Alkyl-dihydroxyacetonephosphate synthase. Presence and role of flavin adenine dinucleotide

J Biol Chem. 2000 Mar 3;275(9):6276-83. doi: 10.1074/jbc.275.9.6276.

Abstract

Alkyl-dihydroxyacetonephosphate synthase is a peroxisomal enzyme involved in ether lipid synthesis. It catalyzes the exchange of the acyl chain in acyl-dihydroxyacetonephosphate for a long chain fatty alcohol, yielding the first ether linked intermediate, i.e. alkyl-dihydroxyacetonephosphate, in the pathway of ether lipid biosynthesis. Although this reaction is not a net redox reaction, the amino acid sequence of the enzyme suggested the presence of a flavin adenine dinucleotide (FAD)-binding domain. In this study we show that alkyl-dihydroxyacetonephosphate synthase contains an essential FAD molecule as cofactor, which is evidenced by fluorescence properties, UV-visible absorption spectra and the observation that the enzyme activity is dependent on the presence of this cofactor in a coupled in vitro transcription/translation assay. Furthermore, we could demonstrate that the FAD cofactor directly participates in catalysis. Upon incubation of the enzyme with the substrate palmitoyl-dihydroxyacetonephosphate, the flavin moiety is reduced, indicating that in this initial step the substrate is oxidized. Stopped flow experiments show that the reduction of the flavin moiety is a monophasic process yielding a oxygen stable, reduced enzyme species. Upon addition of hexadecanol to the reduced enzyme species, the flavin moiety is efficiently reoxidized. A hypothetical reaction mechanism is proposed that is consistent with the data in this paper and with previous studies.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkyl and Aryl Transferases / chemistry*
  • Alkyl and Aryl Transferases / genetics
  • Animals
  • Dihydroxyacetone Phosphate / analogs & derivatives
  • Dihydroxyacetone Phosphate / metabolism
  • Flavin Mononucleotide / metabolism
  • Flavin-Adenine Dinucleotide / chemistry*
  • Flavin-Adenine Dinucleotide / metabolism
  • Guinea Pigs
  • Kinetics
  • Mutagenesis
  • Oxidation-Reduction
  • Protein Biosynthesis
  • Recombinant Proteins / chemistry
  • Recombinant Proteins / metabolism
  • Spectrometry, Fluorescence
  • Spectrophotometry
  • Transcription, Genetic

Substances

  • Recombinant Proteins
  • Flavin-Adenine Dinucleotide
  • palmitoyl dihydroxyacetone phosphate
  • Dihydroxyacetone Phosphate
  • Flavin Mononucleotide
  • Alkyl and Aryl Transferases
  • alkylglycerone-phosphate synthase