An official website of the United States government
Abstract Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KOtAmyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (>90 %) after only 2 h at 40 °C. Traditionally challenging silanes such as Ph3SiH were also easily coupled to simple primary and secondary amines under mild conditions, with reactivity that rivals many rare earth and transition‐metal catalysts for this transformation. Preliminary evidence suggests the formation of hypercoordinated intermediates, but radicals were detected under catalytic conditions, indicating a mechanism that is rare for Si−N bond formation.
more »
« less
Structural and biochemical characterization of iminodiacetate oxidase from Chelativorans sp. BNC1
Summary Ethylenediaminetetraacetate (EDTA) is the most abundant organic pollutant in surface water because of its extensive usage and the recalcitrance of stable metal‐EDTA complexes. A few bacteria includingChelativorans sp.BNC1 can degrade EDTA with a monooxygenase to ethylenediaminediacetate (EDDA) and then use iminodiacetate oxidase (IdaA) to further degrade EDDA into ethylenediamine in a two‐step oxidation. To alleviate EDTA pollution into the environment, deciphering the mechanisms of the metabolizing enzymes is an imperative prerequisite for informed EDTA bioremediation. Although IdaA cannot oxidize glycine, the crystal structure of IdaA shows its tertiary and quaternary structures similar to those of glycine oxidases. All confirmed substrates, EDDA, ethylenediaminemonoacetate, iminodiacetate and sarcosine are secondary amines with at least one N‐acetyl group. Each substrate was bound at there‐side face of the isoalloxazine ring in a solvent‐connected cavity. The carboxyl group of the substrate was bound by Arg265and Arg307. The catalytic residue, Tyr250, is under the hydrogen bond network to facilitate its deprotonation acting as a general base, removing an acetate group of secondary amines as glyoxylate. Thus, IdaA is a secondary amine oxidase, and our findings improve understanding of molecular mechanism involved in the bioremediation of EDTA and the metabolism of secondary amines.
more »
« less
- Award ID(s):
- 1804699
- PAR ID:
- 10459557
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Molecular Microbiology
- Volume:
- 112
- Issue:
- 6
- ISSN:
- 0950-382X
- Page Range / eLocation ID:
- p. 1863-1874
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Direct preparation of alkylated amide‐derivatives by cross‐coupling chemistry using sustainable protocols is challenging due to sensitivity of the amide functional group to reaction conditions. Herein, we report the synthesis of alkyl‐substituted amides by iron‐catalyzed C(sp2)−C(sp3) cross‐coupling of Grignard reagents with aryl chlorides. The products of these reactions are broadly used in the synthesis of pharmaceuticals, agrochemicals and other biologically‐active molecules. Furthermore, amides are used as versatile intermediates that can participate in the synthesis of valuable ketones and amines, providing access to motifs of broad synthetic interest. The reaction is characterized by its good substrate scope, tolerating a range of amide substitution, including sterically‐bulky, sensitive and readily modifiable amides. The reaction is compatible with challenging organometallics possessing β‐hydrogens, and proceeds under very mild, operationally‐simple conditions. Optimization of the catalyst system demonstrated the beneficial effect of O‐coordinating ligands on the cross‐coupling. The reaction was found to be fully chemoselective for the mono‐substitution at the less sterically‐hindered position. Mechanistic studies establish the order of reactivity and provide insight into the role of amide to control mono‐selectivity of the alkylation. The protocol provides the possibility for convenient access to alkyl‐amide structural building blocks using sustainable cross‐coupling conditions with high efficiency. magnified imagemore » « less
-
Abstract Ethylenediaminetetraacetic acid (EDTA), which has two amine and four carboxylate protonation sites, forms stable complexes with lanthanide ions. This work analyzes the coordination structure, in atomic resolution, of the Eu3+ion complexed with EDTA in all its protonation states in aqueous solution. Eu‐EDTA complexes were modeled using classical molecular dynamics (MD) simulations using force field parameters optimized with ab initio molecular dynamics (AIMD) simulations. Structures from the MD simulations were used to predict extended X‐ray absorption fine structure (EXAFS) spectra and compared with EXAFS measurements of the Eu3+aqua ion and Eu‐EDTA complexes at pH 3 and 11. This work details how Eu‐EDTA complex coordination structures change with increasing protonation of the EDTA ligand in the complex, from the tightly bound unprotonated complex to the unbinding of the fully protonated EDTA ligand from the Eu3+ion as both become solvated by water. Agreement between predicted and measured EXAFS spectra supports the findings from simulation.more » « less
-
Abstract This study investigates dioxygen binding and 2‐oxoglutarate (2OG) coordination by two model non‐heme FeII/2OG enzymes: a class 7 histone demethylase (PHF8) that catalyzes the hydroxylation of its H3K9me2 histone substrate leading to demethylation reactivity and the ethylene‐forming enzyme (EFE), which catalyzes two competing reactions of ethylene generation and substratel‐Arg hydroxylation. Although both enzymes initially bind 2OG by using anoff‐line2OG coordination mode, in PHF8, the substrate oxidation requires a transition to anin‐linemode, whereas EFE is catalytically productive for ethylene production from 2OG in theoff‐linemode. We used classical molecular dynamics (MD), quantum mechanics/molecular mechanics (QM/MM) MD and QM/MM metadynamics (QM/MM‐MetD) simulations to reveal that it is the dioxygen binding process and, ultimately, the protein environment that control the formation of thein‐lineFeIII‐OO⋅−intermediate in PHF8 and theoff‐lineFeIII‐OO⋅−intermediate in EFE.more » « less
-
Abstract We report synthesis of a radical scavenging aminated thermoplastic polymer through reactive extrusion of polyethyleneimine (PEI) with a polypropylene and polypropylene‐graft‐maleic anhydride (PP‐g‐MA) meltblend. The reaction was confirmed using acid orange 7 (AO7) amine density assay, toluidine blue O (TBO) carboxylic acid density assay, Fourier transform infrared spectroscopy (FTIR), and a migration assay. FTIR spectra revealed a reduction of the asymmetric stretching of the maleic anhydride (MA) carbonyl group at 1777 cm−1and the emergence of the maleimide carbonyl peak at 1702 cm−1. AO7 supported surface orientation of grafted amine groups by introduction of 7.22 nmol cm−2primary amines, corresponding to the reduction of surface carboxylic acids quantified by TBO from 12.46 nmol cm−2to 0.43 nmol cm−2. After incubation (40°C, 10 days) in ethanol, acetic acid, and water, < 0.1 mg cm−2PEI migrated from the materials, supporting the covalent nature of the grafting. Antioxidant activity was demonstrated exhibiting 5.90 and 4.31 nmol Troloxeqcm−2in aqueous and organic environments, respectively. Results indicate a successful condensation reaction during reactive extrusion, producing an aminated thermoplastic polymer with antioxidant activity for target applications such as food packaging, wastewater treatment, carbon capture, and others.more » « less
