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Addressing the properties of "Metallo-DNA" with a Ag(i)-mediated supramolecular duplex
The silver-nucleoside complex [Ag(i)-( 3-cytidine) ], , self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-he...
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Published in: | Chemical science (Cambridge) 2019-03, Vol.10 (11), p.3186-3195 |
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creator | Mistry, Liam El-Zubir, Osama Dura, Gema Clegg, William Waddell, Paul G Pope, Thomas Hofer, Werner A Wright, Nick G Horrocks, Benjamin R Houlton, Andrew |
description | The silver-nucleoside complex [Ag(i)-(
3-cytidine)
],
, self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-helix with a continuous silver core. Electrical measurements on
show that despite having Ag···Ag distances within |
doi_str_mv | 10.1039/c8sc05103h |
format | article |
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3-cytidine)
],
, self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-helix with a continuous silver core. Electrical measurements on
show that despite having Ag···Ag distances within <5% of the metallic radii, the material is electrically insulating. This is due to the electronic structure which features a filled valence band, an empty conduction band dominated by the ligand, and a band gap of 2.5 eV. Hence, as-prepared, such Ag(i)-DNA systems should not be considered molecular nanowires but, at best, proto-wires. The structural features seen in
are essentially retained in the corresponding organogel which exhibits thixotropic self-healing that can be attributed to the reversible nature of the intermolecular interactions. Photo-reduced samples of the gel exhibit luminescence confirming that these poly-cytidine sequences appropriately pre-configure silver ions for the formation of quantum-confined metal clusters in line with contemporary views on DNA-templated clusters. Microscopy data reveals the resulting metal cluster/particles are approximately spherical and crystalline with lattice spacing (111) similar to bulk Ag.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c8sc05103h</identifier><identifier>PMID: 30996900</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Chemistry ; Conduction bands ; Crystallography ; Data analysis ; Deoxyribonucleic acid ; DNA ; Electrical measurement ; Electronic structure ; Hydrogen bonding ; Image processing ; Metal clusters ; Metallography ; Nanowires ; Silver ; Valence band</subject><ispartof>Chemical science (Cambridge), 2019-03, Vol.10 (11), p.3186-3195</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><rights>This journal is © The Royal Society of Chemistry 2019 2019</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c447t-f216d604f7d23a9dc7adc358a736a9702cff01a09b407b631d65f8a77ae531733</citedby><cites>FETCH-LOGICAL-c447t-f216d604f7d23a9dc7adc358a736a9702cff01a09b407b631d65f8a77ae531733</cites><orcidid>0000-0001-7552-9812 ; 0000-0002-2859-2509 ; 0000-0003-1643-5298 ; 0000-0001-5633-4630 ; 0000-0002-1305-4716</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC6429620/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC6429620/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,881,27903,27904,53769,53771</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30996900$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mistry, Liam</creatorcontrib><creatorcontrib>El-Zubir, Osama</creatorcontrib><creatorcontrib>Dura, Gema</creatorcontrib><creatorcontrib>Clegg, William</creatorcontrib><creatorcontrib>Waddell, Paul G</creatorcontrib><creatorcontrib>Pope, Thomas</creatorcontrib><creatorcontrib>Hofer, Werner A</creatorcontrib><creatorcontrib>Wright, Nick G</creatorcontrib><creatorcontrib>Horrocks, Benjamin R</creatorcontrib><creatorcontrib>Houlton, Andrew</creatorcontrib><title>Addressing the properties of "Metallo-DNA" with a Ag(i)-mediated supramolecular duplex</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>The silver-nucleoside complex [Ag(i)-(
3-cytidine)
],
, self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-helix with a continuous silver core. Electrical measurements on
show that despite having Ag···Ag distances within <5% of the metallic radii, the material is electrically insulating. This is due to the electronic structure which features a filled valence band, an empty conduction band dominated by the ligand, and a band gap of 2.5 eV. Hence, as-prepared, such Ag(i)-DNA systems should not be considered molecular nanowires but, at best, proto-wires. The structural features seen in
are essentially retained in the corresponding organogel which exhibits thixotropic self-healing that can be attributed to the reversible nature of the intermolecular interactions. Photo-reduced samples of the gel exhibit luminescence confirming that these poly-cytidine sequences appropriately pre-configure silver ions for the formation of quantum-confined metal clusters in line with contemporary views on DNA-templated clusters. Microscopy data reveals the resulting metal cluster/particles are approximately spherical and crystalline with lattice spacing (111) similar to bulk Ag.