Ternary complexes in solution. XVIII. Stability enhancement of nucleotide-containing charge-transfer adducts through the formation of a metal ion bridge

Naumann, Christoph F.; Sigel, Helmut

doi:10.1021/ja00816a016

Cited by 92 publications

(49 citation statements)

References 5 publications

(5 reference statements)

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“…This distance agrees favorably with the corresponding ones of Cu(Bipy)(ATP)2-(0.43 nm) and Cu(Bipy)-(ITP)Z-(0.5 nm), and for these ternary complexes it has been shown that an intramolecular charge-transfer adduct is formed between the aromatic parts of the two ligands, i.e. the purine moieties and 2,2'-bipyridyl [8,26]. In fact, the formation of such a metal ionbridged charge-transfer complex between 2,2'-bipyridyl and the guanosine moiety of GTP could be confirmed by the detection of an additional absorption in the ultraviolet region of the spectrum.…”

Section: E a Y~-a Y O supporting

confidence: 83%

A Comparison on the Coordination Tendency towards Cu²⁺ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

Sigel¹,

Naumann²,

Prus³

1974

European Journal of Biochemistry

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The chemical shift of the proton H(8) in the proton magnetic resonance spectrum of GTP was measured in aqueous solution in dependence on pH (2 to 12). Based hereon the acidity constants for protonation at N(7) and deprotonation at N( 1) were determined. From the line broadening effects in the presence of Cu2+ it is concluded that this metal ion interacts with N(7) of the guanine moiety in Cu(GTP)2-. Hence, the structure of this latter complex corresponds to the one of Cu(ATP)2-, while in Cu(1TP)Z-only a very minor interaction with N(7) occurs (cf. Eur. J. Biochem. 41, [I9741 209-216). There is also evidence that in the complex CU(GTP-~H)~-a 5-membered chelate involving N(7) and O(6) is formed, while in Cu(ITP-IH)3-the interaction with Cu2+ occurs only with the N(1), O(6)-site of the base moiety. The decrease in line broadening observed at higher pH indicates that the Cuz+-nucleic-base interaction is depressed in CU(ATP)(OH)~-, Cu(GTP-1 H)(OH)4-and Cu(1TP-1H)(OH)4-, as well. In all the mixed-ligand systems which consist of Cu2+, 2,2'-bipyridyl (Bipy) and one of the three nucleotides (NTP) the ternary complexes, Cu(Bipy) (NTP)2-, are formed. Within these ternary complexes a charge-transfer interaction occurs between the purine part of the nucleotides and 2,2'-bipyridyl.Recent studies on the dephosphorylation of the binary and ternary complexes, Cu(ATP)2-and Cu-(Bipy)(ATP)2-[1,2], and the extension of this work to the corresponding complexes with ITP4-and GTP4-

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Section: E a Y~-a Y O supporting

confidence: 83%

A Comparison on the Coordination Tendency towards Cu²⁺ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

Sigel¹,

Naumann²,

Prus³

1974

European Journal of Biochemistry

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“…In the present context it may also be pointed out that the existence of intramolecular stacks in Cu(Bpy)(S'AMP) complexes had been discovered about 15 years ago [17] in ultraviolet spectrophotometric measurements by the observation of a charge-transfer band due to the purine-pyridyl interaction; a tentative and simplified structure of this species is shown in Fig. 2.…”

Section: Note This Is Part 52 Of the Series Ternary Complexes In Solmentioning

confidence: 54%

Metal‐ion‐governed molecular recognition: extent of intramolecular stack formation in mixed‐ligand–copper(II) complexes containing a heteroaromatic N base and an adenosine monophosphate (2′AMP, 3′AMP, or 5′AMP)

