Nonlinear optical chemosensor for sodium ion based on rhodol chromophore.

As part of a strategy to identify good fluorescent probes based on two-photon excited fluorescence (TPEF), the sensor for sodium cation has been designed bearing a rhodol chromophore linked with an aza-crown ether. An efficient synthetic route to rhodol derivatives possessing five-membered heterocycles at position 9 and their precursors that contain xanthylium salt has been developed. The synthesis involves condensation of xanthylium salts bearing vinamidinium moiety at position 9, with phenylhydrazine derivatives as the key step. To accomplish the synthesis of derivatives bearing 1-aza-15-crown-5 and 1,10-diaza-18-crown-6, the Buchwald-Hartwig reaction has been employed in the final stage. Electronic spectra of all prepared rhodols display strong absorption in the range of 450-550 nm with well-resolved vibronic bands, which maintains its fine structure in a wide range of solvents. The most intensive two-photon absorption (2PA) band in the rhodol spectrum (165 GM), located at shorter wavelengths, matches well with the short-wavelength absorption band in the linear electronic spectrum and is most probably related to the two-photon allowed electronic transition S0→S2. The influence of cation binding on one- and two-photon spectroscopic properties of rhodol linked with 1-aza-15-crown-5 via the phenylpyrazole bridge has been investigated. This probe exhibits high sensitivity and good selectivity for Na(+) in CH3CN. The mechanism involves the complexation of the Na(+) by 1-aza-15-crown-5 in the probe, which induces prominent fluorescence enhancement via quenching of electron-transfer. Interestingly, the complexation with Na(+) led to a significant increase of the 2PA band in the 750-800 nm region (corresponding to a two-photon allowed, one-photon forbidden transition) for rhodol bearing 1-aza-15-crown-5, which led to the overall enhancement of the TPEF signal (approximately an order of magnitude). Thus, a turn-on fluorescent probe for sodium ion, which does not respond to many other metal species, has been constructed.

[1]  M. Blanchard‐Desce,et al.  Two-photon polarity probes built from octupolar fluorophores: synthesis, structure-properties relationships, and use in cellular imaging. , 2013, Chemistry, an Asian journal.

[2]  Debabrata Sen,et al.  A ratiometric two-photon fluorescent probe reveals reduction in mitochondrial H2S production in Parkinson's disease gene knockout astrocytes. , 2013, Journal of the American Chemical Society.

[3]  Xiao-Feng Yang,et al.  Spirolactamized benzothiazole-substituted N,N-diethylrhodol: a new platform to construct ratiometric fluorescent probes. , 2013, Chemical communications.

[4]  K. Belfield,et al.  Design, synthesis, and structural and spectroscopic studies of push-pull two-photon absorbing chromophores with acceptor groups of varying strength. , 2013, The Journal of organic chemistry.

[5]  Ji Hee Han,et al.  Simultaneous imaging of mitochondria and lysosomes by using two-photon fluorescent probes. , 2012, Chemistry.

[6]  Xu-Hua Wang,et al.  Small molecule fluorophore and copolymer RGD peptide conjugates for ex vivo two-photon fluorescence tumor vasculature imaging. , 2012, Biomaterials.

[7]  M. Blanchard‐Desce,et al.  Fluorescence and two-photon absorption of push—pull aryl(bi)thiophenes: structure—property relationships , 2012, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[8]  Ji Hee Han,et al.  A small-molecule two-photon probe for nitric oxide in living tissues. , 2012, Chemistry.

[9]  Ji Hee Han,et al.  Dual-color imaging of magnesium/calcium ion activities with two-photon fluorescent probes. , 2012, Analytical chemistry.

[10]  Ji Hee Han,et al.  A small molecule two-photon probe for hydrogen sulfide in live tissues. , 2012, Chemical communications.

[11]  M. Blanchard‐Desce,et al.  Octupolar merocyanine dyes: a new class of nonlinear optical chromophores. , 2012, Chemistry.

[12]  I. Beletskaya,et al.  Synthesis, characterization and cation-induced dimerization of new aza-crown ether-appended metalloporphyrins. , 2012, Dalton transactions.

[13]  K. Belfield,et al.  Two‐Photon Fluorescent Probes for Bioimaging , 2012 .

