Intramolecular vs intermolecular formation of bityrosine upon photoreaction of poly(l-tyrosine) in dilute aqueous solution


The molecular weight dependence of the rate of the formation of bityrosine upon irradiation of poly(L-tyrosine) at 300 nm has been investigated in dilute aqueous solution, pH 12. The samples studied were the monodisperse monomer, dimer, trimer, and hexamer, as well as two polydisperse polymers with average degrees of polymerization of ∼ 102 and ∼ 103. The reaction is predominantly intermolecular in the monodisperse oligomers, but it is predominantly intramolecular in the two polymers. The intramolecular reaction in the polymers involves phenolic rings on monomers i and i+j, with j>5. The steric restraints imposed by the backbone of the chain make it unlikely that two rings will approach one another with the appropriate geometry for reaction if j<5. © 1992 Springer-Verlag.

Publication Title

Polymer Bulletin