</description><subject>Chemistry</subject><subject>Conduction bands</subject><subject>Crystallography</subject><subject>Data analysis</subject><subject>Deoxyribonucleic acid</subject><subject>DNA</subject><subject>Electrical measurement</subject><subject>Electronic structure</subject><subject>Hydrogen bonding</subject><subject>Image processing</subject><subject>Metal clusters</subject><subject>Metallography</subject><subject>Nanowires</subject><subject>Silver</subject><subject>Valence band</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpdkUFP3DAQha0KVBBw4QcgCy60UujYTuz4grTaUqgE7aEtV8trO7tG3jjYSQv_niwLK8pcZqT59OaNHkKHBM4IMPnF1NlANY6LD2iXQkkKXjG5tZkp7KCDnO9gLMZIRcVHtMNASi4BdtHtxNrkcvbtHPcLh7sUO5d67zKODT6-cb0OIRZff0yO8T_fL7DGk_mp_1QsnfW6dxbnoUt6GYMzQ9AJ26EL7mEfbTc6ZHfw0vfQn28Xv6dXxfXPy-_TyXVhylL0RUMJtxzKRljKtLRGaGtYVWvBuJYCqGkaIBrkrAQx44xYXjXjVmhXMSIY20Pna91umI2OjGv7pIPqkl_q9Kii9ur_TesXah7_Kl5SySmMAqcvAineDy73aumzcSHo1sUhK0oJYZTXdHXr5B16F4fUju8pSiTwWrK6HqnPa8qkmHNyzcYMAbVKTE3rX9PnxK5G-Oit_Q36mg97Am3Kj_c</recordid><startdate>20190321</startdate><enddate>20190321</enddate><creator>Mistry, Liam</creator><creator>El-Zubir, Osama</creator><creator>Dura, Gema</creator><creator>Clegg, William</creator><creator>Waddell, Paul G</creator><creator>Pope, Thomas</creator><creator>Hofer, Werner A</creator><creator>Wright, Nick G</creator><creator>Horrocks, Benjamin R</creator><creator>Houlton, Andrew</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-7552-9812</orcidid><orcidid>https://orcid.org/0000-0002-2859-2509</orcidid><orcidid>https://orcid.org/0000-0003-1643-5298</orcidid><orcidid>https://orcid.org/0000-0001-5633-4630</orcidid><orcidid>https://orcid.org/0000-0002-1305-4716</orcidid></search><sort><creationdate>20190321</creationdate><title>Addressing the properties of "Metallo-DNA" with a Ag(i)-mediated supramolecular duplex</title><author>Mistry, Liam ; El-Zubir, Osama ; Dura, Gema ; Clegg, William ; Waddell, Paul G ; Pope, Thomas ; Hofer, Werner A ; Wright, Nick G ; Horrocks, Benjamin R ; Houlton, Andrew</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c447t-f216d604f7d23a9dc7adc358a736a9702cff01a09b407b631d65f8a77ae531733</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Chemistry</topic><topic>Conduction bands</topic><topic>Crystallography</topic><topic>Data analysis</topic><topic>Deoxyribonucleic acid</topic><topic>DNA</topic><topic>Electrical measurement</topic><topic>Electronic structure</topic><topic>Hydrogen bonding</topic><topic>Image processing</topic><topic>Metal clusters</topic><topic>Metallography</topic><topic>Nanowires</topic><topic>Silver</topic><topic>Valence band</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mistry, Liam</creatorcontrib><creatorcontrib>El-Zubir, Osama</creatorcontrib><creatorcontrib>Dura, Gema</creatorcontrib><creatorcontrib>Clegg, William</creatorcontrib><creatorcontrib>Waddell, Paul G</creatorcontrib><creatorcontrib>Pope, Thomas</creatorcontrib><creatorcontrib>Hofer, Werner A</creatorcontrib><creatorcontrib>Wright, Nick G</creatorcontrib><creatorcontrib>Horrocks, Benjamin R</creatorcontrib><creatorcontrib>Houlton, Andrew</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mistry, Liam</au><au>El-Zubir, Osama</au><au>Dura, Gema</au><au>Clegg, William</au><au>Waddell, Paul G</au><au>Pope, Thomas</au><au>Hofer, Werner A</au><au>Wright, Nick G</au><au>Horrocks, Benjamin R</au><au>Houlton, Andrew</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Addressing the properties of "Metallo-DNA" with a Ag(i)-mediated supramolecular duplex</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2019-03-21</date><risdate>2019</risdate><volume>10</volume><issue>11</issue><spage>3186</spage><epage>3195</epage><pages>3186-3195</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The silver-nucleoside complex [Ag(i)-(
3-cytidine)
],
, self-assembles to form a supramolecular metal-mediated base-pair array highly analogous to those seen in metallo-DNA. A combination of complementary hydrogen-bonding, hydrophobic and argentophilic interactions drive the formation of a double-helix with a continuous silver core. Electrical measurements on
show that despite having Ag···Ag distances within <5% of the metallic radii, the material is electrically insulating. This is due to the electronic structure which features a filled valence band, an empty conduction band dominated by the ligand, and a band gap of 2.5 eV. Hence, as-prepared, such Ag(i)-DNA systems should not be considered molecular nanowires but, at best, proto-wires. The structural features seen in
are essentially retained in the corresponding organogel which exhibits thixotropic self-healing that can be attributed to the reversible nature of the intermolecular interactions. Photo-reduced samples of the gel exhibit luminescence confirming that these poly-cytidine sequences appropriately pre-configure silver ions for the formation of quantum-confined metal clusters in line with contemporary views on DNA-templated clusters. Microscopy data reveals the resulting metal cluster/particles are approximately spherical and crystalline with lattice spacing (111) similar to bulk Ag.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>30996900</pmid><doi>10.1039/c8sc05103h</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0001-7552-9812</orcidid><orcidid>https://orcid.org/0000-0002-2859-2509</orcidid><orcidid>https://orcid.org/0000-0003-1643-5298</orcidid><orcidid>https://orcid.org/0000-0001-5633-4630</orcidid><orcidid>https://orcid.org/0000-0002-1305-4716</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Chemistry Conduction bands Crystallography Data analysis Deoxyribonucleic acid DNA Electrical measurement Electronic structure Hydrogen bonding Image processing Metal clusters Metallography Nanowires Silver Valence band |
title | Addressing the properties of "Metallo-DNA" with a Ag(i)-mediated supramolecular duplex |
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