Model dyads for 2PA uncaging of a protecting group via photoinduced electron transfer.

Three dyads with a fluorene derivative as an electron-donor and with electron-acceptors of variable redox potentials were synthesized as models for two-photon activated uncaging via electron transfer. A spectroscopic and photophysical study of the component units and the dyads in solvents of different polarities demonstrated an efficient electron transfer (efficiencies > 80%) followed by charge recombination in the arrays (30 ps < τ < 1.6 ns). Recombination takes place to the ground state in all cases except for the dyad displaying the highest driving force for charge recombination in the apolar solvent. The effects of changing the solvent polarity, as well as the driving force, for electron-transfer are discussed in the frame of the current theories of electron transfer.

[1]  H. Kasai,et al.  Caged glutamates with π-extended 1,2-dihydronaphthalene chromophore: design, synthesis, two-photon absorption property, and photochemical reactivity. , 2014, The Journal of organic chemistry.

[2]  G. Ellis‐Davies,et al.  Wavelength-selective one- and two-photon uncaging of GABA. , 2014, ACS chemical neuroscience.

[3]  C. Katan,et al.  Synthesis and photochemical reactivity of caged glutamates with a π-extended coumarin chromophore as a photolabile protecting group , 2013 .

[4]  M. Blanchard‐Desce,et al.  Octupolar chimeric compounds built from quinoline caged acetate moieties: a novel approach for 2-photon uncaging of biomolecules , 2013 .

[5]  D. Ogden,et al.  Tandem triad systems based on FRET for two-photon induced release of glutamate. , 2013, Chemical communications.

[6]  David Ogden,et al.  From one-photon to two-photon probes: "caged" compounds, actuators, and photoswitches. , 2013, Angewandte Chemie.

[7]  G. Ellis‐Davies,et al.  Optically selective two-photon uncaging of glutamate at 900 nm. , 2013, Journal of the American Chemical Society.

[8]  Graham CR Ellis-Davies,et al.  A chemist and biologist talk to each other about caged neurotransmitters , 2013, Beilstein journal of organic chemistry.

[9]  R. Givens,et al.  Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy , 2012, Chemical reviews.

[10]  D. Ogden,et al.  Substitution effect on the one- and two-photon sensitivity of DMAQ "caging" groups. , 2012, Organic letters.

[11]  A. Heckel,et al.  Light-controlled tools. , 2012, Angewandte Chemie.

[12]  A. Losonczy,et al.  Two-photon uncaging: The chemist point of view , 2012 .

[13]  Sébastien Charon,et al.  The donor–acceptor biphenyl platform: A versatile chromophore for the engineering of highly efficient two-photon sensitive photoremovable protecting groups , 2012, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[14]  C. M. Davenport,et al.  Water-soluble, donor-acceptor biphenyl derivatives in the 2-(o-nitrophenyl)propyl series: highly efficient two-photon uncaging of the neurotransmitter γ-aminobutyric acid at λ = 800 nm. , 2012, Angewandte Chemie.

[15]  Linyong Zhu,et al.  Styryl conjugated coumarin caged alcohol: efficient photorelease by either one-photon long wavelength or two-photon NIR excitation. , 2012, Organic letters.

[16]  G. Ellis‐Davies,et al.  In vivo two‐photon uncaging of glutamate revealing the structure–function relationships of dendritic spines in the neocortex of adult mice , 2011, The Journal of physiology.

[17]  G. Ellis‐Davies Two-photon microscopy for chemical neuroscience. , 2011, ACS chemical neuroscience.

[18]  A. Mourot,et al.  Two-photon uncaging: New prospects in neuroscience and cellular biology. , 2010, Bioorganic & medicinal chemistry.

[19]  M. Pirrung,et al.  Sensitized two-photon photochemical deprotection. , 2010, Chemical communications.

[20]  Rafael Yuste,et al.  A fast ruthenium polypyridine cage complex photoreleases glutamate with visible or IR light in one and two photon regimes. , 2010, Journal of inorganic biochemistry.

[21]  G. Ellis‐Davies,et al.  Two-photon uncaging of gamma-aminobutyric acid in intact brain tissue. , 2010, Nature chemical biology.

