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Although it is believed that formaldehyde is released from the crosslinking reactions of \u03b2NAs, the mechanism by which \u03b2NAs react with amine\u2010functionalized polymers has yet to be known. In this study, we present the reaction mechanism of the \u03b2NA crosslinking. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) data provide strong evidence that formaldehyde is released during the reaction. Catalytic studies show that sodium bicarbonate (NaHCO<jats:sub>3<\/jats:sub>) and salmon testes DNA accelerate the reaction while hydroxynitrile lyase from Arabidopsis thaliana decelerates the crosslinking reaction. These results suggest that \u03b2NAs are potential self\u2010administered crosslinking agents for future clinical use. \u00a9 2012 Wiley Periodicals, Inc. J. Appl. Polym. 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