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Solvation effects on the 31P-nmr chemical shifts and infrared spectra of phosphate diesters

✍ Scribed by D. B. Lerner; W. J. Becktel; R. Everett; M. Goodman; D. R. Kearns

Publisher
Wiley (John Wiley & Sons)
Year
1984
Tongue
English
Weight
823 KB
Volume
23
Category
Article
ISSN
0006-3525

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✦ Synopsis

The effects of organic solvents on the 3'P-mr chemical shifts of various phosphate diesters have been investigated in water and mixed-organic solvent systems. The addition of organic solvents to cyclic phosphates and to diethyl phosphate causes large upfield shifts of the phosphorus resonance which are attributed to solvent-induced changes in the local hydration of the phosphodiester group. This is consistent with the fact that there is an inverse correlation between the hydrogen-bond-donating ability of the solvents and the magnitude of the shifts they induce. Other possible interpretations, such as solvent-induced ion pairing and solvent-induced conformational changes, appear to be eliminated. Fourier-transform ir study of the cyclic nucleotides reveals that there are also large solvent-induced shifts in the frequency of the antisymmetric OPO stretching frequency, and a comparison of the two types of measurements indicates that there is a linear correlation between shifts observed in the ir and in the 31P-nmr spectra. With UpU, the solvent-induced 31P-nmr shifts are -3 times smaller than those observed with the cyclic phosphates and the solvent-induced shift of the OPO band is reduced (factor of -1.7) as compared with the cyclic phosphates. With the single-stranded polynucleotides, poly(C) and poly(U), the solvent-induced shifts in both the nmr and ir are quite small (-0.1 ppm and -1 cm-l). The very small solvent effects observed with poly(U) and poly(C) are attributed to a combination of steric effects and a polyelectrolyte effect which maintains a high density of counterions with waters of hydration in the vicinity of the charged backbone and makes the phosphates much less susceptible to solvent-induced changes in hydration.

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