The effect of adding borax and boric acids on the nucleobase orientation and recognition behavior of novel mono- and oligomeric peptide ribonucleic acids (PRNAs) has been investigated. The base orientation of 5'-amino-5'-deoxyuridine and 5'-amino-5'-deoxycytidine was shown by CD and NOE difference spectral studies to switch from anti to syn in berate buffer or upon addition of borax. The origin of this phenomenon is elucidated to be the cooperative effect of the cyclic berate esterification of the sugar's cis-2',3'-diol and the hydrogen-bonding interaction between the sugar's 5'-amino proton and the base's 2-carbonyl oxygen. Because this new strategy for switching the base orientation through the addition of berate is potentially applicable to the recognition control of nucleic acids if the sugar's 5'-proton and cis-2',3'-diol remain unmodified, we synthesized a series of PRNAs, in which the 5'-amino-5'-deoxypyrimidine ribonucleoside moiety was appended to a mono- or oligo(gamma-L-glutamic acid) backbone through the 5'-amino group. The orientation switching through the addition of berate was also confirmed with the monomeric model, and the switching efficiency was enhanced for oligomeric gamma-PRNA. Finally, it was unambiguously demonstrated that the gamma-PRNA 8-mer with an isopoly-(L-glutamic acid) backbone can form a tight complex with DNA, and further, the recognition of DNA with gamma-PRNA 8-mer is controlled by the berate added as an external factor.