[14]  S. Bottle,et al.  Two-Photon Fluorescence Microscopy Imaging of Cellular Oxidative Stress Using Profluorescent Nitroxides , 2012, Journal of the American Chemical Society.

[15]  D. Churchill,et al.  Labile zinc-assisted biological phosphate chemosensing and related molecular logic gating interpretations. , 2012, Inorganic chemistry.

[16]  I. Beletskaya,et al.  Pd-catalyzed amination in the synthesis of cyclen-based macrotricycles , 2012 .

[17]  W. Guo,et al.  Rhodafluor-based chromo- and fluorogenic probe for cyanide anion , 2011 .

[18]  Y. Urano,et al.  β-Galactosidase fluorescence probe with improved cellular accumulation based on a spirocyclized rhodol scaffold. , 2011, Journal of the American Chemical Society.

[19]  Yoon Sup Lee,et al.  Control of on-off or off-on fluorescent and optical [Cu²⁺] and [Hg²⁺] responses via formal Me/H substitution in fully characterized thienyl "scorpionate"-like BODIPY systems. , 2011, Inorganic chemistry.

[20]  Madhavi Gangapuram,et al.  Dansyl - Substituted Aza Crown Ethers: Complexation with Alkali, Alkaline Earth Metal Ions and Ammonium. , 2011, International journal of chemistry.

[21]  Hwan Myung Kim,et al.  Two-photon fluorescent probes for metal ions. , 2011, Chemistry, an Asian journal.

[22]  S. Lippard,et al.  Ratiometric and intensity-based zinc sensors built on rhodol and rhodamine platforms. , 2010, Inorganic chemistry.

[23]  T. Peng,et al.  HKGreen-3: a rhodol-based fluorescent probe for peroxynitrite. , 2010, Organic letters.

[24]  Ji Hee Han,et al.  Dual-color imaging of sodium/calcium ion activities with two-photon fluorescent probes. , 2010, Angewandte Chemie.

[25]  M. Hiraoka,et al.  Indolequinone-rhodol conjugate as a fluorescent probe for hypoxic cells: enzymatic activation and fluorescence properties , 2010 .

[26]  Xu-Hua Wang,et al.  Donor-acceptor-donor fluorene derivatives for two-photon fluorescence lysosomal imaging. , 2010, The Journal of organic chemistry.

[27]  T. Nabeshima,et al.  Remarkable Mg2+-selective emission of an azacrown receptor based on Ir(III) complex. , 2010, Chemical communications.

[28]  K. Belfield,et al.  A series of fluorene-based two-photon absorbing molecules: synthesis, linear and nonlinear characterization, and bioimaging. , 2010, The Journal of organic chemistry.

[29]  D. Churchill,et al.  Crystallographic, photophysical, NMR spectroscopic and reactivity manifestations of the "8-heteroaryl effect" in 4,4-difluoro-8-(C(4)H(3)X)-4-bora-3a,4a-diaza-s-indacene (X = O, S, Se) (BODIPY) systems. , 2010, Inorganic chemistry.

[30]  T. Peng,et al.  Construction of a library of rhodol fluorophores for developing new fluorescent probes. , 2010, Organic letters.

[31]  Ji Hee Han,et al.  Sodium-ion-selective two-photon fluorescent probe for in vivo imaging. , 2010, Angewandte Chemie.

[32]  Dietmar Keil,et al.  Relationship between the molecular structure of merocyanine dyes and the vibrational fine structure of their electronic absorption spectra. , 2009, Angewandte Chemie.

[33]  M. V. Bondar,et al.  Nonlinear absorption in a series of Donor–π–Acceptor cyanines with different conjugation lengths , 2009 .

[34]  K. Belfield,et al.  Two-photon absorption and lasing properties of new fluorene derivatives , 2009 .

[35]  H. L. Anderson,et al.  Zweiphotonenabsorption und das Design von Zweiphotonenfarbstoffen , 2009 .

[36]  B. Cho,et al.  Two-photon probes for intracellular free metal ions, acidic vesicles, and lipid rafts in live tissues. , 2009, Accounts of chemical research.

[37]  S. Ernst,et al.  Relationship between the molecular structure of cyanine dyes and the vibrational fine structure of their electronic absorption spectra. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[38]  A. Ishchenko,et al.  Merocyanine dyes: synthesis, structure, properties and applications , 2009 .

