Self-assembly of graphene oxide with a silyl-appended spiropyran dye for rapid and sensitive colorimetric detection of fluoride ions.

Fluoride ion (F(-)), the smallest anion, exhibits considerable significance in a wide range of environmental and biochemical processes. To address the two fundamental and unsolved issues of current F(-) sensors based on the specific chemical reaction (i.e., the long response time and low sensitivity) and as a part of our ongoing interest in the spiropyran sensor design, we reported here a new F(-) sensing approach that, via assembly of a F(-)-specific silyl-appended spiropyran dye with graphene oxide (GO), allows rapid and sensitive detection of F(-) in aqueous solution. 6-(tert-Butyldimethylsilyloxy)-1',3',3'-trimethylspiro [chromene- 2,2'-indoline] (SPS), a spiropyran-based silylated dye with a unique reaction activity for F(-), was designed and synthesized. The nucleophilic substitution reaction between SPS and F(-) triggers cleavage of the Si-O bond to promote the closed spiropyran to convert to its opened merocyanine form, leading to the color changing from colorless to orange-yellow with good selectivity over other anions. With the aid of GO, the response time of SPS for F(-) was shortened from 180 to 30 min, and the detection limit was lowered more than 1 order of magnitude compared to the free SPS. Furthermore, due to the protective effect of nanomaterials, the SPS/GO nanocomposite can function in a complex biological environment. The SPS/GO nanocomposite was characterized by XPS and AFM, etc., and the mechanism for sensing F(-) was studied by (1)H NMR and ESI-MS. Finally, this SPS/GO nanocomposite was successfully applied to monitoring F(-) in the serum.

[1]  L. D. Taylor,et al.  Photochromic chelating agents , 1967 .

[2]  Chang-Hee Lee,et al.  Highly sensitive fluorescence "turn-on" indicator for fluoride anion with remarkable selectivity in organic and aqueous media. , 2011, The Journal of organic chemistry.

[3]  C. Lieber,et al.  Nanowire Nanosensors for Highly Sensitive and Selective Detection of Biological and Chemical Species , 2001, Science.

[4]  Philip A. Gale.  Anion receptor chemistry: highlights from 1999 , 2001 .

[5]  Shuangqing Wang,et al.  Sensing in 15 s for aqueous fluoride anion by water-insoluble fluorescent probe incorporating hydrogel. , 2013, Analytical chemistry.

[6]  E. Akkaya,et al.  Reaction-based sensing of fluoride ions using built-in triggers for intramolecular charge transfer and photoinduced electron transfer. , 2010, Organic letters.

[7]  Jannik C. Meyer,et al.  The structure of suspended graphene sheets , 2007, Nature.

[8]  W. H. Slabaugh,et al.  INTERACTIONS OF AMMONIA WITH GRAPHITE OXIDE , 1962 .

[9]  Huang-Hao Yang,et al.  A graphene platform for sensing biomolecules. , 2009, Angewandte Chemie.

[10]  SUPARNA DUTTASINHA,et al.  Graphene: Status and Prospects , 2009, Science.

[11]  Julius Rebek,et al.  Fluorescent sensors for organophosphorus nerve agent mimics. , 2006, Journal of the American Chemical Society.

[12]  H. Tian,et al.  A colorimetric and fluorescent chemodosimeter: fluoride ion sensing by an axial-substituted subphthalocyanine , 2005 .

[13]  Xungai Wang,et al.  Graphene oxide nanoparticles as a nonbleaching optical probe for two-photon luminescence imaging and cell therapy. , 2012, Angewandte Chemie.

[14]  M. Ravikanth,et al.  Boron complexes of oxasmaragdyrin, a core-modified expanded porphyrin. , 2011, The Journal of organic chemistry.

[15]  Xiao-Feng Yang.  Novel fluorogenic probe for fluoride ion based on the fluoride-induced cleavage of tert-butyldimethylsilyl ether. , 2007, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[16]  Rong-Hua Yang,et al.  A spiropyran-based ensemble for visual recognition and quantification of cysteine and homocysteine at physiological levels. , 2006, Angewandte Chemie.

[17]  Michael C Breadmore,et al.  On-column ion-exchange preconcentration of inorganic anions in open tubular capillary electrochromatography with elution using transient-isotachophoretic gradients. 3. Implementation and method development. , 2002, Analytical chemistry.

[18]  Rosanne M Guijt,et al.  Identification of inorganic improvised explosive devices by analysis of postblast residues using portable capillary electrophoresis instrumentation and indirect photometric detection with a light-emitting diode. , 2007, Analytical chemistry.

