Fluorescent Sensing of Chlorophenols in Water Using an Azo Dye Modified β-Cyclodextrin Polymer

A water soluble azo dye modified β-cyclodextrin polymer 4 was synthesized and used as a chemosensor for the detection of chlorinated phenols, model chlorinated by-products (CBPs) of water treatment for drinking purposes. The characterization of the intermediates and the azo dye modified β-CD polymer was done by UV/Vis Spectrophotometry, FT-IR and 1H-NMR spectroscopies. The chlorophenols were capable of quenching the fluorescence of the polymer. The polymer showed greater sensitivity towards 2,4-dichlorophenol, with a sensitivity factor of 0.35 compared to 0.05 and 0.12 for phenol and 4-chlorophenol, respectively. The stability constants (Ks) of the pollutants were also determined by the Benesi-Hildebrand method to be 2.104 × 103 M−1 for 2,4-dichlorophenol and 1.120 × 102 M−1 for 4-chlorophenol.

[1]  David Landy,et al.  Fluorescent Indolizine-β-Cyclodextrin Derivatives for the Detection of Volatile Organic Compounds , 2008, Sensors.

[2]  Mercedes Crego-Calama,et al.  Design of fluorescent materials for chemical sensing. , 2007, Chemical Society reviews.

[3]  J. Szejtli,et al.  Charge-transfer chromatographic study on inclusion complex formation between two hydroxypropyl-β-cyclodextrins and some chlorophenols , 1990 .

[4]  S. W. Thomas,et al.  Chemical sensors based on amplifying fluorescent conjugated polymers. , 2007, Chemical reviews.

[5]  Krishna Gopal,et al.  Chlorination byproducts, their toxicodynamics and removal from drinking water. , 2007, Journal of hazardous materials.

[6]  R. Marchelli,et al.  Enantioselective sensing of amino acids by copper(II) complexes of phenylalanine-based fluorescent β-cyclodextrins , 2000 .

[7]  É. Fenyvesi,et al.  Reversed-phase thin-layer chromatography of some chlorophenols in the presence of a soluble β-cyclodextrin polymer , 1988 .

[8]  W. L. Jorgensen.  Supramolecular chemistry. , 1993, Proceedings of the National Academy of Sciences of the United States of America.

[9]  M. Cedergren,et al.  Chlorination byproducts and nitrate in drinking water and risk for congenital cardiac defects. , 2002, Environmental research.

[10]  N. Kuramoto,et al.  Host-guest complexation affected by pH and length of spacer for hydroxyazobenzene-modified cyclodextrins. , 2006, The journal of physical chemistry. A.

[11]  David Landy,et al.  Photochemical behaviour upon the inclusion for some volatile organic compounds in new fluorescent indolizine β-cyclodextrin sensors , 2007 .

[12]  A. Ueno,et al.  Naphthol‐modified β‐cyclodextrins as fluorescent sensors for detecting contaminants in drinking water , 2000 .

[13]  Y. Sakata,et al.  A color version of the Hinsberg test: permethylated cyclodextrin and crown-appended azophenol for highly selective sensing of amines , 2008 .

[14]  F. Hamada,et al.  Photochromic molecular recognition of β-cyclodextrin bearing spiropyran moiety for organic guests , 1996 .

[15]  Manuel C Martos-Maldonado,et al.  Synthesis of β-cyclodextrin derivatives functionalized with azobenzene , 2008 .

[16]  Akira Harada,et al.  Chemical Sensors Based on Cyclodextrin Derivatives , 2008, Sensors.

[17]  S. Al-Shihry.  Spectroscopic studies of inclusion complexes of 1-naphthol-4-sulfonate with beta-cyclodextrin in aqueous solution. , 2005, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[18]  M. Garcia‐Garibay,et al.  Spectrometric and 2D NMR Studies on the Complexation of Chlorophenols with Cyclodextrins , 2001 .

[19]  Robert Bittman,et al.  An improved synthesis of 6-O-monotosyl-6-deoxy-β-cyclodextrin , 1998 .

[20]  K. Toth,et al.  Synthesis and optical characterization of novel azacrown ethers containing an acridinone or an N-methylacridinone unit as potential fluorescent chemosensors , 2010 .

[21]  R. Marchelli,et al.  Fast parallel enantiomeric analysis of unmodified amino acids by sensing with fluorescent β-cyclodextrins , 2005 .

[22]  Y. Takashima,et al.  Cyclodextrin-grafted poly(phenylene ethynylene) with chemically-responsive properties. , 2006, Chemical communications.

[23]  T. Iijima,et al.  The interaction of acid azo dyes with chemically modified β-cyclodextrins , 1998 .

[24]  C. Len,et al.  Azobenzenes—synthesis and carbohydrate applications , 2009 .

[25]  C. Ching,et al.  A reliable synthesis of 2- and 6-amino-β-cyclodextrin and permethylated-β-cyclodextrin , 2005 .

[26]  H. Nakashima,et al.  Fluorescent detection for cyclic and acyclic alcohol guests by naphthalene-appended amino-beta-cyclodextrins. , 2006, Organic letters.

[27]  Dong-Sheng Guo,et al.  Novel Permethylated β-Cyclodextrin Derivatives Appended with Chromophores as Efficient Fluorescent Sensors for the Molecular Recognition of Bile Salts. , 2008 .