Metal–Salen‐Base‐Pair Complexes Inside DNA: Complexation Overrides Sequence Information

Clever, Guido H.; Söltl, Yvonne; Burks, Heather E.; Spahl, W.; Carell, Thomas

doi:10.1002/chem.200600558

Cited by 109 publications

(56 citation statements)

References 80 publications

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“…From these results we can conclude that the Pz-base binds preferentially to Cu(II) followed by Mn(III), in a similar way to what is observed for the salen ligandoside. [18][19][20] The 1 : 1 ratio of duplex X1/Y1-Cu(II) of the structure was confirmed by UV titration (Fig. 2B).…”

mentioning

confidence: 65%

Synthesis and properties of a Cu(ii) complexing pyrazole ligandoside in DNA

Tomás‐Gamasa

Serdjukow

et al. 2014

Chem. Commun.

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The development of metal base pairs is of immense importance for the construction of DNA nanostructures. Here we report the synthesis of a biaryl pyrazole-phenol nucleoside that forms in DNA a stable self-pair upon complexation of a Cu(II) ion. A sequence with five consecutive pyrazole nucleotides allows the complexation of five Cu(II) ions in a row.We are currently experiencing the increased use of DNA strands for the defined construction of two and three dimensional nanoobjects. 1-3 Nowadays DNA nanoconstructions allow not only the assembly of nanoobjects with complex shapes, but also of nanosystems that feature new unusual functions. [4][5][6] Examples include the decoration of DNA structures with catalytically competent or sensoring proteins, 7-9 and the construction of cage-like DNA nanoobjects for the encapsulation of cargo that is released by a defined outside stimulus. 10 Currently it is of interest to create DNA nanostructures that exhibit novel electronic and magnetic properties. This would allow the controlled assembly of nanomagnets or electronically switchable devices. Taking advantage of the interesting electronic and magnetic properties of the metal ions with unpaired electrons, research has focused on the design of metal complexing ligandosides capable of complexing such metal ions in the DNA duplex. 11 Alternatively, the incorporation of metal ions into DNA might allow the design of new catalytically competent nanosystems at the boundary between homogenous and heterogenous catalysis. 12 Fig. 1 shows the ligandosides 1-3, which were so far designed for the stable incorporation of Cu(II) ions into the duplex. [13][14][15] Here we report the preparation of a new Cu(II) complexing ligandoside 4, and its easy incorporation into the DNA duplex by using standard phosphoramidite chemistry. With this new biaryl-type ligandoside the system is able to accomodate five Cu(II) ions on top of each other within the duplex.The straightforward synthesis is depicted in Scheme 1A. The starting point is 2-amino-5-bromo-anisole (5) which was, after nitrosation, converted to the pyrazole 6 by generation of the diazonium salt. Deprotection of the methoxy group to the phenol derivative 7 followed by silyl protection provided the key intermediate 8 in 58% overall yield. Cuprate based coupling of 8 with the toluoylprotected a-2 0 -deoxyribosylchloride 9 16 led to the b-configured nucleoside 10 in 53% yield. 17 Saponification of the sugar ester groups in methanol to give 11 was followed by 5 0 -DMT protection (compound 12) and generation of the desired phosphoramidite 13 using standard procedures. To unambiguously determine the geometry of the ligandoside, compound 11 was deprotected, crystallized and the crystal structure of the resulting compound 14 was solved.In order to learn more about the complexing behaviour we next synthesized the ligandoside 17 in which the phenolic hydroxyl group is permanently blocked (Scheme 1B). To this end the TIPS and toluoyl-protected intermediate 10 was selectively TIPS-deprotected (compou...

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confidence: 65%

Synthesis and properties of a Cu(ii) complexing pyrazole ligandoside in DNA

Tomás‐Gamasa

Serdjukow

et al. 2014

Chem. Commun.

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“…64,7982 Two Sal nucleosides were covalently crosslinked with ethylenediamine (en) and the resulting salen ligand coordinated to the Cu 2+ ions under basic conditions. The structure of the SalCu II (en)Sal base pair was confirmed by X-ray crystallography of a monomeric Cu(II) complex 79 as well as a DNA duplex containing a single metallobase pair. 80 The melting temperature of a DNA duplex, d(5¤-CAC ATT ASalT GTT GTA-3¤)¢d(3¤-GTG TAA TSalA CAA CAT-5¤), containing two salicylic aldehyde-bearing nucleosides (Sal) at a complementary position, was 39.9°C in the absence of Cu 2+ ions.…”

Section: Cu(ii)-mediated Base Pairingmentioning

confidence: 93%

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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“…[77] Die beiden Metall-Basenpaare PyA-PyA (17) ). [80] Es wurde gezeigt, dass der Assemblierungsprozess kooperativ abläuft. Zuerst wird das Diamin zur reversiblen Bildung des Salens benötigt, während das koordinierte Metall im Anschluss die Hydrolyse des gebildeten Imins in Wasser verhindert.…”

Section: Von 22'-bipyridin Abgeleitete Metall-basenpaareunclassified

“…In der Tat können viele DNA-Doppelstränge, die Metall-Salen-Komplexe enthalten, durch Chromatographie gereinigt werden, ohne zu Einzelsträngen zu denaturieren. [80] 3.6. Stapeln von Metallen mit dem Salen-Basenpaar Die überdurchschnittliche Doppelstrang-Stabilität, die man durch das Metall-Salen-Basenpaar erhält, wurde in weiteren Studien genutzt, um einen Stapel aus zehn Metallionen innerhalb des DNA-Doppelstrangs zu erzeugen (Abbildung 11 a).…”

Section: Von 22'-bipyridin Abgeleitete Metall-basenpaareunclassified

DNA‐Metall‐Basenpaare

Clever¹,

Kaul²,

Carell³

2007

Angewandte Chemie

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160

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Neuere Entwicklungen, die darauf abzielen, DNA als funktionelles Baumaterial für Nanoobjekte zu verwenden, zeigen vielversprechende Ergebnisse. In der Vergangenheit wurden molekulare DNA‐Nanoarchitekturen aus unmodifizierten oder bestenfalls endgruppenmodifizierten Oligonucleotiden aufgebaut, sodass derzeit die Entwicklung von funktionalisierten DNA‐Strukturen im Rampenlicht der Forschung steht. Eine der neuesten Entwicklungen in diese Richtung ist der Austausch der kanonischen Watson‐Crick‐Basenpaare durch Metallkomplexe zur Erzeugung von Metall‐Basenpaaren, die DNA‐Nanostrukturen magnetische oder elektrisch leitende Eigenschaften verleihen könnten. Dieser Kurzaufsatz fasst die Forschung auf diesem Gebiet zusammen, die vor fast 45 Jahren mit der Untersuchung der Interaktion von Metallen mit unmodifizierter DNA begann und nun ihren Höhepunkt in der Synthese künstlicher, ligandenähnlicher Nucleobasen findet, die bereits imstande sind, bis zu zehn Metallionen innerhalb eines einzelnen DNA‐Doppelstrangs programmierbar zu koordinieren.

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Metal–Salen‐Base‐Pair Complexes Inside DNA: Complexation Overrides Sequence Information

Cited by 109 publications

References 80 publications

Synthesis and properties of a Cu(ii) complexing pyrazole ligandoside in DNA

Synthesis and properties of a Cu(ii) complexing pyrazole ligandoside in DNA

Artificial DNA Base Pairing Mediated by Diverse Metal Ions

DNA‐Metall‐Basenpaare

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