2026-09-18T21:24:05Zhttps://ecommons.cornell.edu/server/oai/request

oai:ecommons.cornell.edu:1813/342572026-05-14T13:53:40Zcom_1813_35col_1813_47

Mann, Jason Dichtel, William Robert Coates, Geoffrey Abruna, Hector D 2013-09-16T16:42:46Z 2018-08-20T06:00:40Z 2013-08-19 https://hdl.handle.net/1813/34257 8267213 Graphene is a newly available conductive material ideally suited for forming well-defined interfaces with electroactive compounds. Aromatic moieties typically interact with the graphene surface to maximize Van der Waals interactions, predisposing most compounds to lie flat on its basal plane. A tripodal motif binds multivalently to graphene through three pyrene moieties and projects easily varied functionality away from the surface. The thermodynamic and kinetic binding parameters of a tripod bearing a redox-active Co(II) bisterpyridyl complex were investigated electrochemically. The complex binds strongly to graphene and forms monolayers with a molecular footprint of 2.3 nm2 and a [DELTA]Gads = -38.8 ± 0.2 kJ mol-1. Its monolayers are stable in fresh electrolyte for more than 12 h and desorb from graphene 1000 times more slowly than model compounds bearing a single aromatic binding group. Tripods with naphthalene or phenanthrene moieties also desorb more rapidly than those with pyrene, but reach greater monolayer densities. Noncovalent functionalization also allows assembled functionality to behave dynamically on the surface, afeature not observed in conventional self assembled monolayers. In addition, while biomacromolecuels adsorbed on bare graphene can lose their function, tripods bearing N-hydroxy succinimidyl ester groups immobilize both antibodies and Concanavalin A without loss of function. This result represents an important step forward in the design of flexible biosensors and provides a modular method for engineering the surface chemistry of graphene for biological applications. en_US Synthesis self-assembly organic coordination biosensor analytical QCM electrochemistry noncovalent graphene Noncovalent Functionalization Of Graphene dissertation or thesis application/pdf Chemistry and Chemical Biology Cornell University Doctor of Philosophy Ph. D., Chemistry and Chemical Biology Publication Cornell Theses and Dissertations Mann, Jason 5893a6ea-7af3-41d7-abc6-04bcd26ab5df open.access open.access <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="05877ebd-5262-49f5-aca3-3dc4d19e0c8a"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>en_US</Language> <Title>Noncovalent Functionalization Of Graphene</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2013-08-19</PublicationDate> <Authors> <Author> <DisplayName>Mann, Jason</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <OrgUnit /> </Publisher> </Publishers> <Keyword>Synthesis</Keyword> <Keyword>self-assembly</Keyword> <Keyword>organic</Keyword> <Keyword>coordination</Keyword> <Keyword>biosensor</Keyword> <Keyword>analytical</Keyword> <Keyword>QCM</Keyword> <Keyword>electrochemistry</Keyword> <Keyword>noncovalent</Keyword> <Keyword>graphene</Keyword> <Abstract>Graphene is a newly available conductive material ideally suited for forming well-defined interfaces with electroactive compounds. Aromatic moieties typically interact with the graphene surface to maximize Van der Waals interactions, predisposing most compounds to lie flat on its basal plane. A tripodal motif binds multivalently to graphene through three pyrene moieties and projects easily varied functionality away from the surface. The thermodynamic and kinetic binding parameters of a tripod bearing a redox-active Co(II) bisterpyridyl complex were investigated electrochemically. The complex binds strongly to graphene and forms monolayers with a molecular footprint of 2.3 nm2 and a [DELTA]Gads = -38.8 ± 0.2 kJ mol-1. Its monolayers are stable in fresh electrolyte for more than 12 h and desorb from graphene 1000 times more slowly than model compounds bearing a single aromatic binding group. Tripods with naphthalene or phenanthrene moieties also desorb more rapidly than those with pyrene, but reach greater monolayer densities. Noncovalent functionalization also allows assembled functionality to behave dynamically on the surface, afeature not observed in conventional self assembled monolayers. In addition, while biomacromolecuels adsorbed on bare graphene can lose their function, tripods bearing N-hydroxy succinimidyl ester groups immobilize both antibodies and Concanavalin A without loss of function. This result represents an important step forward in the design of flexible biosensors and provides a modular method for engineering the surface chemistry of graphene for biological applications.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>