Fluoride Reduces Binding of MMP-20 to Amelogenin
K. TANIMOTO, T.Q. LE, Z. LI, P. HWANG, W. LI, and P. DENBESTEN, University of California, San Francisco, USA

During enamel formation, hydrolysis of amelogenin by matrix metalloproteinase-20 (MMP-20) is critical to enamel biomineralization. Excessive fluoride during enamel formation results in a delay in the removal of amelogenin, possibly related to an effect on MMP-20 hydrolysis.  In this study, we mutated MMP-20 to prevent autolysis, allowing us to measure binding between amelogenin and MMP-20, and to determine whether fluoride alters this enzyme/substrate interaction. Objectives:  To measure the binding affinity of amelogenin to MMP-20, and to determine the effect of fluoride on binding affinity. Methods:  A point mutation was introduced in recombinant human MMP-20 (rhMMP-20), resulting in a substitution of A at position 227 to E.  This substitution prevented MMP-20 autolysis. rhMMP-20 and inactive rhMMP-20 (E227A) were synthesized from E. coli, purified by His-tag affinity chromatograph, and characterized by SDS-PAGE and Western blot analysis.  Enzymatic activities of these proteases were analyzed using zymography and fluorescent quenched-peptide assay.  Biacore analysis was used to quantify the affinity between an inactive rhMMP-20 and rH174 by immobilizing inactive rhMMP-20 onto a Ni-containing NTA sensor chip via His-tag, followed by injections of solutions containing rH174 with various concentration of NaF (0-50 µM F-).  Results: Wild-type rhMMP-20 was autolysed- into smaller fragments; the predominant active form having a molecular weight of 25-kDa protein.  However, inactive rhMMP-20 had no catalytic activity, and remained as a 50-kDa protein.  Biacore analysis revealed that inactive rhMMP-20 bound specifically to rH174 with a Kd = 5.16 x 10-8 M. Fluoride inhibited the binding of inactive rhMMP-20 to amelogenin in a concentration-dependent manner.  Conclusions: MMP-20 specifically binds to amelogenin.  This binding is significantly reduced by micromolar levels of fluoride.  This effect of fluoride on enzyme/substrate binding may have a role in the delayed removal of amelogenins, resulting in enamel fluorosis.  Support: NIH/NIDCR R01-DE015821

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