[39]  A. Ishchenko,et al.  Nonlinear optical characteristics and lasing ability of merocyanine dyes having different solvatochromic behaviour , 2008 .

[40]  A. V. Tsukanov,et al.  Organic chemosensors with crown-ether groups (review) , 2008 .

[41]  Yuka Horio,et al.  Design and synthesis of regioisomerically pure unsymmetrical xanthene derivatives for staining live cells and their photochemical properties. , 2008, Bioorganic & medicinal chemistry letters.

[42]  I. Leray,et al.  Synthesis, fluorescence, and two-photon absorption of bidentate phosphane oxide derivatives: complexation with pb(2+) and cd(2+) cations. , 2008, Chemistry.

[43]  M. V. Bondar,et al.  Comparison of nonlinear absorption in three similar dyes: Polymethine, squaraine and tetraone , 2008 .

[44]  P. Prasad,et al.  Multiphoton absorbing materials: molecular designs, characterizations, and applications. , 2008, Chemical reviews.

[45]  M. Alfimov,et al.  Design principles for optical molecular sensors and photocontrolled receptors based on crown ethers , 2008 .

[46]  Claudine Katan,et al.  Two-photon transitions in quadrupolar and branched chromophores: experiment and theory. , 2007, The journal of physical chemistry. B.

[47]  B. Cho,et al.  A Two‐Photon Fluorescent Probe for Lipid Raft Imaging: C‐Laurdan , 2007, Chembiochem : a European journal of chemical biology.

[48]  Jie Fu,et al.  High two-photon cross-sections in bis(diarylaminostyryl) chromophores with electron-rich heterocycle and bis(heterocycle)vinylene bridges. , 2007, Chemical communications.

[49]  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.

[50]  A. Jen,et al.  Two-Photon Absorption in Quadrupolar Bis(acceptor)-Terminated Chromophores with Electron-Rich Bis(heterocycle)vinylene Bridges , 2007 .

[51]  S. Charpak,et al.  Water-soluble dendrimeric two-photon tracers for in vivo imaging. , 2006, Angewandte Chemie.

[52]  John F. Callan,et al.  Luminescent sensors and switches in the early 21st century , 2005 .

[53]  J. Perry,et al.  Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers. , 2005, Journal of the American Chemical Society.

[54]  Y. Le Grand,et al.  Action cross sections of two-photon excited luminescence of some Eu(iii) and Tb(iii) complexes , 2005, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[55]  H. Meier.  Konjugierte Oligomere mit terminaler Donor‐Acceptor‐Substitution , 2005 .

[56]  J. Verkade,et al.  Synthesis of N-aryl-aza-crown ethers via Pd-catalyzed amination reactions of aryl chlorides with aza-crown ethers , 2004 .

[57]  Hwan Myung Kim,et al.  Two-photon sensor for metal ions derived from azacrown ether. , 2004, The Journal of organic chemistry.

[58]  Egbert Zojer,et al.  Metal-ion sensing fluorophores with large two-photon absorption cross sections: aza-crown ether substituted donor-acceptor-donor distyrylbenzenes. , 2004, Journal of the American Chemical Society.

[59]  W. M. Leevy,et al.  Crown ethers: sensors for ions and molecular scaffolds for materials and biological models. , 2004, Chemical reviews.

[60]  W. Webb,et al.  Water-Soluble Quantum Dots for Multiphoton Fluorescence Imaging in Vivo , 2003, Science.

[61]  S. Lippard,et al.  Synthesis and metal-binding properties of chelating fluorescein derivatives. , 2003, Organic letters.

[62]  S. Lippard,et al.  The rhodafluor family. An initial study of potential ratiometric fluorescent sensors for Zn2+. , 2002, Inorganic chemistry.

[63]  Jerome Mertz,et al.  Synthesis and photophysical properties of new conjugated fluorophores designed for two-photon-excited fluorescence. , 2002, Organic letters.

[64]  Jerome Mertz,et al.  Nanoscale Push-Push Dihydrophenanthrene Derivatives as Novel Fluorophores for Two-Photon-Excited Fluorescence. , 2001, Angewandte Chemie.

