Abstract The artificial base 2-aza-2′-deoxyadenosine (see figure) forms a strong and selective purine-purine base pair with 2′-deoxyguanosine. As a dangling nucleotide, 2-aza- 2′-deoxyadenosine stabilizes DNA duplexes less than 2′-deoxyadenosine, while 7- deaza-2′-deoxyadenosine, a more hydrophobic base, has the greatest duplex-stabilizing effect.