Nitric oxide-induced deamidation retards and reverses fibril formation by an oligo(glutamine/asparagine) peptide

TOXI 120

Li Kong, kongl@ncifcrf.gov1, Joseph E. Saavedra2, kunio Nagashima3, jiwen zheng4, Anil Patri4, and Larry K. Keefer1. (1) Chemistry Section, Laboratory of Comparative Carcinogenesis, National Cancer Institute at Frederick, Frederick, MD 21702, (2) Basic Research Program, SAIC-Frederick, Inc, Frederick, MD 21702, (3) SAIC-Frederick, Image Analysis Laboratory, Research Technology Program, National Cancer Institute at Frederick, Frederick, MD 21702, (4) SAIC-Frederick, Nanotechnology Characterization Laboratory, National Cancer Institute at Frederick, Frederick, MD 21702
As a post-translational modification, the hydrolytic deamidation of internal asparaginyl and glutaminyl protein residues leads to significant changes in protein function. We have previously reported on a non-hydrolytic mechanism of deamidation that can occur in the presence of aerobic nitric oxide (NO). Here we show that such nitrosative deamidation can slow and even reverse aggregation of a model poly(glutamine/asparagine) peptide, the amyloidogenic GNNQQNY domain of the yeast prion protein Sup35. When the initially monomeric peptide was dissolved at a concentration of 1.2 mM in water at 37 oC, abundant aggregates consisting primarily of thick, elongated, needle-like structures were quickly visible by transmission electron micrography (TEM), and the course of aggregation as followed by dynamic light scattering (DLS) converted essentially all the ~1-nm monomer to ~100-nm fibrils within 25 min. When the procedure was repeated in the presence of the NO donor compound DEA/NO [Et2NN(O)=NONa, 7.5 mM], fibril formation was reduced, no aggregates being seen by TEM until 50 min, with DLS showing the virtual absence of 100-nm particles over 6 h. When the preformed fibrils were exposed to 8.5 mM DEA/NO for 24 h, the initially needle-like fibrils were strikingly changed in size, shape, number, and general appearance, as revealed by TEM. The possible significance of nitrosative peptide deamidation with respect to protein folding and function in health and disease will be discussed.