ADAMTS4 cleaves at the aggrecanase site (Glu373-Ala374) and secondarily at the matrix metalloproteinase site (Asn341-Phe342) in the aggrecan interglobular domain

J Biol Chem. 2002 May 3;277(18):16059-66. doi: 10.1074/jbc.M108607200. Epub 2002 Feb 19.

Abstract

Two major proteolytic cleavages, one at NITEGE(373)/A(374)RGSVI and the other at VDIPEN(341)/F(342)FGVGG, have been shown to occur in vivo within the interglobular domain of aggrecan. The Glu(373)-Ala(374) site is cleaved in vitro by aggrecanase-1 (ADAMTS4) and aggrecanase-2 (ADAMTS5), whereas the other site, at Asn(341)-Phe(342), is efficiently cleaved by matrix metalloproteinases (MMPs) and by cathepsin B at low pH. Accordingly, the presence of the cleavage products globular domain 1 (G1)-NITEGE(373) and G1-VDIPEN(341) in vivo has been widely interpreted as evidence for the specific involvement of ADAMTS enzymes and MMPs/cathepsin B, respectively, in aggrecan proteolysis in situ. We show here, in digests with native human aggrecan, that purified ADAMTS4 cleaves primarily at the Glu(373)-Ala(374) site, but also, albeit slowly and secondarily, at the Asn(341)-Phe(342) site. Cleavage at the Asn(341)-Phe(342) site in these incubations was due to bona fide ADAMTS4 activity (and not a contaminating MMP) because the cleavage was inhibited by TIMP-3 (a potent inhibitor of ADAMTS4), but not by TIMP-1 and TIMP-2, at concentrations that totally blocked MMP-3-mediated cleavage at this site. Digestion of recombinant human G1-G2 (wild-type and cleavage site mutants) confirmed the dual activity of ADAMTS4 and supported the idea that the enzyme cleaves primarily at the Glu(373)-Ala(374) site and secondarily generates G1-VDIPEN(341) by removal of the Phe(342)-Glu(373) peptide from G1-NITEGE(373). These results show that G1-VDIPEN(341) is a product of both MMP and ADAMTS4 activities and challenge the widely held assumption that this product represents a specific indicator of MMP- or cathepsin B-mediated aggrecan degradation.

MeSH terms

  • ADAM Proteins
  • ADAMTS4 Protein
  • Alanine
  • Amino Acid Sequence
  • Asparagine
  • Binding Sites
  • Cathepsin B / metabolism
  • Glutamic Acid
  • Humans
  • Hydrogen-Ion Concentration
  • Matrix Metalloproteinases / metabolism*
  • Metalloendopeptidases / chemistry
  • Metalloendopeptidases / metabolism*
  • Oligopeptides / pharmacology
  • Phenylalanine
  • Procollagen N-Endopeptidase
  • Substrate Specificity
  • Tissue Inhibitor of Metalloproteinase-1 / pharmacology

Substances

  • Oligopeptides
  • Tissue Inhibitor of Metalloproteinase-1
  • Glutamic Acid
  • Phenylalanine
  • Asparagine
  • Cathepsin B
  • ADAM Proteins
  • Matrix Metalloproteinases
  • Metalloendopeptidases
  • Procollagen N-Endopeptidase
  • ADAMTS4 Protein
  • ADAMTS4 protein, human
  • Alanine