Optical Rotatory Dispersion of Nucleic Acid Derivatives. VIII. The Conformation of Pyrimidine Nucleosides in Solution<sup>*</sup>

Emerson, T. R.; Swan, R. J.; Ulbricht, T. L. V.

doi:10.1021/bi00855a026

Cited by 114 publications

(28 citation statements)

References 24 publications

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“…These studies have yielded some useful rules and diagrams (1)(2)(3)(4)(5)(6)(7)(8)(9)(10) relating the sign of the first CD band to anomeric configuration and to sugar-base torsion angle. Several excellent reviews in this area are now available (11)(12)(13)(14)(15).…”

mentioning

confidence: 99%

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Miles¹,

Farmer²,

Eyring³

1980

Proc. Natl. Acad. Sci. U.S.A.

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The rotational strengths of the four longer wavelength transitions, BsU, Bju, and the two El , of adenosine derivatives constrained in the syn form have been investigated theoretically and experimentally. The theory combines a complete neglect of differential overlap version S (CNDO/S) description of the base with a generalized bond exciton metho by means of a matrix method. Rotational strength wheels for these transitions showing the rotational strength as a function of the glycosidic rotational angles are presented and sector rules discussed. Similar sector rules are predicted for purine nucleoside derivatives containing the 6-amino substituent, regardless of heteroatom content at positions 1 or 3 of the base. The sector rules for the Bs" rotational strength of purine nucleosides lacking the 6-amino substituent are strongly influenced by aza substitution. The circular dichroism spectra of 3-deazaadenosine, 8-a-hydroxyisopropyl)adenosine, and other purine nucleosides having a strong preference for the syn conformation are presented and compared with the theoretical results.Circular dichroism (CD) has been used extensively to study the conformation of nucleosides and nucleotides in solution. These studies have yielded some useful rules and diagrams (1-10) relating the sign of the first CD band to anomeric configuration and to sugar-base torsion angle. Several excellent reviews in this area are now available (11)(12)(13)(14)(15) We report here a theoretical CD study of some purine nucleosides closely related to adenosine which are conformationally restricted more or less to the syn conformation. The complete neglect of differential overlap version S (CNDO/S) procedure of Del Bene and Jaffe (27, 28) is used to calculate the optical parameters of the purine bases instead of our PariserParr-Pople method used in previous calculations (17,18). This and other modifications of the theoretical procedure have improved agreement between experimental data and theoretical results.COMPUTATIONAL METHODS The self-consistent field method has been widely used for the study of the electronic structure of molecules. The molecular orbitals 0t are expressed as linear combination of atomic orbitals 4u according to the equationThe coefficients Ct of the molecular orbital matrix are the solutions of the Hartree-Fock-Roothaan equations 3398The publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked "advertisement" in accordance with 18 U. S. C. §1734 solely to indicate this fact.

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mentioning

confidence: 99%

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Miles¹,

Farmer²,

Eyring³

1980

Proc. Natl. Acad. Sci. U.S.A.

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“…The evidence that the anti conformations of U and dU are favored over syn in the solid state as well as in solution is not disputed (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11). That syn conformations are not present to any detectable extent is generally agreed to be a consequence of unfavorable steric interactions (between the 2-keto oxygen and the endo ribose substituents) not present when the molecules are anti.…”

Section: Resultsmentioning

confidence: 99%

Long-range Spin–Spin Coupling in Pyrimidine Nucleosides

Hruska¹

1971

Can. J. Chem.

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A study has been made of the 100 MHz p.m.r. spectra of a number of pyrimidine nucleosides in aqueous solution. Long-range five-bond spin–spin coupling interactions between the H-5 and H-1′ hydrogens were noted in uridine, 2′-deoxyuridine, 6-azauridine, and 6-azacytidine and rationalized by a predominantly anti conformation for each nucleoside. The absence of a detectable five-bond coupling in orotidine suggested that the syn conformation is preferred in this instance. The relative magnitudes of the four-bond and five-bond interactions in uridine and pseudouridine were shown to be consistent with the calculated mobile π-bond orders of the C6—N1 and C6—C5 bonds of the uracil base.

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“…From the results on the optical activity of nucleosides Ulbricht et al [7] have deduced certain empirical rules on the conformation of these compounds. It is thus not surprising that the Cotton effects of nucleosides containing L-ribose are the mirror images of those of the D-series [8].…”

Section: Optical Properties Of Chemically Synthetised Polynucleotidesmentioning

confidence: 99%

Optical properties of chemically synthetised polynucleotides containing D‐ or L‐ribonucleosides

Frič¹,

Guschlbauer²

1970

FEBS Letters

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Optical Rotatory Dispersion of Nucleic Acid Derivatives. VIII. The Conformation of Pyrimidine Nucleosides in Solution^*

Cited by 114 publications

References 24 publications

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Long-range Spin–Spin Coupling in Pyrimidine Nucleosides

Optical properties of chemically synthetised polynucleotides containing D‐ or L‐ribonucleosides

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Optical Rotatory Dispersion of Nucleic Acid Derivatives. VIII. The Conformation of Pyrimidine Nucleosides in Solution*

Cited by 114 publications

References 24 publications

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Calculations of the circular dichroism of adenosine derivatives constrained in the syn form

Long-range Spin–Spin Coupling in Pyrimidine Nucleosides

Optical properties of chemically synthetised polynucleotides containing D‐ or L‐ribonucleosides

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Optical Rotatory Dispersion of Nucleic Acid Derivatives. VIII. The Conformation of Pyrimidine Nucleosides in Solution^*