Artificial DNA Base Pairing Mediated by Diverse Metal Ions

Takezawa, Yusuke; Müller, Jens; Shionoya, Mitsuhiko

doi:10.1246/cl.160985

Cited by 137 publications

(77 citation statements)

References 106 publications

(98 reference statements)

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“…[6] While metal-mediated base pairs can be obtained from natural nucleobases,w ith T-Hg II -T and C-Ag I -C representing the best-known examples, [7] av ariety of artificial nucleobases has been introduced to diversify the metal ion scope. [8] To date,a bout ad ozen NMR and crystal structures have been published of DNAand RNAd uplexes with metal-mediated base pairs. [9] Numerous possible applications,i ncluding an expansion of the genetic code,m olecular magnets,atuning of the charge-transfer properties of DNA, sensors for oligonucleotides and other analytes,a nd nanocluster generation have made metalmediated base pairs an attractive field of research.…”

Section: Introductionmentioning

confidence: 99%

Metal‐Modified Nucleic Acids: Metal‐Mediated Base Pairs, Triples, and Tetrads

2019

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The incorporation of metal ions into nucleic acids by means of metal‐mediated base pairs represents a promising and prominent strategy for the site‐specific decoration of these self‐assembling supramolecules with metal‐based functionality. Over the past 20 years, numerous nucleoside surrogates have been introduced in this respect, broadening the metal scope by providing perfectly tailored metal‐binding sites. More recently, artificial nucleosides derived from natural purine or pyrimidine bases have moved into the focus of AgI‐mediated base pairing, due to their expected compatibility with regular Watson–Crick base pairs. This minireview summarizes these advances in metal‐mediated base pairing but also includes further recent progress in the field. Moreover, it addresses other aspects of metal‐modified nucleic acids, highlighting an expansion of the concept to metal‐mediated base triples (in triple helices and three‐way junctions) and metal‐mediated base tetrads (in quadruplexes). For all types of metal‐modified nucleic acids, proposed or accomplished applications are briefly mentioned, too.

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Section: Introductionmentioning

confidence: 99%

Metal‐Modified Nucleic Acids: Metal‐Mediated Base Pairs, Triples, and Tetrads

2019

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“…These unique properties render it an ideal building block in the context of supramolecular chemistry and DNA nanotechnology [1,2]. The modular composition of DNA can be exploited to arrange metal ions within its helix in a predetermined fashion [3][4][5]. Historically, the interaction of transition metal ions with nucleic acids was first demonstrated using simple viscosimetry experiments of DNA solutions in the presence of various inorganic salts [6].…”

Section: Introductionmentioning

confidence: 99%

Stable Hg(II)-mediated base pairs with a phenanthroline-derived nucleobase surrogate in antiparallel-stranded DNA

Jash

Müller

2020

J Biol Inorg Chem

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Metal-mediated base pairs involving artificial nucleobases have emerged as a promising means for the site-specific functionalization of nucleic acids with metal ions. In this context, a GNA-appended (GNA: glycol nucleic acid) nucleoside analogue containing the artificial nucleobase 1H-imidazo[4,5-f][1,10]phenanthroline (P) has already been applied successfully in a variety of homo-and heteroleptic metal-mediated base pairs, mainly involving Ag(I) ions. Herein, we report a thorough investigation of the Hg(II)-binding properties of P when incorporated into antiparallel-stranded DNA duplexes. The artificial nucleobase P is able to form Hg(II)-mediated homoleptic base pairs of the type P-Hg(II)-P with a [2 + 2] coordination environment. In addition, the heteroleptic P-Hg(II)-T pair was investigated. The addition of a stoichiometric amount of Hg(II) to a duplex comprising either a P:P pair or a P:T pair stabilizes the DNA duplex by 4.3 °C and 14.5 °C, respectively. The P-Hg(II)-T base pair, hence, represents the most stabilizing non-organometallic Hg(II)-mediated base pair reported to date. The formation of the Hg(II)-mediated base pairs was investigated by means of temperature-dependent UV spectroscopy and CD spectroscopy. Graphic abstractKeywords Nucleic acid · Metal-mediated base pair · Phenanthroline · Mercury

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“…[2] In this context, alternative base-pairing patterns were devised to introduce av ariety of functional entities into the DNAs caffold. [4] Here,the nucleobases are held together by coordinate bonds to metal ions in the center of the helix, formally replacing the canonical base pairs.B oth natural nucleosides and artificial nucleosides are capable of engaging in metal-mediated base pairing. [4] Here,the nucleobases are held together by coordinate bonds to metal ions in the center of the helix, formally replacing the canonical base pairs.B oth natural nucleosides and artificial nucleosides are capable of engaging in metal-mediated base pairing.…”

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confidence: 99%

“…[3] Since the 1960s,m etal-mediated base pairing has been one of the well-established methods for the introduction of metalbased functionality into nucleic acids. [4] Here,the nucleobases are held together by coordinate bonds to metal ions in the center of the helix, formally replacing the canonical base pairs.B oth natural nucleosides and artificial nucleosides are capable of engaging in metal-mediated base pairing. [5] Even organometallic metal-mediated base pairs are known.…”

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Stable Copper(I)‐Mediated Base Pairing in DNA

Jash

Müller

2018

Angew Chem Int Ed

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A GNA (glycol nucleic acid) functionalized nucleoside analogue containing the artificial nucleobase 1H-imidazo[4,5-f][1,10]phenanthroline (P) was used to form a copper(I)-mediated base pair within a DNA duplex. The geometrical constraints imposed by the artificial nucleobase play a pivotal role in this unprecedented stabilization of copper(I) in aqueous medium via metal-mediated base pairing. The formation of the copper(I)-mediated base pair was investigated by temperature-dependent UV spectroscopy and CD spectroscopy. The metal-mediated base pair stabilizes the DNA oligonucleotide duplex by 23 °C. A redox chemistry approach confirmed that this base pair formation was due to the incorporation of copper(I) into the duplex. This first report of a copper(I)-mediated base pair adds metal-based diversity to the field and consequently opens up the range of possible applications of metal-modified nucleic acids.

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Artificial DNA Base Pairing Mediated by Diverse Metal Ions

Cited by 137 publications

References 106 publications

Metal‐Modified Nucleic Acids: Metal‐Mediated Base Pairs, Triples, and Tetrads

Metal‐Modified Nucleic Acids: Metal‐Mediated Base Pairs, Triples, and Tetrads

Stable Hg(II)-mediated base pairs with a phenanthroline-derived nucleobase surrogate in antiparallel-stranded DNA

Stable Copper(I)‐Mediated Base Pairing in DNA

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