Studies of inter- and intramolecular interaction in mononucleotides by proton magnetic resonance

Schweizer, Martin; Broom, Arthur D.; Ts’o, Paul O. P.; Hollis, Donald P.

doi:10.1021/ja01006a035

Cited by 313 publications

(128 citation statements)

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“…To answer this question, we compared the chemical shift of adenine amino protons in FAD with that in AMP or ADP-ribose as a function of temperature. ADP-ribose is a more suitable control for the adenine moiety of FAD, although dilute solutions of AMP and ADP-ribose showed significant differences only in the temperature dependence of the chemical shift of H-8, a proton most sensitive to phosphate ionization in the predominantly anti conformation between adenine and ribose (15).…”

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confidence: 99%

Intra molecular Hydrogen Bonding in Flavin Adenine Dinucleotide

Raszka

Kaplan

1974

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

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Data obtained by means of proton magnetic resonance spectroscopy indicate that specific association of FMN Proton magnetic resonance (PMR) spectroscopy has been widely applied to detect the specific interactions of molecules in solution. By the use of water as the solvent, we have recently applied the technique to monitoring those hydrogen bonding interactions that involve the amino groups of mononucleotides (1). We have examined the specificity conferred by hydrogen bonding between FMN and AMP, and extended this study to the intramolecular interaction between the flavin and adenine moieties of FAD. Earlier PMR studies of FAD and its components have established the assignment of proton resonances and proposed various models of intramolecular stacking as the predominant mode of association in aqueous media (2-4).It is generally believed that nonpolar solvents obliterate stacking interactions. Using infrared spectroscopy, Kyogoku and Yu (5, 6) have reported the specific association of riboflavin with adenine derivatives in chloroform, and indicated that a hydrogen bonded dimer is not formed between the derivatives of riboflavin and guanosine, cytidine, or uracil. Furthermore, Voet and Rich (7)

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confidence: 99%

Intra molecular Hydrogen Bonding in Flavin Adenine Dinucleotide

Raszka

Kaplan

1974

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

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“…5'-deoxy-5'-methylammonium adenosine iodide [9]. In solution, adenine nucleotides such as AMP and ATP are known to possess the anti-conformation because in their proton magnetic resonance (PMR) spectra the C-8 proton of the purine ring is subject to specific deshielding by the phosphate anion, indicating their close spatial proximity [10,11]. This is paralleled by a preference of the gauche, gauche-C-5' conformation [12].…”

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confidence: 99%

Adenine Nucleosides in Solution: Stabilisation of the anti‐Conformation by C‐5′ Substituents

Follmann

Gremels

1974

European Journal of Biochemistry

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Proton magnetic resonance spectra of 30 adenine nucleosides have been obtained in dilute (0.001 to 0.05 M) aqueous or dimethyl sulfoxide solutions and have been analysed with respect to structuredependent variations of the purine proton chemical shifts. In 2Hz0 the resonance signal of H-8 shows a marked dependence upon the nature of substituents linked to C-4' of adenine ribofuranoside derivatives and upon the presence of a 2': 3'-O-isopropylidene group while H-2 is relatively unaffected.Therefore the chemical shift difference, 6H-8 -6H-2 = Ad, may serve as an indicator of intramolecular ribose-base interact ons. d6 varies with the chemical nature of C-4' or C-5' substituents in the order: ammonium, sulfonium (0 ppm) < hydrogen < hydroxyl amino < thio < halogen < phosphate, carboxylate (0.4 ppm), and decreases with increasing chain length of these substituents. These results suggest the existence of electrostatic and dipolar repulsion or, in the majority of cases, attractive forces between the C-5' and C8-H regions of adenine nucleosides which have been previously demonstrated for 5'-nucleotides only. They imply a strong preference of most adenosine derivatives with unsubstituted 2' and 3'-hydroxyl groups for the anti-conformation range and the gauche, gauche C-5' conformation. In dimethyl sulfoxide, basically the same situation exists but different substituents exhibit smaller individual A6 variations than in water, indicating different solvation shells. In this solvent two additional conformation-stabilizing contributions can be recognized, viz. an interaction of the bridge oxygen (0-4') of ribose with adenine, and a hydrogen bond between H-8 and a 5'-carboxylate anion. This energetic stabilisation of the anti and g,g-conformers by most types of adenosine C-5' substituents supports the "rigidity" concept of nucleotides, extending it to the nucleoside level. The only exception found is 5'-nitromethyladenosine in which ultraviolet, circular dichroism and magnetic resonance spectra suggest rotation of the adenine base to a "non-classical" conformation due to base-chain n-electron interaction. The anti-conformation of the adenosine derivatives used in this study can in some cases be correlated with their enzymatic deamination by adenosine and AMP aminohydrolase.The biochemical function of nucleosides and nucleotides as substrates or effectors of the degrading and polymerizing enzymes of nucleic acid metabolism depends critically upon the molecular conformation which they assume in solution. The three substructures of a typical nucleoside, viz. the heterocyclic base, the pentofuranose ring and the exocyclic 5'-carbon atom carrying various substituents, are known to be arranged in certain relative orientations which have been Part 1 of a series entitled Forces Stabilizing the Conformation of Nucleosides in Solution.