[65]  D. Bassani,et al.  Novel alkali cation chemosensors based on n-9-anthrylaza-crown ethers. , 2001, Organic letters.

[66]  Buchwald,et al.  Efficient synthesis of N-aryl-aza-crown ethers via palladium-catalyzed amination , 2000, The Journal of organic chemistry.

[67]  Mireille Blanchard-Desce,et al.  Molecular engineering of push–pull dipolar and quadrupolar molecules for two-photon absorption: A multivalence-bond states approach , 2000 .

[68]  W. Webb,et al.  Two-Photon Fluorescence Excitation Cross Sections of Biomolecular Probes from 690 to 960 nm. , 1998, Applied optics.

[69]  W. Webb,et al.  Design of organic molecules with large two-photon absorption cross sections. , 1998, Science.

[70]  W. Webb,et al.  Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690 to 1050 nm , 1996 .

[71]  I. L. Arbeloa,et al.  Flourescence self-quenching of the molecular forms of Rhodamine B in aqueous and ethanolic solutions , 1989 .

[72]  L. G. Lee,et al.  Vita Blue: a new 633-nm excitable fluorescent dye for cell analysis. , 1989, Cytometry.

[73]  K. Kimura,et al.  Lipophilic bis(monoaza crown ether) derivatives: synthesis and cation-complexing properties , 1986 .

[74]  V. J. Gatto,et al.  Syntheses of calcium-selective, substituted diaza-crown ethers: a novel, one-step formation of bibracchial lariat ethers (BiBLES) , 1984 .

[75]  R. Williams,et al.  STRUCTURAL STUDIES OF ORGANOSULFUR COMPOUNDS. 2. CONFORMATIONAL ANALYSIS OF 2-METHOXY-TRANS-HEXAHYDRO-1,4-BENZOXATHIANES , 1977 .

[76]  B. M. Heron,et al.  Palladium-catalysed amination of bromofluorans and an investigation of their thermochromic behaviour , 2012 .

[77]  C. Fahrni,et al.  Metal Ion-Responsive Fluorescent Probes for Two-Photon Excitation Microscopy. , 2011, Chemistry of materials : a publication of the American Chemical Society.

[78]  I. Johnson,et al.  The molecular probes handbook : a guide to fluorescent probes and labeling technologies , 2010 .

[79]  J. Perry,et al.  Two-Photon Absorbing Materials and Two-Photon-Induced Chemistry , 2008 .

[80]  Y. Kovtun,et al.  Series of polymethine dyes derived from 2,2-difluoro-1,3,2-(2H)-dioxaborine of 3-acetyl-7-diethylamino-4-hydroxycoumarin , 2008 .

[81]  Yevgen M Poronik,et al.  New heterocyclic analogues of rhodamines , 2007 .

[82]  Yevgen M Poronik,et al.  Substituted xanthylocyanines. III. Dyes containing non-symmetrically substituted xanthylium core , 2007 .

[83]  M. Blanchard‐Desce.  DOSSIER PHOTONIQUE MOLECULAIRE : MATÉRIAUX, PHYSIQUE ET COMPOSANTS MOLECULAR PHOTONICS: MATERIALS, PHYSICS AND DEVICES Molecular engineering of NLO-phores for new NLO microscopies , 2002 .

[84]  Jerome Mertz,et al.  New quadrupolar fluorophores with high two-photon excited fluorescence , 1999 .

[85]  O. Wolfbeis,et al.  Near-Infrared Dyes for High Technology Applications , 1998 .

[86]  L. Fabbrizzi,et al.  Sensors and switches from supramolecular chemistry , 1995 .

[87]  G. Gokel.  Crown Ethers and Cryptands , 1991 .

[88]  G. Bird,et al.  Shaping the absorption and fluorescence bands of a class of efficient, photoactive chromophores: synthesis and properties of some new 3H-xanthen-3- , 1987 .

[89]  V. J. Gatto,et al.  Novel synthetic access to 15- and 18-membered ring diaza-bibracchial lariat ethers (BiBLEs) and a study of sidearm-macroring cooperativity in cation binding , 1986 .

[90]  K. Drexhage,et al.  Dyestuff Lasers and Light Collectors — Two New Fields of Application for Fluorescent Heterocyclic Compounds , 1984 .