Metal Complexes as Alternative Base Pairs or Triplets in Natural and Synthetic Nucleic Acid Structures

De, Arnie; Kong, Jing; Achim, Catalina

doi:10.1002/9781118517413.ch10

Cited by 2 publications

(3 citation statements)

References 150 publications

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“…60,61 A pair of HQ pair has more extended aromatic ligands, which attain additional stabilization by efficient π-stacking as well as the hydrophobic effect. The other hydroxyquinoline-based metallo-base pair, 7 HQCu II 7 HQ, also showed significant duplex stabilization (¦T m M = +22.0°C). 61 The formation of the metallo-base pairs was confirmed by UV absorption spectroscopy and EPR measurements, which established a square-planar coordination geometry of the Cu(II) complex.…”

Section: Cu(ii)-mediated Base Pairingmentioning

confidence: 99%

Artificial DNA Base Pairing Mediated by Diverse Metal Ions

2017

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Metal-mediated artificial DNA base pairs, consisting of two ligand-type nucleosides and a bridging metal ion, are promising building units for constructing DNA-based supermolecules. Metallo-base pairing allows the thermal stabilization and sitespecific functionalization of DNA duplexes. In this review, representative examples of the metallo-base pairs are classified according to the metal species, and their structures and properties are highlighted. Recent applications including polymerase synthesis are also overviewed to illustrate the future directions of this research field.

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Section: Cu(ii)-mediated Base Pairingmentioning

confidence: 99%

Artificial DNA Base Pairing Mediated by Diverse Metal Ions

2017

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“…The selective self-assembly of ligand-modified nucleic acids allows the programmable arrangement of functional elements in nanoscale systems. , The synthesis of PNA monomers that contain ligands instead of nucleobases makes possible the creation of metal-mediated, alternative base pairs and triplets at specific locations in nucleic acid duplexes and triplexes, respectively . In the last 15 years, several research groups have developed numerous nucleic acid duplexes that contain a variety of transition-metal-based, alternative base pairs. , Given the planar geometry of natural nucleobase pairs as well as the contribution of π-stacking interactions to the stabilization of nucleic acid duplexes, square planar metal complexes with aromatic ligands have been the first, and are the preponderant, type of inorganic alternative base pairs that have been incorporated in nucleic acid duplexes. The substitution of two complementary bases with two aromatic ligands makes possible the formation of planar complexes that are structurally similar to nucleobase pairs.…”

Section: Introductionmentioning

confidence: 99%

“…12 In the last 15 years, several research groups have developed numerous nucleic acid duplexes that contain a variety of transition-metal-based, alternative base pairs. 13,14 Given the planar geometry of natural nucleobase pairs as well as the contribution of π-stacking interactions to the stabilization of nucleic acid duplexes, square planar metal complexes with aromatic ligands have been the first, and are the preponderant, type of inorganic alternative base pairs that have been incorporated in nucleic acid duplexes. The substitution of two complementary bases with two aromatic ligands makes possible the formation of planar complexes that are structurally similar to nucleobase pairs.…”

Section: ■ Introductionmentioning

confidence: 99%

Metal Coordination to Ligand-Modified Peptide Nucleic Acid Triplexes

2018

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A challenging goal in nanotechnology is the precise and programmable arrangement of specific elements in nanosystems in the three-dimensional space. The use of ligand-modified nucleic acids represents an accurate and selective tool to achieve this goal when it comes to metal ion organization. The synthesis of peptide nucleic acid (PNA) monomers that contain ligands instead of nucleobases makes possible the creation of metal-mediated alternative base pairs and triplets at specific locations in PNA duplexes and triplexes, respectively. We report the formation of four- and six-coordinate metal complexes between PNA triplexes modified with 2,2'-bipyridine (Bpy) or 8-hydroxyquinoline (Q) ligands and 3d metal ions. These metal complexes function as alternative base triplets or pairs in that they increase the thermal stability of the triplexes if the stability constants of the metal complexes are relatively high. The increase in the triplex melting temperature correlates with the stability constants of the metal complexes with ligand-containing PNA determined by UV-vis titrations. The metal complexes coordinate two or three ligands although three bidentate ligands are in close proximity of each other within a triplex. Metal coordination to ligand-modified PNA triplexes was further studied by electron paramagnetic resonance (EPR) spectroscopy and circular dichrosim (CD) spectroscopy. EPR spectroscopy indicated the formation of a square planar [CuQ] complex between Cu and Q-containing PNA triplex. Taken together, the spectroscopic results indicate that in the presence of 1 equiv of Fe or Ni the majority, but not all, of the Bpy-containing PNA triplexes contain [MBpy] complexes, with a minority of them being metal free. We attribute this behavior to a supramolecular chelate effect exerted by the triplex, which favors the formation of tris-ligand complexes, that is balanced by the steric interactions between the metal complex and the adjacent nucleobase triplets, which decrease the stability of the complex and triplex. In contrast, the very high stability of square planar [MQ] complexes of Cu and Ni leads to formation of bis-ligand complexes instead of tris-ligand complexes with Q-containing PNA triplexes. The metal-containing PNA triplexes have a terminal l-lysine and adopt a left-handed chiral structure in solution. The handedness of the PNA triplex determines that of the metal complexes formed with the Bpy-containing PNA triplexes.

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Metal Complexes as Alternative Base Pairs or Triplets in Natural and Synthetic Nucleic Acid Structures

Cited by 2 publications

References 150 publications

Artificial DNA Base Pairing Mediated by Diverse Metal Ions

Artificial DNA Base Pairing Mediated by Diverse Metal Ions

Metal Coordination to Ligand-Modified Peptide Nucleic Acid Triplexes

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