Massoud

Tribolet

Sigel

1990

European Journal of Biochemistry

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Stability constants of mixed-ligand Cu(Arm)(AMP) complexes [where Arm = 2,2'-bipyridyl (Bpy) or 1,10-phenanthroline (Phen) and AMP2-= 2'AMP2-, 3'AMP2-or 5'AMP2 -1 were determined by potentiometric pH titrations in aqueous solution at I = 0.1 M (NaNO,) and 25°C. The ternary Cu(Arm)(AMP) complexes are more stable than corresponding Cu(Arm)(R-MP) complexes, where R-MP2 represents a phosphate monoester with a group R that is unable to participate in any kind of interaction within the complexes as, for example, D-ribose 5'-monophosphate. This increased stability is attributed, in agreement with previous results, to intramolecular stack formation in the Cu(Arm)(AMP) complexes between the purine residue of the AMPs and the aromatic rings of Bpy or Phen. Based on correlation lines (previously obtained from log K versus pK, plots) for Cu(Arm)(R-MP) complexes without a ligand-ligand interaction, a quantitative evaluation was carried out. The degree of formation of the species with the intramolecular stacks increases for the Cu(Arm)(AMP) complexes in the series :3'AMP2-< 5'AMP2-< 2'AMP2-; e.g. in Cu(Bpy)(3'AMP) the stack reaches a formation degree of 45 & 11% and in Cu(Bpy)(2'AMP) one of 96.1 0.7% is obtained. It must be emphasized that these differences are due to the different steric orientations of the bridging metal ion, which result from the varying position of the phosphate group on the ribose ring. As shown by 'H-NMR shift measurements, there is no significant effect of the position of the phosphate group on the stability of the binary (Phen)(AMP)2-adducts ( K z 36 M-' in D20); such an effect is seen only if a metal-ion bridge is formed between the moieties forming the stack, i.e. metal-ion coordination imposes individual properties on the AMPs. By also taking into account some recent results on other nucleoside 5'-monophosphate complexes, the following trend for an increasing stacking tendency of the nucleic base moieties can be established: uracil 5 cytosine 5 thymine < adenine < 7-deazaadenine. Some additional conclusions of general importance are given and the relevance of the results with regard to bio-systems is indicated.Intercalation of aromatic groups between the nucleic base moieties of the strands of DNA and RNA is a widespread reaction [2,3], which is also used as a vehicle to obtain selective cleavages of these nucleic acids [4 -61. Similarly, the corresponding type of interaction, i.e. intramolecular ligand-ligand stacking involving nucleotides in mixed-ligand -metal-ion complexes of low molecular mass gives rise to distinct structures of these complexes in solution [l, 7-91 Abbwviutions. AMP is used as the summary symbol for 2'AMP, 3'AMP and S'AMP; AN, adenine nucleotide; Arm, heteroaromatic nitrogen base, e.g. Bpy or Phcn; Bpy, 2,2'-bipyridyl; MZt, general divalent metal ion; 5'NMP2', nucleoside 5'-monophosphate (other than S'AMP'-); Phen, 1,lO-phenanthroline; Rib5P2 -, o-ribose 5'-monophosphate; R-MPZ-, phosphate monoester where R is any organic residue, e. g. ribosyl or nucleosidyl; 5'TuMP' -, tube...

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“…About 40 years ago intramolecular aromatic-ring stacking was described for the first time [217,218] between heteroaromatic N bases (Arm), i.e., 2,2'-bipyridine or 1,10-phenanthroline, and AMP 2-, ADP 3-or ATP 4-, both ligands being bridged by a metal ion [200,[219][220][221].…”

Section: Of Stacksmentioning

confidence: 99%

“…Originally the interactions had been proven by UV spectrophotometry [217][218][219][220] and 1 H NMR shift measurements [201,222,223]. Later, complexes of the type M(Arm)(adenine nucleotide)…”

Section: Of Stacksmentioning

confidence: 99%

Complex Formation of Cadmium with Sugar Residues, Nucleobases, Phosphates, Nucleotides, and Nucleic Acids

