The kinetics of photomodification of oligodeoxyribonucleotide pd(GTGTG
A) with a derivative of the complementary oligodeoxyribonucleotide pd(
CACACA) bearing a 3-(n-azidotetrafluorobenzoylamino)propylamine residu
e (ArN3) at the terminal phosphate group was studied at 20 degrees C.
It was found that the target's G(3) residue is preferentially modified
. Along with the transformation of the arylazide moiety, degradation o
f the oligonucleotide fragment of the reagent occurred with a partial
loss of affinity. With the use of the reagent labeled at the 5'-end, s
ites of photomodification were found. From the dependence of the modif
ication level on the reagent concentration at the initial time of irra
diation, the association constant (K-x = (1.40 +/- 0.24) x 10(5) M-1)
was determined. From the dependence of the modification level on the c
oncentration of the pre-irradiated reagent, the constant of the transf
ormed reagent-target association in solution (K-r= (2.49 +/- 0.30) x 1
0(4) M-1) was determined. From the time-dependence of the modification
level [PZ]/p(0), the rate constant for the limiting step of photomodi
fication (k(0) = (5.31 +/- 0.28) x 10(-4) s(-1)) and the modification
efficiency of the target in the complex with the reagent (gamma = 1) w
ere found.