title: Screening of pi-basic naphthalene and anthracene amplifiers for pi-acidic synthetic pore sensors.
abstract: Synthetic ion channels and pores attract current attention as multicomponent sensors in complex matrixes. This application requires the availability of reactive signal amplifiers that covalently capture analytes and drag them into the pore. pi-Basic 1,5-dialkoxynaphthalenes (1,5-DAN) are attractive amplifiers because aromatic electron donor-acceptor (AEDA) interactions account for their recognition within pi-acidic naphthalenediimide (NDI) rich synthetic pores. Focusing on amplifier design, we report here the synthesis of a complete collection of DAN and dialkoxyanthracene amplifiers, determine their oxidation potentials by cyclic voltammetry, and calculate their quadrupole moments. Blockage experiments reveal that subtle structural changes in regioisomeric DAN amplifiers can be registered within NDI pores. Frontier orbital overlap in AEDA complexes, oxidation potentials, and, to a lesser extent, quadrupole moments are shown to contribute to isomer recognition by synthetic pores. Particularly important with regard to practical applications of synthetic pores as multianalyte sensors, we further demonstrate that application of the lessons learned with DAN regioisomers to the expansion to dialkoxyanthracenes provides access to privileged amplifiers with submicromolar activity.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Shinya
authors.initials: S
authors.lastname: Hagihara
authors.forename: Ludovic
authors.initials: L
authors.lastname: Gremaud
authors.forename: Guillaume
authors.initials: G
authors.lastname: Bollot
authors.forename: Jiri
authors.initials: J
authors.lastname: Mareda
authors.forename: Stefan
authors.initials: S
authors.lastname: Matile
mesh_terms: D015081:2-Naphthylamine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D000669:Amplifiers, Electronic; D000873:Anthracenes / Q000737:chemistry*; D004566:Electrodes; D006860:Hydrogen Bonding; D007094:Imides; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D010084:Oxidation-Reduction; D010618:Phenanthrolines / Q000737:chemistry*; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D013237:Stereoisomerism
chemical_list: D000873:Anthracenes; D007094:Imides; D009281:Naphthalenes; D010618:Phenanthrolines; C510889:1,5-diaminonaphthalene; C031721:naphthalene; C542131:naphthalenediimide; D015081:2-Naphthylamine; C034020:anthracene