Synthetic studies leading to biomimetic coordination complexes and RNA nanotechnology.

摘要

The structural behavior of Zn(II) complexes of (S)-N,N-Bis(2-quinolylmethyl 1-phenyl-(2-pyridine)methanamine was examined. The ligand adopts propeller-like conformations upon complexation of trigonal bipyramidal metal ions such as Zn(II). The first part of my thesis will describe the synthesis of a novel, chiral derivative of TPA. The second part will discuss the synthesis of an interesting new heterodinuclear ligand that is suitable for modeling the reaction mechanism of DNA polymerase. Complexes involving one Zn(II) ion and one alkaline earth ion catalyze the hydrolysis of bis-(p-nitrophenyl)phosphate. The mechanism is presumed to be similar to the 3′,5 ′-exonuclease activity of DNA polymerase. A synthetic crown ether-TPA conjugate 24 proved to be a host for amino acid guests such as +H₃N-(CH₂)₂-CO ₂−. Optimal complexation was observed with 6-aminohexanoic acid suggesting a cleft-like arrangement of the binding sites aproximately 6.5 Å apart with coordination of the carboxylate to the Cu(II) ion and concomitant binding of the ammonium ion to the oxygen of the crown ether ring. A crystal structure of 24 shows that it binds one K+ and one Zn2+ ion. In addition, new ligands with increased distance between the two metals ions were synthesized.; The third chapter will show the synthesis of a nucleic acid containing pendant groups to the outer part of the RNA double helix skeleton and use these groups to anchor peptidic subunits to fashion new antisense material. Preliminary synthetic studies were conducted leading up to studies of the alkylation of N3-benzoyl-3′,5′ -O-(di-tert-butylsilanediyl)uridine in presence of base to produce the desired building block for such modified RNA molecules.