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“…On the other hand, the nuclear magnetic resonance data of Ts'o et al [3,19] support a hydrogen bond from the 2'OH group to the N-3 of the purine base or the 2-keto moiety of the pyrimidines. The latter hydrogen bond is also conceivable in mononucleotides [20] and in nucleosides [21]. Recent comparative experiments [22,23] with 2'-0-methyloligo-and 2'-0-methylpolyadenylic acid and the respective unmethylated compounds raise doubt that the hydrogen bond donor capabilities of the 2'OH group are an essential requirement for the increased stability of oligo-and polyribonucleotides relative to the deoxy compounds.…”

Section: Resultsmentioning

confidence: 99%

“…I n 5'-nucleoside monophosphates [25,20,27] it is now generally accepted that the orientation of the base relative to the ribose ring is "anti" [28].…”

Section: Resultsmentioning

confidence: 99%

The Influence of the 2′OH Group upon the Binding of Nucleotides by Basic Polyamino Acids

Arav

Wagner

1970

European Journal of Biochemistry

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The position of the phosphate group on the ribose of nucleoside monophosphates markedly influences their binding behavior with basic polyamino acids, such as poly-L-lysine and poly-1;-arginine. Equilibrium dialysis of adenine and guanine derivatives has revealed that the binding of 5'-and 3'-ribonucleotides (group I, possessing a free 2'OH group) to basic polyamino acids is clearly different from that of 2'-rib0 and 5'-deoxyribonucleotides (group 11, the 2'OH group is blocked and absent, respect.). At low nucleotide to poly-L-lysine ratios, where the binding corresponds to the Langmuir isotherm, the binding constants of group I are smaller than those of group 11. At higher nucleotide to polypeptide ratios the binding is cooperative and accompanied by a phase transition : guanine derivatives of group I show precipitation with poly-L-lysine a t O", whereas with group I1 a gel-like phase is separated; with poly-L-arginine only precipitation occurs. Analysis of the cooperative binding with guanine nucleotides and poly-L-arginine revealed that group I possesses considerably higher nearest neighbour interaction energies than group 11.The stacking coefficients decrease in the order 3'-GMP > 5'-GMP > 5'-dGMP 7 2'-GMP. The implications of these results are discussed.

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Studies of inter- and intramolecular interaction in mononucleotides by proton magnetic resonance

Cited by 313 publications

References 5 publications

Intra molecular Hydrogen Bonding in Flavin Adenine Dinucleotide

Intra molecular Hydrogen Bonding in Flavin Adenine Dinucleotide

Adenine Nucleosides in Solution: Stabilisation of the anti‐Conformation by C‐5′ Substituents

The Influence of the 2′OH Group upon the Binding of Nucleotides by Basic Polyamino Acids

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