[19]  Kemin Wang,et al.  Bioconjugated nanoparticles for DNA protection from cleavage. , 2003, Journal of the American Chemical Society.

[20]  Ronghua Yang,et al.  Carbon nanotube-quenched fluorescent oligonucleotides: probes that fluoresce upon hybridization. , 2008, Journal of the American Chemical Society.

[21]  Ana B. Descalzo,et al.  A new method for fluoride determination by using fluorophores and dyes anchored onto MCM-41. , 2002, Chemical communications.

[22]  H. Furuta,et al.  Oxyindolophyrin: a novel fluoride receptor derived from N-confused corrole isomer. , 2001, Journal of the American Chemical Society.

[23]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[24]  R. Mülhaupt,et al.  Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction. , 2009, Journal of the American Chemical Society.

[25]  Yi Wang,et al.  Singlet Oxygen Involved Luminol Chemiluminescence Catalyzed by Graphene Oxide , 2012 .

[26]  B. Wang,et al.  A fluorescent probe for rapid aqueous fluoride detection and cell imaging. , 2013, Chemical communications.

[27]  Zhuang Liu,et al.  PEGylated nanographene oxide for delivery of water-insoluble cancer drugs. , 2008, Journal of the American Chemical Society.

[28]  Félix Sancenón,et al.  Fluorogenic and chromogenic chemosensors and reagents for anions. , 2003, Chemical reviews.

[29]  Yaping Hu,et al.  Graphene signal amplification for sensitive and real-time fluorescence anisotropy detection of small molecules. , 2013, Analytical chemistry.

[30]  Kong,et al.  Nanotube molecular wires as chemical sensors , 2000, Science.

[31]  W. Tan,et al.  Combination of π-π stacking and electrostatic repulsion between carboxylic carbon nanoparticles and fluorescent oligonucleotides for rapid and sensitive detection of thrombin. , 2011, Chemical communications.

[32]  Philip A. Gale,et al.  Anion Recognition and Sensing: The State of the Art and Future Perspectives. , 2001, Angewandte Chemie.

[33]  Dermot Diamond,et al.  Photo- and solvatochromic properties of nitrobenzospiropyran in ionic liquids containing the [NTf2]- anion. , 2008, Physical chemistry chemical physics : PCCP.

[34]  Ashwani Kumar,et al.  Chromofluorescent probes for selective detection of fluoride and acetate ions. , 2008, Organic letters.

[35]  Jong‐In Hong,et al.  Chromogenic and fluorescent chemodosimeter for detection of fluoride in aqueous solution. , 2007, Organic letters.

[36]  Jonathan L. Sessler,et al.  Dipyrrolylquinoxalines: Efficient Sensors for Fluoride Anion in Organic Solution , 1999 .

[37]  K. Loh,et al.  A graphene oxide-organic dye ionic complex with DNA-sensing and optical-limiting properties. , 2010, Angewandte Chemie.

[38]  Hao Wang,et al.  Spiropyran-based fluorescent anion probe and its application for urinary pyrophosphate detection. , 2010, Analytical chemistry.

[39]  Hongje Jang,et al.  A Graphene‐Based Platform for the Assay of Duplex‐DNA Unwinding by Helicase† , 2010, Angewandte Chemie.

[40]  O. Barbier,et al.  Molecular mechanisms of fluoride toxicity. , 2010, Chemico-biological interactions.

[41]  P. P. Singh,et al.  Evidence suggesting that high intake of fluoride provokes nephrolithiasis in tribal populations , 2001, Urological Research.

[42]  H. DatJ.  熱性色性 | 文献情報 | J-GLOBAL 科学技術総合リンクセンター , 1963 .

[43]  F. Gabbaï,et al.  A BODIPY boronium cation for the sensing of fluoride ions. , 2008, Chemical communications.

[44]  B. Liu,et al.  A "naked eye" and ratiometric fluorescent chemosensor for rapid detection of F- based on combination of desilylation reaction and excited-state proton transfer. , 2011, Chemical communications.

[45]  Jonathan L. Sessler,et al.  Naked-Eye Detection of Anions in Dichloromethane: Colorimetric Anion Sensors Based on Calix[4]pyrrole , 2000 .

[46]  Zhuang Liu,et al.  Nano-graphene oxide for cellular imaging and drug delivery , 2008, Nano research.

[47]  Jun Feng Zhang,et al.  A highly selective colorimetric and ratiometric two-photon fluorescent probe for fluoride ion detection. , 2011, Organic letters.

[48]  T. James,et al.  Selective fluorescence detection of fluoride using boronic acids , 1998 .

[49]  Ronghua Yang,et al.  Noncovalent assembly of carbon nanotubes and single-stranded DNA: an effective sensing platform for probing biomolecular interactions. , 2008, Analytical chemistry.

