SummaryAmine-oxide radical 1 a was efficiently converted to the corresponding Nhydroxy-amine 2 a with sodium dithionite in acetone/water. This reaction was used to develop a procedure for monitoring the NMR. spectra of sodium dithionite reduced amine-oxide radicals and of novel reduced amine-oxide-labeled nucleosides.The stable amine-oxide free radicals are among the most sensitive probes in the biophysical study of nucleic-acid conformations. Amine-oxide radicals containing nucleic acids can be monitored directly by ESR. within complex biological systems without isolation [I]. Although non-site-specifically spin-labeled polynucleotides have been useful, the ESR. spectra of site-specifically modified polynucleotides should, theoretically, reflect specific conformational transitions more accurately [2]. Therefore, the site of attachment of the spin label must be known, and is most conveniently established on the nucleoside-monomer level [3]. The valuable structural evidence accessible by NMR. spectroscopy, however, cannot be acquired by conventional techniques, since paramagnetic species yield spectra of low resolution [4]. Conversion of amine-oxide radicals to diamagnetic species renders the molecules suitable for subsequent NMR. analysis. Phenylhydrazine reduces most amine-oxide radicals [5] efficiently to the analogous N-hydroxyamines directly in the NMR. sample tube [6]. A technique exploiting both phenyfhydrazine and ascorbic acid was used to monitor the NMR. spectrum of a spin labeled transfer RNA [7]. High field resonances were observed after reduction with phenylhydrazine, and ascorbate was used to monitor the low field spectrum. Ascorbate was subsequently shown to convert amine-oxide radicals quantitatively to the corresponding N-hydroxy-amines [8]. These methods, however, were not suited for direct application to spin-labeled nucleosides. Phenylhydrazine is known to produce by-products [9] and to contribute resonances in the region of interest I ) 2,
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