title: Anionic fullerenes, calixarenes, coronenes, and pyrenes as activators of oligo/polyarginines in model membranes and live cells.
abstract: We report that the efflux of 5(6)-carboxyfluorescein anions from neutral egg yolk phosphatidylcholine vesicles is mediated by oligo/polyarginines only in the presence of activating amphiphilic anions. Screening of anion activators reveals best synergism for amphiphilic carboxylates (fullerene > calix[4]arene approximately coronene > pyrene > calix[6]arene > alkyl), whereas amphiphilic sulfates show less satisfactory activation despite often lower effective concentrations. The analogous alcohols and one calix[4]arene diphosphate were inactive. These results are discussed in the context of a tentative anion carrier mechanism, where interactions with bilayer (interface-directed translocation) and carrier (arene-templated carboxylate-guanidinium pairing) contribute to activator efficiencies. Applied to HeLa cells, pyrenebutyrate is shown to significantly increase the uptake of a fluorescently labeled octaarginine in a concentration-dependent manner.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland, Institute for Chemical Research, Kyoto University and PRESTO, JST, Kyoto, Japan.
authors.forename: Florent
authors.initials: F
authors.lastname: Perret
authors.forename: Masamichi
authors.initials: M
authors.lastname: Nishihara
authors.forename: Toshihide
authors.initials: T
authors.lastname: Takeuchi
authors.forename: Shiroh
authors.initials: S
authors.lastname: Futaki
authors.forename: Adina N
authors.initials: AN
authors.lastname: Lazar
authors.forename: Anthony W
authors.initials: AW
authors.lastname: Coleman
authors.forename: Naomi
authors.initials: N
authors.lastname: Sakai
authors.forename: Stefan
authors.initials: S
authors.lastname: Matile
mesh_terms: D000838:Anions; D047250:Calixarenes / Q000737:chemistry / Q000493:pharmacokinetics*; D002462:Cell Membrane / Q000737:chemistry / Q000378:metabolism; D004337:Drug Carriers / Q000737:chemistry / Q000493:pharmacokinetics*; D037741:Fullerenes / Q000737:chemistry / Q000493:pharmacokinetics*; D006367:HeLa Cells; D006801:Humans; D008567:Membranes, Artificial; D010455:Peptides / Q000737:chemistry / Q000493:pharmacokinetics*; D010715:Phosphatidylglycerols / Q000737:chemistry; D011083:Polycyclic Compounds / Q000737:chemistry / Q000493:pharmacokinetics*; D011721:Pyrenes / Q000737:chemistry / Q000493:pharmacokinetics*
chemical_list: D000838:Anions; D004337:Drug Carriers; D037741:Fullerenes; D008567:Membranes, Artificial; D010455:Peptides; D010715:Phosphatidylglycerols; D011083:Polycyclic Compounds; D011721:Pyrenes; D047250:Calixarenes; C015462:polyarginine; C012256:coronene