorination by varying certain critical experimental components including electron donor (sludge or fatty acids), inocula (unacclimated or acclima...

Citation Formats

S. Kalyoncu et al., “Enzymatic hydrolysis by transition-metal-dependent nucleophilic aromatic substitution,” NATURE CHEMICAL BIOLOGY, pp. 1031–1039, 2016, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/42673.