The binding and reactions of nucleotides and polynucleotides on iron oxide hydroxide polymorphs.

The iron oxide hydroxide minerals goethite and akaganéite were likely constituents of the sediments present in, for instance, geothermal regions of the primitive earth. They may have adsorbed organics and catalyzed the condensation processes which led to the origins of life. The binding to and reactions of nucleotides and oligonucleotides with these minerals was investigated. The adsorption of adenosine, 5'-AMP, 3'-AMP, 5'-UMP, and 5'-CMP to these minerals was studied. Adenosine did not bind to goethite and akaganéite. The adsorption isotherms for the binding of the nucleotides revealed that they all had close to the same affinity for the mineral. Binding to goethite was about four times stronger than to akaganéite. There was little difference in the adsorption of each nucleotide suggesting the binding was between the negative charge on the phosphate group and the positive charges on the mineral surface. The absence of binding of adenosine is consistent with this explanation. Binding decreases as the pH increases due to the titration of the positive (acidic) centers on the minerals. Two times as many moles of polynucleotides were bound to these minerals as compared to the mononucleotides. Watson-Crick hydrogen bonding of adenosine and 5'-AMP to poly(U) complexes with goethite and akaganéite was observed. There was no interaction of uridine with the poly(U)-goethite complex as expected if Watson-Crick hydrogen bonding is taking place. Neither goethite nor akaganéite catalyzed the oligomerization of the phosphorimidazolide of adenosine (ImpA). The template directed synthesis of oligomers of 5'-GMP on the poly(C) bound to goethite was observed. Higher molecular weight oligomers were observed when the poly(C) was bound to goethite than was found in the absence of the mineral.