title: Synthesis of azobenzenealkylmaleimide probes to photocontrol the enzyme activity of a bacterial histone deacetylase-like amidohydrolase.
abstract: A series of azobenzenealkylmaleimides (AMDs) with different spacer length was synthesized and coupled via Michael-Addition to a specific mutant of a bacterial histone deacetylase-like amidohydrolase (HDAH). Michaelis-Menten parameters (Vmax and Km) were employed to characterize the effect of both, the spacer length and the configuration (cis vs. trans) of the attached azobenzene moiety, on the HDAH enzyme activity. The photoswitch behavior of the AMD/enzyme conjugate activity was clearly influenced by the AMD spacer length. This study highlights the importance of steric rearrangement of the photoswitch with respect to the active site and describes a strategy to optimize the photocontrol of HDAH.
authors.affiliation: Department of Chemical Engineering and Biotechnology, University of Applied Sciences Darmstadt, 64287 Darmstadt, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Horstmann
authors.affiliation: Department of Chemical Engineering and Biotechnology, University of Applied Sciences Darmstadt, 64287 Darmstadt, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Korbus
authors.affiliation: Department of Chemical Engineering and Biotechnology, University of Applied Sciences Darmstadt, 64287 Darmstadt, Germany.
authors.forename: Tatjana
authors.initials: T
authors.lastname: Friedmann
authors.affiliation: Clemens-Schöpf Institute of Organic Chemistry and Biochemistry, Technical University of Darmstadt, 64287 Darmstadt, Germany.
authors.forename: Christiane
authors.initials: C
authors.lastname: Wolff
authors.affiliation: Clemens-Schöpf Institute of Organic Chemistry and Biochemistry, Technical University of Darmstadt, 64287 Darmstadt, Germany.
authors.forename: Christina Marie
authors.initials: CM
authors.lastname: Thiele
authors.affiliation: Department of Chemical Engineering and Biotechnology, University of Applied Sciences Darmstadt, 64287 Darmstadt, Germany. Electronic address: franz-josef.meyer-almes@h-da.de.
authors.forename: Franz-Josef
authors.initials: FJ
authors.lastname: Meyer-Almes
mesh_terms: D000581:Amidohydrolases / Q000737:chemistry / Q000378:metabolism*; D001391:Azo Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D001419:Bacteria / Q000201:enzymology*; D004789:Enzyme Activation; D006655:Histone Deacetylases / Q000737:chemistry / Q000378:metabolism*; D008301:Maleimides / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D055668:Photochemical Processes
chemical_list: D001391:Azo Compounds; D008301:Maleimides; D000581:Amidohydrolases; D006655:Histone Deacetylases; C009850:azobenzene
keywords: Azobenzenes; Deacetylation; External stimulus; Hofmann rearrangement; Maleimides; Methylenemaleimideamide; Photochromism; Photoswitch; Protein engineering