[50]  R. Yu,et al.  Graphene oxide-peptide conjugate as an intracellular protease sensor for caspase-3 activation imaging in live cells. , 2011, Angewandte Chemie.

[51]  Chun Li,et al.  Chemically converted graphene induced molecular flattening of 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin and its application for optical detection of cadmium(II) ions. , 2009, Journal of the American Chemical Society.

[52]  R. Ruoff,et al.  The chemistry of graphene oxide. , 2010, Chemical Society reviews.

[53]  Jongmin Park,et al.  Fluorescent probe for detection of fluoride in water and bioimaging in A549 human lung carcinoma cells. , 2009, Chemical communications.

[54]  Feng Liu,et al.  Copper ion-selective fluorescent sensor based on the inner filter effect using a spiropyran derivative. , 2005, Analytical chemistry.

[55]  A bidentate borane as colorimetric fluoride ion sensor. , 2004, Chemical communications.

[56]  Kemin Wang,et al.  A switchable fluorescent quantum dot probe based on aggregation/disaggregation mechanism. , 2011, Chemical communications.

[57]  Rong-Hua Yang,et al.  Tunable photochromism of spirobenzopyran via selective metal ion coordination: an efficient visual and ratioing fluorescent probe for divalent copper ion. , 2008, Analytical chemistry.

[58]  Lin Yuan,et al.  A ratiometric fluorescent probe for specific detection of cysteine over homocysteine and glutathione based on the drastic distinction in the kinetic profiles. , 2011, Chemical communications.

[59]  M. S. Frant,et al.  Electrode for Sensing Fluoride Ion Activity in Solution , 1966, Science.

[60]  I. Dékány,et al.  Selective liquid sorption properties of hydrophobized graphite oxide nanostructures , 1998 .

[61]  Philip A. Gale,et al.  Structural and molecular recognition studies with acyclic anion receptors. , 2006, Accounts of chemical research.

[62]  K. Loh,et al.  High-throughput synthesis of graphene by intercalation-exfoliation of graphite oxide and study of ionic screening in graphene transistor. , 2009, ACS nano.

[63]  Gang Wang,et al.  A ratiometric fluorescent probe for fluoride ion employing the excited-state intramolecular proton transfer. , 2009, Talanta.

[64]  Vincent M Rotello,et al.  Nanoscale graphene oxide (nGO) as artificial receptors: implications for biomolecular interactions and sensing. , 2012, Journal of the American Chemical Society.

[65]  Xiaogang Qu,et al.  Graphene Oxide: Intrinsic Peroxidase Catalytic Activity and Its Application to Glucose Detection , 2010, Advanced materials.

[66]  Yi Li,et al.  A rapid aqueous fluoride ion sensor with dual output modes. , 2010, Angewandte Chemie.

[67]  Huan Yu,et al.  Simultaneous nucleophilic-substituted and electrostatic interactions for thermal switching of spiropyran: a new approach for rapid and selective colorimetric detection of thiol-containing amino acids. , 2012, Analytical chemistry.

[68]  P Coriat,et al.  Fluoride Ion Toxicity in Human Kidney Collecting Duct Cells , 1996, Anesthesiology.

[69]  K. Tamao,et al.  Photophysical Properties Changes Caused by Hypercoordination of Organosilicon Compounds: From Trianthrylfluorosilane to Trianthryldifluorosilicate , 2000 .

[70]  T. Swager,et al.  A fluorescent self-amplifying wavelength-responsive sensory polymer for fluoride ions. , 2003, Angewandte Chemie.

[71]  Suning Wang,et al.  Charge-transfer emission in nonplanar three-coordinate organoboron compounds for fluorescent sensing of fluoride. , 2006, Angewandte Chemie.

[72]  A. Mouriz.  [Pharmacology of fluorine ion in the preventive use of fluorides]. , 1968, Revista de sanidad e higiene publica.

[73]  R. Ruoff,et al.  Graphene and Graphene Oxide: Synthesis, Properties, and Applications , 2010, Advanced materials.

[74]  Hao Wang,et al.  Design of bis-spiropyran ligands as dipolar molecule receptors and application to in vivo glutathione fluorescent probes. , 2010, Journal of the American Chemical Society.

[75]  K. Bowman-James.  Alfred Werner revisited: the coordination chemistry of anions. , 2005, Accounts of chemical research.

[76]  R. Yu,et al.  New strategy for label-free and time-resolved luminescent assay of protein: conjugate Eu3+ complex and aptamer-wrapped carbon nanotubes. , 2011, Analytical chemistry.