Proton magnetic resonance spectra of adenine 5'-nucleotides. Assignment of H2', H3', and H4' resonance bands and their structural implications

Feldman, Isaac; Agarwal, R. A.

doi:10.1021/ja01028a025

Cited by 32 publications

(15 citation statements)

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“…Figure 3 shows the 220-MHz proton resonance spectrum for the ribose protons of AMP-5' in 0.1 M DzO solution. The assignment of signals in Figure 3 was made on the basis of splitting pattern and chemical shift considerations and is in agreement with an earlier 100-MHz assignment (Feldman and Agarwal, 1968;Fujiwara and Uetsuki, 1968). All of the proton-proton spin coupling constants can be determined at 220 MHz; also, D A V I E S A N D D A N Y L U K with the aid of 3 ' P spin-decoupling experiments a measurement of proton-phosphorus spin-coupling constants is feasible.…”

Section: Resultssupporting

confidence: 86%

“…Comparison of the data in Tables I and I I shows that the major difference between the purine and plValues were reported only for J1.2, J2.3,. J;,q, in thc earlier work (Feldman and Agarwal, 1968;Fujiwara and Uetsuki, 1968). rimidine 5'-ribonucleotides is a near equivalence of C( 5') proton shifts in purines and a substantial nonequivalence in pyrimidine derivatives as well as the fact that the chemical shifts of the furanose ring protons are further downfield for the purine compared to the pyrimidine derivatives.…”

Section: Resultsmentioning

confidence: 80%

“…That the displacement arises as a consequence of the analysis rather than reflecting real conformational differences will be discussed later. The set of curves for different ;.e.. J ( H H ) = 9.8 cos1 0 -0.9 cos 4, Computations were made using the method and equations given by Altona and Sundaralingam (1973) (Feldman and Agarwal, 1968). 0.5Z DzO solution at 28" (Fujiwara and Uetsuki, 1968).…”

Section: Andribose Ring Conformationsmentioning

confidence: 99%

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Nuclear magnetic resonance studies of 5'-ribo- and deoxyribonucleotide structures in solution

Davies¹,

Danyluk²

1974

Biochemistry

286

155

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An extensive proton nuclear magnetic resonance (nmr) study is reported for all common purine and pyrimidine 5'-ribo-and deoxyribonucleotides at 220 MHz.Spectra for these nucleotides were measured in D20 solutions at 20 f 2' and signal assignments made with the aid of selected "-'H and 3'P-'H decoupling experiments.Complete sets of accurate chemical shifts and coupling constants were derived for each nucleotide by iterative procedures and yielded close agreement between observed and calculated spectra. The nmr parameters have been utilized in a quantitative evaluation of several key nucleotide conformational features including equilibrium conformations of ribose and deoxyribose rings, preferred exocyclic group orientations, and base-ribose ring orientation. A quantitative conformational analysis was made for the D-ribose and D-deoxyribose rings of all the 5'-riboncleotides following procedures analogous to those developed recently by Altona and Sundaralingam. The analysis is based on an assumption of a rapidly equilibrating mixture between N type [C(3')-endo, C(2')-exo] and S type [C(2')-endo, C(3')-exo] conformers, N * S. With the aid of graphical plots quantitative estimates were made of pseudorotational angle, P, degree of pucker, T, and ring conformer populations. The results show that the pseudorotational parameters (P, T) do not vary significantly between nucleotides and are generally within ranges found in the crystalline state. An S-type conformation is favored in both ribo-and deoxyribonucleotides at 20° with the equilibrium lying somewhat more in favor of the S conformer in the latter, i.e., 70:30 vs. 60:40. Possible effects of electronegativity change upon pseudorotationa1 parameters were explored and it was concluded that no particular advantage is gained by using adjusted Karplus expressions for individual ring molecular fragments at the present accuracy of measured coupling constants. A confor-T h e structure, conformations, and interactions of purine and pyrimidine nucleosides and 5'-ribo-and deoxyribonucleotides have been the subject of extensive investigations in recent years (Sundaralingam

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Section: Resultssupporting

confidence: 86%

Section: Resultsmentioning

confidence: 80%

Section: Andribose Ring Conformationsmentioning

confidence: 99%

See 1 more Smart Citation

Nuclear magnetic resonance studies of 5'-ribo- and deoxyribonucleotide structures in solution

Davies¹,

Danyluk²

1974

Biochemistry

286

155

View full text Add to dashboard Cite

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“…l), which are well separated from the resonances of the other strongly coupled ribose protons and have been assigned unequivocally in the literature (7,47,48). The resonances of these three protons undergo remarkable upfield shifts (increased shielding) with increasing 5'-AMP concentration, as displayed in Fig.…”

Section: Resultssupporting

confidence: 67%

The self-association of naturally occurring purine nucleoside 5′-monophosphates in aqueous solution

Neurohr¹,

Mantsch²

1979

Can. J. Chem.