[22]  G. Ellis‐Davies,et al.  Two-color, two-photon uncaging of glutamate and GABA , 2010, Nature Methods.

[23]  Jinbo Li,et al.  Chemistry and biological applications of photo-labile organic molecules. , 2010, Chemical Society reviews.

[24]  Rafael Yuste,et al.  RuBi-Glutamate: Two-Photon and Visible-Light Photoactivation of Neurons and Dendritic spines , 2009, Front. Neural Circuits.

[25]  Hazel A. Collins,et al.  Two-photon absorption and the design of two-photon dyes. , 2009, Angewandte Chemie.

[26]  T. M. Dore,et al.  Substituent effects on the sensitivity of a quinoline photoremovable protecting group to one- and two-photon excitation. , 2009, The Journal of organic chemistry.

[27]  J. Nicoud,et al.  Molecular engineering of photoremovable protecting groups for two-photon uncaging. , 2008, Angewandte Chemie.

[28]  Rafael Yuste,et al.  Photorelease of GABA with Visible Light Using an Inorganic Caging Group , 2008, Frontiers in neural circuits.

[29]  D. Ogden,et al.  Photolabile Glutamate Protecting Group with High One‐ and Two‐Photon Uncaging Efficiencies , 2008, Chembiochem : a European journal of chemical biology.

[30]  G. Miesenböck,et al.  Photocontrol of neural activity: biophysical mechanisms and performance in vivo. , 2008, Chemical reviews.

[31]  D. Ogden,et al.  An antenna-sensitised 1-acyl-7-nitroindoline that has good solubility properties in the presence of calcium ions and is suitable for use as a caged l-glutamate in neuroscience , 2008, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[32]  P. Neveu,et al.  Two-photon uncaging with fluorescence reporting: evaluation of the o-hydroxycinnamic platform. , 2007, Journal of the American Chemical Society.

[33]  Haruo Kasai,et al.  4-Carboxymethoxy-5,7-Dinitroindolinyl-Glu: An Improved Caged Glutamate for Expeditious Ultraviolet and Two-Photon Photolysis in Brain Slices , 2007, The Journal of Neuroscience.

[34]  P. Neveu,et al.  Two-photon uncaging with the efficient 3,5-dibromo-2,4-dihydroxycinnamic caging group. , 2007, Angewandte Chemie.

[35]  D. Gryko,et al.  Photoinduced energy and electron transfer in 1,8-naphthalimide–corrole dyads , 2007 .

[36]  Claudine Katan,et al.  Synthesis, fluorescence, and two-photon absorption of a series of elongated rodlike and banana-shaped quadrupolar fluorophores: a comprehensive study of structure-property relationships. , 2007, Chemistry.

[37]  John R. Miller,et al.  Nature and energies of electrons and holes in a conjugated polymer, polyfluorene. , 2006, Journal of the American Chemical Society.

[38]  D. Ogden,et al.  New Photoremovable Protecting Groups for Carboxylic Acids with High Photolytic Efficiencies at Near‐UV Irradiation. Application to the Photocontrolled Release of L‐Glutamate , 2006, Chembiochem : a European journal of chemical biology.

[39]  P. Neveu,et al.  o-nitrobenzyl photolabile protecting groups with red-shifted absorption: syntheses and uncaging cross-sections for one- and two-photon excitation. , 2006, Chemistry.

[40]  Günter Mayer,et al.  Biologically active molecules with a "light switch". , 2006, Angewandte Chemie.

[41]  U. Steiner,et al.  Highly efficient photolabile protecting groups with intramolecular energy transfer. , 2006, Angewandte Chemie.

[42]  Christopher M. Pavlos,et al.  8-Bromo-7-hydroxyquinoline as a photoremovable protecting group for physiological use: mechanism and scope. , 2006, Journal of the American Chemical Society.

[43]  Dirk Trauner,et al.  Photochemical tools for remote control of ion channels in excitable cells , 2005, Nature chemical biology.

[44]  G. Ellis‐Davies,et al.  Synthesis of a caged glutamate for efficient one- and two-photon photorelease on living cells. , 2005, Chemical communications.

[45]  D. Falvey,et al.  Photolytic release of carboxylic acids using linked donor-acceptor molecules: direct versus mediated photoinduced electron transfer to N-alkyl-4-picolinium esters. , 2005, Organic letters.

