The 2‐Amino Group of 8‐Aza‐7‐deaza‐7‐bromopurine‐2,6‐diamine and Purine‐2,6‐diamine as Stabilizer for the Adenine–Thymine Base Pair in Heterochiral DNA with Strands in Anomeric Configuration

Stabilization of DNA is beneficial for many applications in the fields of DNA therapeutics, diagnostics, and materials science. Now, this phenomenon is studied on heterochiral DNA, an autonomous DNA recognition system with complementary strands in α‐D and β‐D configuration showing parallel strand orientation. The 12‐mer heterochiral duplexes were constructed from anomeric (α/β‐D) oligonucleotide single‐strands. Purine‐2,6‐diamine and 8‐aza‐7‐deaza‐7‐bromopurine‐2,6‐diamine 2′‐deoxyribonucleosides having the capability to form tridentate base pairs with dT were used to strengthen the stability of the dA–dT base pair. T m data and thermodynamic values obtained from UV melting profiles indicated that the 8‐aza‐7‐deaza 2′‐deoxyribonucleoside decorated with a bromo substituent is so far the most efficient stabilizer for heterochiral DNA. Compared with that, the stabilizing effect of the purine‐2,6‐diamine 2′‐deoxyribonucleoside is low. Global changes of helix structures were identified by circular dichroism (CD) spectra during melting.
Base pair stabilization: Heterochiral parallel duplexes represent an autonomous recognition system constructed from anomeric (α/β‐D) oligonucleotides. The naturally occurring purine‐2,6‐diamine and the artificial 8‐aza‐7‐deaza‐7‐bromopurine nucleosides 1 and 2 strengthen the dA–dT base pair. The 8‐aza‐7‐deazapurine nucleoside decorated with a bromo substituent is so far the most efficient stabilizer for this pairing system.