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The parameters characterizing the base-stacking self-association of adenosine, inosine, and guanosine 5′-monophosphate have been obtained from 1H nmr dilution studies. The thermodynamic parameters for the formation of adenosine 5′-monophosphate stacks are ΔH0 = −14.5 kJ mol−1 and ΔS0 = −42.3 J K−1 mol−1, with an apparent equilibrium constant of Kc = 1.92 M−1 at 30 °C. The corresponding equilibrium constants for the self-association of inosine and guanosine 5′-monophosphate are 1.36 M−1 and 1.29 M−1, respectively. The negative enthalpy and entropy changes cannot be explained by the concept of classical hydrophobic interactions; however, they strongly support the conclusion that dipole induced dipole forces play a major role for base-stacking in aqueous solution. The sequence of the equilibrium constants for the purine nucleoside 5′-monophosphates can be well explained by the concept of mutual polarization. The stacking geometries for adenosine and inosine 5′-monophosphate are presented as obtained from fitting the experimental shift data to refined isoshielding contours. It is concluded that the stacking pattern is not restricted to a unique geometry.

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“…These experiments were carried out at 27'C in the H2' to lower field (12,25). Consequently, irradiation of one of these protons may affect the other proton.…”

Section: Proton-proton Nuclear Overhauser Effect Measurementsmentioning

confidence: 99%

Nuclear magnetic resonance studies on the self-association of adenosine 5′-triphosphate in aqueous solutions

Lam¹,

Kotowycz²

1977

Can. J. Chem.

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YIU-FAI LAM and GEORGE KOTOWYCZ. Can. J. Chem. 55,3620 (1977). The self-association of adenosine 5'-triphosphate (ATP) in aqueous, basic solutions has been studied. The results indicate that the monomer-dimer-trimer equilibrium model for base association fits the data well, but so does a model which includes higher order species. This indicates that the ATP n~olecules in solution can undergo indefinite linear self-association. The average value of the association constant based on the 'H and 31P chemical shift measurements with indefinite linear self-association and each step has the same equilibrium constant. Heyn and Bretz (2) could not assign a unique geometry for the ATP molecules in the stack but feel that head-to-tail association of the adenine bases is most likely. Further circular dichroism measurements (3) were interpreted in terms of a monomer-dimer model. At a p H of 2.8 and 20°C, a dimerization constant of 88 M-' was obtained. In the complex, the charged phosphate of one ATP molecule interacts electrostatically with the charged adenine ring of the second ATP molecule. In this model, the two adenine rings are stacked head-to-tail and the ATP molecule is in the anti conforn~ation (3). At basic pH's, the model of Heyn and Bretz (2) was applied (3) and an association constant of 51 M-I was obtained (2O0C, p H 8.7) with no MgCI, present. Stacking interactions have also been studied in the presence of 0.154 M NaCl (1) and a monomer-dimer-trimer association model at acidic pH's describes the data best of all.Nuclear magnetic resonance (nmr) experiments also offer valuable information concerning the self-association of ATP. Based on the ring proton chemical shift studies carried out at a Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.213.204.173 on 05/09/18For personal use only.

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Proton magnetic resonance spectra of adenine 5'-nucleotides. Assignment of H2', H3', and H4' resonance bands and their structural implications

Cited by 32 publications

References 1 publication

Nuclear magnetic resonance studies of 5'-ribo- and deoxyribonucleotide structures in solution

Nuclear magnetic resonance studies of 5'-ribo- and deoxyribonucleotide structures in solution

The self-association of naturally occurring purine nucleoside 5′-monophosphates in aqueous solution

Nuclear magnetic resonance studies on the self-association of adenosine 5′-triphosphate in aqueous solutions

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