[46]  R. Yuste,et al.  Two-photon uncaging of neurochemicals using inorganic metal complexes. , 2005, Chemical communications.

[47]  D. Ogden,et al.  An antenna-sensitized nitroindoline precursor to enable photorelease of L-glutamate in high concentrations. , 2004, The Journal of organic chemistry.

[48]  D. Falvey,et al.  Photoremovable protecting groups based on electron transfer chemistry , 2004, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[49]  D. Falvey,et al.  C-O bond fragmentation of 4-picolyl- and N-methyl-4-picolinium esters triggered by photochemical electron transfer. , 2004, The Journal of organic chemistry.

[50]  A. Osuka,et al.  Ultrafast charge separation from the S2 excited state of directly linked porphyrin - Imide dyads: First unequivocal observation of the whole bell-shaped energy-gap law and its solvent dependencies , 2002 .

[51]  Jakob Wirz,et al.  Photoremovable protecting groups: reaction mechanisms and applications , 2002, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[52]  G. Marconi,et al.  Switching of electron- to energy-transfer by selective excitation of different chromophores in arrays based on porphyrins and a polypyridyl iridium complex , 2002 .

[53]  D. Piston,et al.  The efficiency of two-photon photolysis of a "caged" fluorophore, o-1-(2-nitrophenyl)ethylpyranine, in relation to photodamage of synaptic terminals , 2002, European Biophysics Journal.

[54]  Yasushi Miyashita,et al.  Dendritic spine geometry is critical for AMPA receptor expression in hippocampal CA1 pyramidal neurons , 2001, Nature Neuroscience.

[55]  I. Dixon,et al.  Porphyrinic dyads and triads assembled around iridium(III) bis-terpyridine: photoinduced electron transfer processes. , 2001, Inorganic chemistry.

[56]  D. Falvey,et al.  Photochemically Removable Protecting Groups Based on Covalently Linked Electron Donor−Acceptor Systems , 2000 .

[57]  E M Callaway,et al.  Brominated 7-hydroxycoumarin-4-ylmethyls: photolabile protecting groups with biologically useful cross-sections for two photon photolysis. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[58]  A. Banerjee,et al.  Direct Photolysis of Phenacyl Protecting Groups Studied by Laser Flash Photolysis: An Excited State Hydrogen Atom Abstraction Pathway Leads to Formation of Carboxylic Acids and Acetophenone , 1998 .

[59]  A. Moore,et al.  Photoinduced Charge Separation and Charge Recombination to a Triplet State in a Carotene−Porphyrin−Fullerene Triad , 1997 .

[60]  S. Greenfield,et al.  Multistep Photochemical Charge Separation in Rod-like Molecules Based on Aromatic Imides and Diimides , 1996 .

[61]  Rudolph A. Marcus,et al.  Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture) , 1993 .

[62]  N. Mathivanan,et al.  Laser flash photolysis of 9-fluorenol. Production and reactivities of the 9-fluorenol radical cation and the 9-fluorenyl cation , 1990 .

[63]  D. F. Eaton,et al.  International Union of Pure and Applied Chemistry Organic Chemistry Division Commission on Photochemistry. Reference materials for fluorescence measurement. , 1988, Journal of photochemistry and photobiology. B, Biology.

[64]  M. Delcourt,et al.  Photoionization of unsaturated hydrocarbons at 249 nm in acetonitrile. Visible absorption spectra of radical cations , 1982 .

[65]  R. Sioda,et al.  Application of the flow electrolytic method to the study of optical absorption spectra of the radical anions of nitrobenzene, p-nitrotoluene and anthraquinone , 1971 .

[66]  D. Gryko,et al.  New and efficient arrays for photoinduced charge separation based on perylene bisimide and corroles. , 2008, Chemistry.

[67]  F. Würthner,et al.  Photophysical Characterization of a Light-Harvesting Tetra Naphthalene Imide/Perylene Bisimide Array , 2007 .

[68]  A. Weller Photoinduced Electron Transfer in Solution: Exciplex and Radical Ion Pair Formation Free Enthalpies and their Solvent Dependence , 1982 .

[69]  Steven L. Murov,et al.  Handbook of photochemistry , 1973 .