title: Mechanistic and Catalytic Studies ofβ-Nitroalcohol Crosslinking with Polyamine.
abstract: β-Nitroalcohols (βNAs) are promising corneoscleral crosslinking agents for the treatment of diseases such as keratoconus and myopia. Although it is believed that formaldehyde is released from the crosslinking reactions ofβNAs, the mechanism by whichβNAs react with amine-functionalized polymers has yet to be known. In this study, we present the reaction mechanism of theβNA 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 (NaHCO3) and salmon testes DNA accelerate the reaction while hydroxynitrile lyase from Arabidopsis thaliana decelerates the crosslinking reaction. These results suggest thatβNAs are potential self-administered crosslinking agents for future clinical use.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027.
authors.forename: Xia
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027.
authors.forename: Yongjun
authors.initials: Y
authors.lastname: Li
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027.
authors.forename: Yi
authors.initials: Y
authors.lastname: Rao
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027.
authors.forename: Marissa R
authors.initials: MR
authors.lastname: Solomon
authors.affiliation: Department of Ophthalmology, Columbia University, New York, New York 10032.
authors.forename: David C
authors.initials: DC
authors.lastname: Paik
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027.
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Turro
keywords: biomedical applications; catalysts; crosslinking; gels; swelling