title: Boron Difluoride Curcuminoid Fluorophores with Enhanced Two-Photon Excited Fluorescence Emission and Versatile Living-Cell Imaging Properties.
abstract: The synthesis of boron difluoride complexes of a series of curcuminoid derivatives containing various donor end groups is described. Time-dependent (TD)-DFT calculations confirm the charge-transfer character of the second lowest-energy transition band and ascribe the lowest energy band to a "cyanine-like" transition. Photophysical studies reveal that tuning the donor strength of the end groups allows covering a broad spectral range, from the visible to the NIR region, of the UV-visible absorption and fluorescence spectra. Two-photon-excited fluorescence and Z-scan techniques prove that an increase in the donor strength or in the rigidity of the backbone results in a considerable increase in the two-photon cross section, reaching 5000 GM, with predominant two-photon absorption from the S0-S2 charge-transfer transition. Direct comparisons with the hemicurcuminoid derivatives show that the two-photon active band for the curcuminoid derivatives has the same intramolecular charge-transfer character and therefore arises from a dipolar structure. Overall, this structure-relationship study allows the optimization of the two-photon brightness (i.e., 400-900 GM) with one dye that emits in the NIR region of the spectrum. In addition, these dyes demonstrate high intracellular uptake efficiency in Cos7 cells with emission in the visible region, which is further improved by using porous silica nanoparticles as dye vehicles for the imaging of two mammalian carcinoma cells type based on NIR fluorescence emission.
authors.affiliation: IFMRI, National Institute of Advanced Industrial Science and Technology, Ikeda, Osaka, 563-8577, Japan. k.kamada@aist.go.jp.|Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, Sanda, Hyogo, 669-1337, Japan. k.kamada@aist.go.jp.
authors.forename: Kenji
authors.initials: K
authors.lastname: Kamada
authors.affiliation: Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, Sanda, Hyogo, 669-1337, Japan.
authors.forename: Tomotaka
authors.initials: T
authors.lastname: Namikawa
authors.affiliation: Aix Marseille Université, CNRS, Institutde Biologie du Développement de Marseille, UMR7288, 13288, Marseille 9, France.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Senatore
authors.affiliation: Aix Marseille Université, CNRS, Institutde Biologie du Développement de Marseille, UMR7288, 13288, Marseille 9, France.
authors.forename: Cédric
authors.initials: C
authors.lastname: Matthews
authors.affiliation: Aix Marseille Université, CNRS, Institutde Biologie du Développement de Marseille, UMR7288, 13288, Marseille 9, France.
authors.forename: Pierre-François
authors.initials: PF
authors.lastname: Lenne
authors.affiliation: Université Lyon 1, ENS Lyon, CNRS, UMR 5182, 69364, Lyon, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Maury
authors.affiliation: Université Lyon 1, ENS Lyon, CNRS, UMR 5182, 69364, Lyon, France.
authors.forename: Chantal
authors.initials: C
authors.lastname: Andraud
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 263 Avenue du Général Leclerc, 35042, Rennes Cedex, France.
authors.forename: Miguel
authors.initials: M
authors.lastname: Ponce-Vargas
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 263 Avenue du Général Leclerc, 35042, Rennes Cedex, France.
authors.forename: Boris
authors.initials: B
authors.lastname: Le Guennic
authors.affiliation: Laboratoire CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322, Nantes Cedex 3, France.|Institut Universitaire de France, 1 Rue Descartes, 75005, Paris Cedex 05, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
authors.forename: Peter
authors.initials: P
authors.lastname: Agbo
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
authors.forename: Dahlia D
authors.initials: DD
authors.lastname: An
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
authors.forename: Stacey S
authors.initials: SS
authors.lastname: Gauny
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
authors.forename: Xin
authors.initials: X
authors.lastname: Liu
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA. rjabergel@lbl.gov.
authors.forename: Rebecca J
authors.initials: RJ
authors.lastname: Abergel
authors.affiliation: Aix Marseille Université, CNRS, CINaM UMR 7325, Campus de Luminy, Case 913, 13288, Marseille, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Fages
authors.affiliation: Aix Marseille Université, CNRS, CINaM UMR 7325, Campus de Luminy, Case 913, 13288, Marseille, France. daleo@cinam.univ-mrs.fr.
authors.forename: Anthony
authors.initials: A
authors.lastname: D'Aléo
mesh_terms: D000818:Animals; D001896:Boron Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003474:Curcumin / Q000138:chemical synthesis* / Q000737:chemistry*; D005453:Fluorescence; D005456:Fluorescent Dyes / Q000737:chemistry*; D007476:Ionophores / Q000737:chemistry*; D015394:Molecular Structure; D055668:Photochemical Processes; D017785:Photons; D011789:Quantum Theory; D013050:Spectrometry, Fluorescence
chemical_list: D001896:Boron Compounds; D005456:Fluorescent Dyes; D007476:Ionophores; C579460:boron difluoride; D003474:Curcumin
keywords: cell imaging; density functional calculations; dipolar dyes; photophysics; two-photon processes