Pathways for Photoinduced Charge Separation in DNA Hairpins
By means of correlated quantum-chemical calculations, we explore the chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-de...
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| Veröffentlicht in: | Journal of the American Chemical Society 2003-11, Vol.125 (47), p.14510-14517 |
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| container_issue | 47 |
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| container_title | Journal of the American Chemical Society |
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| creator | Beljonne, D Pourtois, G Ratner, M. A Brédas, J. L |
| description | By means of correlated quantum-chemical calculations, we explore the chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-defined distance along the DNA strand are identified. Importantly, these involve not only the frontier molecular orbitals of the interacting donor, bridge, and acceptor units, but also deeper lying orbitals possessing both the appropriate energy and the symmetry to overlap significantly. The relative efficiency of these channels is found to be sensitive to the chemical structure of the linker, leading to falloff parameters for the charge-transfer rates ranging from ∼0.4 to ∼1.2 Å-1. |
| doi_str_mv | 10.1021/ja035596f |
| format | Article |
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The relative efficiency of these channels is found to be sensitive to the chemical structure of the linker, leading to falloff parameters for the charge-transfer rates ranging from ∼0.4 to ∼1.2 Å-1.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja035596f</identifier><identifier>PMID: 14624600</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Biological and medical sciences ; DNA - chemistry ; Electronic structure ; Fundamental and applied biological sciences. 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A</creatorcontrib><creatorcontrib>Brédas, J. L</creatorcontrib><title>Pathways for Photoinduced Charge Separation in DNA Hairpins</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>By means of correlated quantum-chemical calculations, we explore the chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-defined distance along the DNA strand are identified. Importantly, these involve not only the frontier molecular orbitals of the interacting donor, bridge, and acceptor units, but also deeper lying orbitals possessing both the appropriate energy and the symmetry to overlap significantly. The relative efficiency of these channels is found to be sensitive to the chemical structure of the linker, leading to falloff parameters for the charge-transfer rates ranging from ∼0.4 to ∼1.2 Å-1.</description><subject>Biological and medical sciences</subject><subject>DNA - chemistry</subject><subject>Electronic structure</subject><subject>Fundamental and applied biological sciences. Psychology</subject><subject>Guanine - chemistry</subject><subject>Models, Chemical</subject><subject>Models, Molecular</subject><subject>Molecular biophysics</subject><subject>Nucleic Acid Conformation</subject><subject>Photochemistry</subject><subject>Quantum Theory</subject><subject>Static Electricity</subject><subject>Structure in molecular biology</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0E1Lw0AQBuBFFFs_Dv4ByUXBQ3S_s4unUq2KRYv2vkw3G7u1TepugvbfG2lpL56GYR5ehhehM4KvCabkZgaYCaFlsYe6RFCcCkLlPupijGmaKck66CjGWbtyqsgh6hAuKZcYd9HtCOrpN6xiUlQhGU2ruvJl3liXJ_0phA-XvLslBKh9VSa-TO5eeskj-LD0ZTxBBwXMozvdzGM0HtyP-4_p8PXhqd8bpsAyXacScmWlxhYriTVTDhwILmTOi8xyJbTOaaaU1MAky5SlzuqJdmKiNZZYsmN0uY5dhuqrcbE2Cx-tm8-hdFUTTUaY4oqyFl6toQ1VjMEVZhn8AsLKEGz-ijLbolp7vgltJguX7-SmmRZcbABEC_MiQGl93DnBCFFatS5dOx9r97O9Q_g0MmOZMOPRu9EjPn4evHDztssFG82sakLZVvfPg7-1G4ja</recordid><startdate>20031126</startdate><enddate>20031126</enddate><creator>Beljonne, D</creator><creator>Pourtois, G</creator><creator>Ratner, M. 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Psychology</topic><topic>Guanine - chemistry</topic><topic>Models, Chemical</topic><topic>Models, Molecular</topic><topic>Molecular biophysics</topic><topic>Nucleic Acid Conformation</topic><topic>Photochemistry</topic><topic>Quantum Theory</topic><topic>Static Electricity</topic><topic>Structure in molecular biology</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Beljonne, D</creatorcontrib><creatorcontrib>Pourtois, G</creatorcontrib><creatorcontrib>Ratner, M. A</creatorcontrib><creatorcontrib>Brédas, J. 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Soc</addtitle><date>2003-11-26</date><risdate>2003</risdate><volume>125</volume><issue>47</issue><spage>14510</spage><epage>14517</epage><pages>14510-14517</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>By means of correlated quantum-chemical calculations, we explore the chain-length dependence of the electronic coupling for photoinduced charge separation in DNA hairpins associated to conjugated linkers. Pathways for charge transfer from the linker chromophore to a guanine site located at a well-defined distance along the DNA strand are identified. Importantly, these involve not only the frontier molecular orbitals of the interacting donor, bridge, and acceptor units, but also deeper lying orbitals possessing both the appropriate energy and the symmetry to overlap significantly. 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| source | MEDLINE; ACS Publications |
| subjects | Biological and medical sciences DNA - chemistry Electronic structure Fundamental and applied biological sciences. Psychology Guanine - chemistry Models, Chemical Models, Molecular Molecular biophysics Nucleic Acid Conformation Photochemistry Quantum Theory Static Electricity Structure in molecular biology |
| title | Pathways for Photoinduced Charge Separation in DNA Hairpins |
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