Self‐Assembly of Cyclic Metal–DNA Nanostructures using Ruthenium Tris(bipyridine)‐Branched Oligonucleotides

Mitra, Debbie; Cesare, Nicolas Di; Sleiman, Hanadi F.

doi:10.1002/ange.200460255

Cited by 31 publications

(29 citation statements)

References 36 publications

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“…[1,2] In contrast, the incorporation of transition metals into the vertices of DNA nanostructures is much less explored. [3] This is despite the tremendous potential of metals to influence both the function of DNA nanostructures, through their redox, photophysical, magnetic, and catalytic properties, as well as the structure of DNA nanoassemblies, through the plethora of geometries and coordination numbers available to them. [3][4][5][6][7][8][9] The development of metal-DNA nanostructures is currently hampered by the need to use metals that are kinetically inert, resist the harsh conditions of oligonucleotide solid-phase synthesis, and do not preferentially bind or react with the DNA bases or phosphate backbone.…”

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confidence: 99%

“…[3] This is despite the tremendous potential of metals to influence both the function of DNA nanostructures, through their redox, photophysical, magnetic, and catalytic properties, as well as the structure of DNA nanoassemblies, through the plethora of geometries and coordination numbers available to them. [3][4][5][6][7][8][9] The development of metal-DNA nanostructures is currently hampered by the need to use metals that are kinetically inert, resist the harsh conditions of oligonucleotide solid-phase synthesis, and do not preferentially bind or react with the DNA bases or phosphate backbone.[3] Furthermore, the limited examples of metal-DNA nanostructures have contained metal centers separated by DNA double strands, which reduces metal-metal interactions.[3] In order to harness the potential of transition metals as functional corner units in DNA assembly, a more systematic approach that bypasses these limitations is necessary.Herein, we present a template approach that allows for the incorporation of normally labile metal centers, such as copper(I), copper(II), and silver(I), into DNA branch points (Scheme 1 a). Remarkably high structural stability and chirality transfer to the metal complex are demonstrated.…”

mentioning

confidence: 99%

“…[3][4][5][6][7][8][9] The development of metal-DNA nanostructures is currently hampered by the need to use metals that are kinetically inert, resist the harsh conditions of oligonucleotide solid-phase synthesis, and do not preferentially bind or react with the DNA bases or phosphate backbone. [3] Furthermore, the limited examples of metal-DNA nanostructures have contained metal centers separated by DNA double strands, which reduces metal-metal interactions. [3] In order to harness the potential of transition metals as functional corner units in DNA assembly, a more systematic approach that bypasses these limitations is necessary.…”

mentioning

confidence: 99%

“…[3] Furthermore, the limited examples of metal-DNA nanostructures have contained metal centers separated by DNA double strands, which reduces metal-metal interactions. [3] In order to harness the potential of transition metals as functional corner units in DNA assembly, a more systematic approach that bypasses these limitations is necessary.…”

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confidence: 99%

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Templated Synthesis of Highly Stable, Electroactive, and Dynamic Metal–DNA Branched Junctions

Yang

Sleiman

2008

Angew Chem Int Ed

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DNA has recently emerged as a promising template to create nanostructures with precisely programmed features.[1] Typical approaches involve the assembly of branched units containing unmodified oligonucleotides. [1,2] In contrast, the incorporation of transition metals into the vertices of DNA nanostructures is much less explored. [3] This is despite the tremendous potential of metals to influence both the function of DNA nanostructures, through their redox, photophysical, magnetic, and catalytic properties, as well as the structure of DNA nanoassemblies, through the plethora of geometries and coordination numbers available to them. [3][4][5][6][7][8][9] The development of metal-DNA nanostructures is currently hampered by the need to use metals that are kinetically inert, resist the harsh conditions of oligonucleotide solid-phase synthesis, and do not preferentially bind or react with the DNA bases or phosphate backbone.[3] Furthermore, the limited examples of metal-DNA nanostructures have contained metal centers separated by DNA double strands, which reduces metal-metal interactions.[3] In order to harness the potential of transition metals as functional corner units in DNA assembly, a more systematic approach that bypasses these limitations is necessary.Herein, we present a template approach that allows for the incorporation of normally labile metal centers, such as copper(I), copper(II), and silver(I), into DNA branch points (Scheme 1 a). Remarkably high structural stability and chirality transfer to the metal complex are demonstrated. Moreover, we have used this approach to generate the first example of a dynamic multimetallic metal-DNA assembly, with three metal complexes as the corners, single-stranded DNA as the sides, and multiple DNA double strands at the periphery (Scheme 1 d). We demonstrate quantitative and reversible structural switching of these metal-DNA nanostructures by adding specific DNA strands, resulting in controlled modulation of the metal-metal distances. This contribution thus allows the programmable generation of structurally dynamic multimetallic metal-DNA assemblies, with anticipated applications in nanoelectronics, nanooptics, artificial photosynthesis, high-density data storage, and catalysis.To create stable and electroactive metal-DNA junctions, we examined the attachment of the ligand bis(2,9-diphenyl)-1,10-phenanthroline (dpp) to DNA (Scheme 1 a). This ligand has been used by the groups of Sauvage and others to generate interwoven structures.[10] It forms complexes such as [Cu(dpp) 2 ] + , whose redox potential falls within the compatible window for DNA bases (+ 0.8 to À0.7 V vs. saturated calomel electrode, SCE), [11] and evidence of partial intercalation of these complexes into DNA has been provided.[12] An ethylene glycol substituted, monotritylated phosphoramidite derivative of dpp was thus synthesized (Scheme 1 b, dpp vertex). [13,15] The resulting molecule can be incorporated at any position of a DNA strand using standard solid-phase DNA synthesis, allowing for in-strand com...

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Templated Synthesis of Highly Stable, Electroactive, and Dynamic Metal–DNA Branched Junctions

Yang

Sleiman

2008

Angew Chem Int Ed

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“…[19] Ein Beispiel für die Verwendung dieser Verbindungen beschrieben Han et al, die komplexe Nanostrukturen aus DNA-Einzelsträngen mit am Ende angehängten Terpyridin-Einheiten über stabile Bis(terpyridin)eisen(II)-Komplexe aufbauten. [20] [27,28] Werden die über Wasserstoffbrücken zusammengehaltenen Watson-Crick-Basenpaare durch Metall-Ligand-Wechselwirkungen im Innern der Doppelhelix ersetzt, wird ein "Metall-Basenpaar" gebildet. Bestimmte Metallionen kön-nen entweder durch ein Paar natürlicher Nucleobasen oder durch speziell entwickelte Ligand-Nucleoside, die in der Doppelhelix gegenübergestellt werden, koordiniert werden.…”

Section: Introductionunclassified

DNA‐Metall‐Basenpaare

Clever¹,

Kaul²,

Carell³

2007

Angewandte Chemie

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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Sequential Self‐Assembly of a DNA Hexagon as a Template for the Organization of Gold Nanoparticles

Aldaye

Sleiman

2006

Angewandte Chemie

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Self‐Assembly of Cyclic Metal–DNA Nanostructures using Ruthenium Tris(bipyridine)‐Branched Oligonucleotides

Cited by 31 publications

References 36 publications

Templated Synthesis of Highly Stable, Electroactive, and Dynamic Metal–DNA Branched Junctions

Templated Synthesis of Highly Stable, Electroactive, and Dynamic Metal–DNA Branched Junctions

DNA‐Metall‐Basenpaare

Sequential Self‐Assembly of a DNA Hexagon as a Template for the Organization of Gold Nanoparticles

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