Nitrogen-15 Nuclear Magnetic Resonance Evidence That Mg<sup>2+</sup> Does Not Complex with Nitrogen Atoms of Adenosine Triphosphate

Happe, James A.; Morales, Manuel F.

doi:10.1021/ja00961a060

Cited by 72 publications

(18 citation statements)

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“…Here it should be mentioned that Mg2+, the metal ion naturally preferred in these enzyme reactions, coordinates like Cu2+ and Zn2+ to the p and y-phosphate groups [ l l , 361 ; hence, a shift along the phosphate back-bone with resulting a,p-coordination is also possible with Mg2+. The reason for the relative ineffectiveness of Mg2+ to promote the dephosphorylation in vitro [8,9] is due to its very low tendency to interact with the nucleic bases [12,18,63].…”

Section: Genmd Conclusioizsmentioning

confidence: 99%

Comparison of the Metal-Ion-Promoted Dephosphorylation of the 5'-Triphosphates of Adenosine, Inosine, Guanosine and Cytidine by Mn2+, Ni2+ and Zn2+ in Binary and Ternary Complexes

Amsler

Sigel

1976

Eur J Biochem

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The dependence of the rate of dephosphorylation of ATP, ITP, GTP and CTP (= NTP), expressed as first-order rate constants (50 "C; I = 0.1 M, NaCIO,), on pH (2 to lo), in the absence and presence of Mn2+, Ni2+ and Zn2+, was investigated. The reaction is accelerated by Zd2+ and passes through a pH optimum at about 8 for the system Zn2f.-ATP or 9 for Zn2+-ITP and Zn2+-GTP; this is analogous to observations made earlier with the corresponding Cu2+ systems. By computing the pH dependence of the distribution of the several species present in these systems it is shown that the highest rates are observed in the pH regions where the concentration of Zn(ATP)2-, Zn(lTP-H)3-, or Zn(GTP-H)3 -dominates. By evaluating the pH dependence evidence is given that the attacking nucleophije is OH-or H 2 0 for Zn(ATP)'-and H20 for Zn(ITP-H)3-or Zn(GTP-H)3 -. For all these complexes metal-ion/nucleic-base interactions are known, leading to the formation of macrochelates. These metal-ion/nucleic-base interactions are crucial for the observation of a metal-ion-promoted dephosphorylation ; in agreement with this, and the small tendency of the cytosine moiety to coordinate, the CTP systems are rather stable towards dephosphorylation. It should be noted that these experimental results do not necessarily mean that the macrochelates usually described are the reactive complexes, but only that the active complex must be closely related to them (e.g. isomers, etc.). Although for the Ni2+ systems with ATP, ITP and GTP, and for the Mn2+-ATP system a metal-ion/nucleic-base interaction is also known, these systems are not very sensitive to hydrolytic cleavage of the terminal P-0-P bond. The only known significant structural difference between the Ni2 +-NTP or the Mn2 +-ATP complexes and those of Cu2+ or Zn2+ is that Ni2+ and Mn2+ coordinate to all three phosphate groups, whereas Cu2 + and Zn2 + involve only the fl and y ones. This structure-reactivity relationship is rationalized by the suggestion that in the active species the metal ion should be coordinated to the a,/?-phosphate groups leaving the 1'-group open to nucleophilic attack. Obviously, an initial PJ-COordination is suitable for a shift of the metal ion along the phosphate back-bone into the reactive a,P-position, while for an a,/?,?-coordination only the less favorable removal of the coordinated pgroup remains. The metal-ion/nucleic-base interaction is considered as being important for achieving this reactive structure. The connection between trans-phosphorylations in vitro and in vivo is discussed. It is also shown that the formation of mixed-ligand or ternary complexes inhibits the dephosphorylation process. This is on the one hand of interest with regard to the transport of hydrolysis-sensitive phosphates in nature, while on the other it casts doubts on conclusions based on experiments carried out in the presence of buffers, because these contain weak bases and hence potential ligands.Considering the importance of phosphoryl and nucleotidyl transfers in nature and because the enzymes ...

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Section: Genmd Conclusioizsmentioning

confidence: 99%

Comparison of the Metal-Ion-Promoted Dephosphorylation of the 5'-Triphosphates of Adenosine, Inosine, Guanosine and Cytidine by Mn2+, Ni2+ and Zn2+ in Binary and Ternary Complexes

Amsler

Sigel

1976

Eur J Biochem

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“…2 is a representative 2D 1 H- 15 N HMBC spectrum, obtained with 20 mM ATP at pH 3.2. A high-resolution 1 H spectrum is also displayed in x-dimension, along with a y-projection for nitrogen peaks and peak assignments according to earlier studies [23,24]. The 2D spectrum shows well-resolved four correlation peaks for ATP base, i.e.…”

Section: Resultsmentioning

confidence: 87%

Elucidation of spermidine interaction with nucleotide ATP by multiple NMR techniques

Song¹,

Parker²,

Enoh³

et al. 2009

Magnetic Reson in Chemistry

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Interaction of polyamines with nucleotides plays a key role in many biological processes. Here we use multiple NMR techniques to characterize interaction of spermidine with adenosine 5′-triphosphate (ATP). Two-dimensional 1 H-15 N spectra obtained from gs-HMBC experiments at varied pH show significant shift of N-1 peak around pH 2.0-7.0 range, suggesting that spermidine binds to N-1 site of ATP base. The binding facilitates N-1 deprotonation, shifting its pK a from 4.3 to 3.4. By correlating 15 N and 31 P chemical shift data, it is clear that spermidine is capable of concurrently binding to ATP base and phosphate sites around pH 4.0-7.0. The self-diffusion constants derived from 1 H PFG-diffusion measurements provide evidence that binding of spermidine to ATP is in 1:1 ratio, and pH variations do not induce significant nucleotide selfassociation in our samples. 31 P spectral analysis suggests that at neutral pH, Mg 2+ ion competes with spermidine and shows stronger binding to ATP phosphates. From 31 P kinetic measurements of myosin catalyzed ATP hydrolysis, it is found that binding of spermidine affects the stability and reactivity of ATP. These NMR results are important for advancing the studies on nucleotidepolyamine interaction and its impact on nucleotide structures and activities under varied conditions.

