Optical and conformational properties of the 7‐(beta‐<scp>D</scp>‐ribofuranosyl) purines

Miles, Daniel W.; Inskeep, Warren H.; Townsend, Leroy B.; Eyring, Henry

doi:10.1002/bip.1972.360110606

Cited by 15 publications

(15 citation statements)

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“…The quantities relevant for the calculation of DK and RK can be found by means of molecular exciton theory, which makes use of the transition moments and other base spectroscopic parameters predetermined by the CNDO/S calculation (10,18). Each type of saturated ribose bond is characterized by two parameters, the excitation energy and the transition dipole moment u,,, of that bond when in an (hypothetical) isolated condition in which it does not interact with any other bonds.…”

Section: Alpmentioning

confidence: 99%

“…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.…”

mentioning

confidence: 99%

“…The theoretical work on nucleoside optical activity has been carried out principally by the Eyring group, who published the first quantum mechanical studies that gave theoretical diagrams showing the dependency of the nucleoside CD bands on the sugar-base torsion angle (4-6, 10, [16][17][18]. The theoretical diagrams predicted a positive CD band for fl-pyrimidine nu-cleosides in the anti conformation, a negative CD band for the syn conformation, and a large negative CD band for-the high-anti conformation (5).…”

mentioning

confidence: 99%

“…The treatment was limited to a consideration of dynamic field effects with the effects of static fields, and effects of n a lr* transitions on the calculated CD were entirely ignored. Applications to pyrimidine nucleosides improved agreement between experimental and theoretical CD magnitudes (10,18). However, the theory has not been particularly satisfactory with regard to ordinary purine nucleosides, which exhibit weak rotational strengths.…”

mentioning

confidence: 99%

“…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.…”

mentioning

confidence: 99%

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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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Section: Alpmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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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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Circular dichroism of some mononucleosides

Brunner

Maestre

1975

Biopolymers

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SynopsisThe circular dichroism (CD) and absorption spectra of uridine, thymidine, purine ribonucleoside, and the four adenine derivat.ives 2'-deoxyadenosine, adenosine, adenosine-3',5'-cyclic phosphate, and arabinosyl adenine were measured in water at pH 7 and pH 2. The absorption and CD spectra of the pyrimidines were simultaneously fitted to four Gaussian bands, and the dipole and rotational strengths of the electronic transitions determined. Adenine-derivative CD spectra were determined by computer averaging six runs.The band at 226 nm probably is an n-r* transition; the band a t 209 nm cannot be detected without a computer. The CD and absorption spectra of purine ribonucleoside indicate three transitions in the 230-310-nm region.The spectra showed CD bands at 268, 226, 209, and 195 nm. The circular dichroism and absorption spectra of uridine, thymidine, purine ribonucleoside, and the four adenine derivatives 2'-deoxyadenosine, adenosine, adenosine-3'-5'-cyclic phosphate, and arabinosyl adenine were measured in water a t p H 7 and pH 2. The purpose is to identify the electronic transitions of the molecules. Such information is necessary both as a starting point for theoretical calculations of the optical properties of polymers' and to evaluate the results of theoretical electronic calculations on monomers. 2 , 3 MATERIALS AND METHODSThe compounds used in this study were purchased from P.L. Biochemicals, Nutritional Biochemicals, or from Cal-Bio-Chem. All materials were used straight from the bottle and dissolved in glass distilled water. Solutions at pH 2 were obtained by acidifying to 0.01 N HCI. Optical measurements were made using cells of 0.1-or 0.05-cm path length; absorption measurements were done with a Cary 14 or Cary 15 spectrophotometer. The circular dichroism of deoxyadenosine, arabinosyl adenine, adenosine 3'-5'-cyclic phosphate, and adenosine were measured with a 6001 CD attachment to a Cary 60 spectropolarimeter. Uridine, thymidine, purine ribonucleoside, and adenosine were measured with a 6003 attachment to a Cary 60. The spectropolarimeters were equipped with Osram suprasil lamps, whose strong far-uv output allowed measurements down to 185 nm with the short-path-length cells employed. The 555

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8‐Oxo‐7,8‐dihydroadenine and 8‐Oxo‐7,8‐dihydroadenosine—Chemistry, Structure, and Function in RNA and Their Presence in Natural Products and Potential Drug Derivatives

Choi

Chang

Gibala

et al. 2017

Chemistry A European J

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A description and history of the role that 8-oxo-7,8-dihydroadenine (8-oxoAde) and 8-oxo-7,8-dihydroadenosine (8-oxoA) have in various fields has been compiled. This Review focusses on 1) the formation of this oxidatively generated modification in RNA, its interactions with other biopolymers, and its potential role in the development/progression of disease; 2) the independent synthesis and incorporation of this modified nucleoside into oligonucleotides of RNA to display the progress that has been made in establishing its behavior in biologically relevant systems; 3) reported synthetic routes, which date back to 1890, along with the progress that has been made in the total synthesis of the nucleobase, nucleoside, and their corresponding derivatives; and 4) the isolation, total synthesis, and biological activity of natural products containing these moieties as the backbone. The current state of research regarding this oxidatively generated lesion as well as its importance in the context of RNA, natural products, and potential as drug derivatives is illustrated using all available examples reported to date.

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Optical and conformational properties of the 7‐(beta‐D‐ribofuranosyl) purines

Cited by 15 publications

References 35 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

Circular dichroism of some mononucleosides

8‐Oxo‐7,8‐dihydroadenine and 8‐Oxo‐7,8‐dihydroadenosine—Chemistry, Structure, and Function in RNA and Their Presence in Natural Products and Potential Drug Derivatives

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