title: Catalytic mechanisms and biocatalytic applications of aspartate and methylaspartate ammonia lyases.
abstract: Ammonia lyases catalyze the formation of α,β-unsaturated bonds by the elimination of ammonia from their substrates. This conceptually straightforward reaction has been the emphasis of many studies, with the main focus on the catalytic mechanism of these enzymes and/or the use of these enzymes as catalysts for the synthesis of enantiomerically pure α-amino acids. In this Review aspartate ammonia lyase and 3-methylaspartate ammonia lyase, which represent two different enzyme superfamilies, are discussed in detail. In the past few years, the three-dimensional structures of these lyases in complex with their natural substrates have revealed the details of two elegant catalytic strategies. These strategies exploit similar deamination mechanisms that involve general-base catalyzed formation of an enzyme-stabilized enolate anion (aci-carboxylate) intermediate. Recent progress in the engineering and application of these enzymes to prepare enantiopure l-aspartic acid derivatives, which are highly valuable as tools for biological research and as chiral building blocks for pharmaceuticals and food additives, is also discussed.
authors: Department of Pharmaceutical Biology, Groningen Research Institute of Pharmacy, University of Groningen, Groningen, The Netherlands.
authors: Marianne
authors: M
authors: de Villiers
authors: Vinod
authors: V
authors: Puthan Veetil
authors: Hans
authors: H
authors: Raj
authors: Jandré
authors: J
authors: de Villiers
authors: Gerrit J
authors: GJ
authors: Poelarends
mesh_terms: D000641:Ammonia / Q000737:chemistry; D000642:Ammonia-Lyases / Q000737:chemistry / Q000378:metabolism*; D001220:Aspartate Ammonia-Lyase / Q000737:chemistry / Q000378:metabolism*; D001419:Bacteria / Q000201:enzymology; D055162:Biocatalysis; D020134:Catalytic Domain; D008958:Models, Molecular; D015202:Protein Engineering
chemical_list: D000641:Ammonia; D000642:Ammonia-Lyases; D001220:Aspartate Ammonia-Lyase; C034881:methylaspartate ammonia-lyase