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“…A still interesting feature is the larger shifts of H-8 > H-2 in Zn(II)-L-ATP systems (Table 5), which indicates that N-7(purine)/Zn(II) interaction occurs to some extent in the ternary systems (Martin, 1985;Happe and Morales, 1966). On the other hand, the existence of the additional phenyl or pyridyl groups in the L b,c -ATP system decreases the extent of stacking between phen and nucleobase residue of ATP.…”

Section: Y Guo Et Almentioning

confidence: 97%

“…Since the model of electrostatic interactions suggested sometimes cannot efficiently explain the high specificity of a certain process, 31 P and 1 H NMR spectra were usually used as conventional and direct methods to determine interactions relative to phosphorous and p-stacking interaction between aromatic groups, respectively (Du and Mao, 2000;Happe and Morales, 1966).…”

Section: P and 1 H Nmr Spectramentioning

confidence: 99%

“…The fluxing of electron cloud from Zn(II) to the stronger donor nitrogens of L leads to a decrease in the attractability of Zn(II) to the phosphate oxygens and thus the susceptibility of the phosphorous center of ATP toward nucleophilic attack. In the Zn(II)-ATP system, for adenosine there is a dichotomy in metal ion binding of N-1 vs N-7 depending on the pH (Martin, 1985;Happe and Morales, 1966). Another feature of Zn(II)-nucleotide interactions is the open-macrochelate isomeric equilibrium, since N-7 is orientated towards the phosphate group in the dominating anti conformation of ATP.…”

Section: Zn(ii) Complexes Of L Recognize Atpmentioning

confidence: 99%

See 1 more Smart Citation

Recognition promoted by Zn²⁺ between phenanthroline bridging polyaza ligands and nucleotides — Zn²⁺ acts as ‘messenger’ between the receptor and substrate

Guo

Lin

et al. 2003

J of Molecular Recognition

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The stability constants of the supramolecular complexes formed between L ((a,b,c,d)) or their Zn(2+) complexes, and adenosine 5'-triphosphate (ATP) in aqueous solution were determined by potentiometric titrations (25 degrees C, I = 0.1 mol dm(-3) KNO(3)). The results show that protonated aliphatic-substituted L (a,d) and aromatic-substituted L (b,c) ligands and/or Zn(II) ion can efficiently recognition the substrate, ATP. All of the equilibrium studies, (1)H and (31)P nuclear magnetic resonance spectra indicate that multiple interactions, including coordination, pi-stacking, ion-pairing, H-bonding, and possible ion-pi-donor, hydrophobic and even van der Waals interactions exist in the Zn(II)-L-ATP systems. On the other hand, the recognition of the substrates by the protonated ligands was significantly promoted by the addition of Zn(II), which leads to coordination competition between the mixed ligands, L and nucleotide. In Zn(II)/L/ATP systems the tendency for phosphate chain to receive proton and metal ion increases, facilitating the cleavage of the phosphate chain of the nucleotide.

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Nitrogen-15 Nuclear Magnetic Resonance Evidence That Mg²⁺ Does Not Complex with Nitrogen Atoms of Adenosine Triphosphate

Cited by 72 publications

References 1 publication

Comparison of the Metal-Ion-Promoted Dephosphorylation of the 5'-Triphosphates of Adenosine, Inosine, Guanosine and Cytidine by Mn2+, Ni2+ and Zn2+ in Binary and Ternary Complexes

Comparison of the Metal-Ion-Promoted Dephosphorylation of the 5'-Triphosphates of Adenosine, Inosine, Guanosine and Cytidine by Mn2+, Ni2+ and Zn2+ in Binary and Ternary Complexes

Elucidation of spermidine interaction with nucleotide ATP by multiple NMR techniques

Recognition promoted by Zn²⁺ between phenanthroline bridging polyaza ligands and nucleotides — Zn²⁺ acts as ‘messenger’ between the receptor and substrate

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Nitrogen-15 Nuclear Magnetic Resonance Evidence That Mg2+ Does Not Complex with Nitrogen Atoms of Adenosine Triphosphate

Cited by 72 publications

References 1 publication

Comparison of the Metal-Ion-Promoted Dephosphorylation of the 5'-Triphosphates of Adenosine, Inosine, Guanosine and Cytidine by Mn2+, Ni2+ and Zn2+ in Binary and Ternary Complexes

Comparison of the Metal-Ion-Promoted Dephosphorylation of the 5'-Triphosphates of Adenosine, Inosine, Guanosine and Cytidine by Mn2+, Ni2+ and Zn2+ in Binary and Ternary Complexes

Elucidation of spermidine interaction with nucleotide ATP by multiple NMR techniques

Recognition promoted by Zn2+ between phenanthroline bridging polyaza ligands and nucleotides — Zn2+ acts as ‘messenger’ between the receptor and substrate

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Nitrogen-15 Nuclear Magnetic Resonance Evidence That Mg²⁺ Does Not Complex with Nitrogen Atoms of Adenosine Triphosphate

Recognition promoted by Zn²⁺ between phenanthroline bridging polyaza ligands and nucleotides — Zn²⁺ acts as ‘messenger’ between the receptor and substrate