Sigel

Skilandat

Sigel

et al. 2012

Metal Ions in Life Sciences

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Cadmium(II), commonly classified as a relatively soft metal ion, prefers indeed aromaticnitrogen sites (e.g., N7 of purines) over oxygen sites (like sugar-hydroxyl groups). However, matters are not that simple, though it is true that the affinity of Cd(2+) towards ribose-hydroxyl groups is very small; yet, a correct orientation brought about by a suitable primary binding site and a reduced solvent polarity, as it is expected to occur in a folded nucleic acid, may facilitate metal ion-hydroxyl group binding very effectively. Cd(2+) prefers the guanine(N7) over the adenine(N7), mainly because of the steric hindrance of the (C6)NH(2) group in the adenine residue. This Cd(2+)-(N7) interaction in a guanine moiety leads to a significant acidification of the (N1)H meaning that the deprotonation reaction occurs now in the physiological pH range. N3 of the cytosine residue, together with the neighboring (C2)O, is also a remarkable Cd(2+) binding site, though replacement of (C2)O by (C2)S enhances the affinity towards Cd(2+) dramatically, giving in addition rise to the deprotonation of the (C4)NH(2) group. The phosphodiester bridge is only a weak binding site but the affinity increases further from the mono-to the di-and the triphosphate. The same also holds for the corresponding nucleotides. Complex stability of the pyrimidine-nucleotides is solely determined by the coordination tendency of the phosphate group(s), whereas in the case of purine-nucleotides macrochelate formation takes place by the interaction of the phosphate-coordinated Cd(2+) with N7. The extents of the formation degrees of these chelates are summarized and the effect of a non-bridging sulfur atom in a thiophosphate group (versus a normal phosphate group) is considered. Mixed ligand complexes containing a nucleotide and a further mono-or bidentate ligand are covered and it is concluded that in these species N7 is released from the coordination sphere of Cd(2+). In the case that the other ligand contains an aromatic residue (e.g., 2,2'-bipyridine or the indole ring of tryptophanate) intramolecular stack formation takes place. With buffers like Tris or Bistris mixed ligand complexes are formed. Cd(2+) coordination to dinucleotides and to dinucleoside monophosphates provides some insights regarding the interaction between Cd(2+) and nucleic acids. Cd(2+) binding to oligonucleotides follows the principles of coordination to its units. The available crystal studies reveal that N7 of purines is the prominent binding site followed by phosphate oxygens and other heteroatoms in nucleic acids. Due to its high thiophilicity, Cd(2+) is regularly used in so-called thiorescue experiments, which lead to the identification of a direct involvement of divalent metal ions in ribozyme catalysis.

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Ternary complexes in solution. XVIII. Stability enhancement of nucleotide-containing charge-transfer adducts through the formation of a metal ion bridge

Cited by 92 publications

References 5 publications

A Comparison on the Coordination Tendency towards Cu²⁺ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

A Comparison on the Coordination Tendency towards Cu²⁺ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

Metal‐ion‐governed molecular recognition: extent of intramolecular stack formation in mixed‐ligand–copper(II) complexes containing a heteroaromatic N base and an adenosine monophosphate (2′AMP, 3′AMP, or 5′AMP)

Complex Formation of Cadmium with Sugar Residues, Nucleobases, Phosphates, Nucleotides, and Nucleic Acids

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Ternary complexes in solution. XVIII. Stability enhancement of nucleotide-containing charge-transfer adducts through the formation of a metal ion bridge

Cited by 92 publications

References 5 publications

A Comparison on the Coordination Tendency towards Cu2+ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

A Comparison on the Coordination Tendency towards Cu2+ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

Metal‐ion‐governed molecular recognition: extent of intramolecular stack formation in mixed‐ligand–copper(II) complexes containing a heteroaromatic N base and an adenosine monophosphate (2′AMP, 3′AMP, or 5′AMP)

Complex Formation of Cadmium with Sugar Residues, Nucleobases, Phosphates, Nucleotides, and Nucleic Acids

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A Comparison on the Coordination Tendency towards Cu²⁺ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates

A Comparison on the Coordination Tendency towards Cu²⁺ of the Base Moieties in Guanosine, Inosine and Adenosine 5′‐Triphosphates