Experimental and Theoretical Study on the Inclusion Capability of a Fluorescent Indolizine β-Cyclodextrin Sensor Towards Volatile and Semi-volatile Organic Guest

Inclusion equilibria of a new fluorescent indolizine modified β-cyclodextrin were studied in aqueous solution to evaluate its use as a fluorescent chemo-sensor for volatile organic compounds (VOCs). The host compound shows a decrease of the fluorescence intensity by adding adamantanol, benzene, toluene, phenol and p-cresol as guest. The sensing parameter (ΔI/I0) was used to show the sensing ability of the host. The formation constant values measured using a spectral displacement method and a specific algorithm treatment are reported. Although the guest binding ability of the sensor is not enhanced by the existence of the hydrophobic cap, this new cyclodextrin sensor shows a very strong sensing ability. The experimental values of the constants were in good agreement with the computed complexation energies, ΔE, from molecular mechanics modelling of the inclusion process.

[1]  A. Ueno.  Review: fluorescent cyclodextrins for molecule sensing , 1996 .

[2]  E. D. Valle,et al.  Cyclodextrins and their uses: a review , 2004 .

[3]  Terence E. Rice,et al.  Signaling Recognition Events with Fluorescent Sensors and Switches. , 1997, Chemical reviews.

[4]  F. Hamada,et al.  Fluorescent Pyrrolinone-modified Cyclodextrins as a Chemo-sensor for Organic Guests , 1999 .

[5]  Qing-Xiang Guo,et al.  Substituent Effects on the Driving Force for Inclusion Complexation of α- and β-Cyclodextrin with Monosubstituted Benzene Derivatives , 1998 .

[6]  C. T. Chen,et al.  Fluorescent, sequence-selective peptide detection by synthetic small molecules. , 1998, Science.

[7]  H. Yamamura,et al.  Dependence of guest-binding ability on cavity shape of deformed cyclodextrins , 1996 .

[8]  D. Ficheux,et al.  Fluorescent amino acids as reporter systems in peptido-cyclodextrin inclusion compounds , 1996 .

[9]  François Delattre,et al.  Structural investigations of pyridin-4-yl indolizine modified beta-cyclodextrin derivatives as fluorescent chemosensors for organic guest molecules. , 2005, Carbohydrate research.

[10]  Hao Wang,et al.  Inclusion complexation behavior of dyestuff guest molecules by a bridged bis(cyclomaltoheptaose)[bis(beta-cyclodextrin)] with a pyromellitic acid diamide tether. , 2003, Carbohydrate research.

[11]  T. Hayashita,et al.  Boronic acid fluorophore/beta-cyclodextrin complex sensors for selective sugar recognition in water. , 2001, Analytical chemistry.

[12]  Luca Prodi,et al.  Luminescent chemosensors for transition metal ions , 2000 .

[13]  F. Hamada,et al.  The synthesis of a fluorescent chemo-sensor system based on regioselectively dansyl-tosyl-modified β- and γ-cyclodextrins , 2000 .

[14]  A. Marsura,et al.  A new symmetrically modified α-cyclodextrin tripode: selective metal complexation and fluorescence properties , 2004 .

[15]  H. Nakashima,et al.  Fluorescent behaviour in host–guest interactions. Part 2. Thermal and pH-dependent sensing properties of two geometric isomers of fluorescent amino-β-cyclodextrin derivatives , 2001 .

[16]  S. Augustat.  M. L. Bender und M. Komiyama: Cyclodextrin Chemistry. 96 Seiten, 14 Abb., 37 Tab. Springer‐Verlag, Berlin, Heidelberg, New York 1978. Preis: 44,— DM , 1981 .

[17]  R. Marchelli,et al.  Fluorescent Chemosensor for Organic Guests and Copper(II) Ion Based on Dansyldiethylenetriamine-Modified β-Cyclodextrin , 1997 .

[18]  François Delattre,et al.  1,3-Dipolar cycloaddition reaction of bipyridinium ylides with the propynamido-β-cyclodextrin. A regiospecific synthesis of a new class of fluorescent β-cyclodextrins , 2004 .

[19]  M. Salome,et al.  Analytical Improvement in Measuring Formation Constants of Inclusion Complexes between β-Cyclodextrin and Phenolic Compounds , 2000 .

[20]  S. Matsumura,et al.  Association of α-helix peptides that have γ-cyclodextrin and pyrene units in their side chain, and induction of dissociation of the association dimer by external stimulant molecules , 2000 .

[21]  F. Bright,et al.  Comparison of inter- and intramolecular cyclodextrin complexes , 1994 .

[22]  Franz L. Dickert,et al.  Supramolecular strategies in chemical sensing , 1999 .

[23]  I. Sanemasa,et al.  Association of Benzene and Alkylbenzenes with Cyclodextrins in Aqueous Medium , 1987 .

[24]  J. Szejtli.  Cyclodextrins and their inclusion complexes , 1982 .

[25]  Y. Inoue,et al.  Complexation Thermodynamics of Cyclodextrins. , 1998, Chemical reviews.

[26]  S. Matsumura,et al.  Construction of α‐Helix Peptides with β‐Cyclodextrin and Dansyl Units and Their Conformational and Molecular Sensing Properties , 2000 .

[27]  Jean-Marie Lehn,et al.  Comprehensive Supramolecular Chemistry , 1996 .

[28]  M. Hisamatsu,et al.  Synthesis and enhanced chemiluminescence of new cyclomaltooligosaccharide (cyclodextrin)-bound 6-phenylimidazo[1,2-a]pyrazin-3(7H)-one , 1998 .

[29]  T Tanabe,et al.  Immobilized fluorescent cyclodextrin on a cellulose membrane as a chemosensor for molecule detection. , 2001, Analytical chemistry.

[30]  François Delattre,et al.  Synthesis of a new fluorinated fluorescent β-cyclodextrin sensor , 2005 .

[31]  R. Nugent,et al.  The synthesis of indolizines: the reaction of .alpha.-halo pyridinium salts with .beta.-dicarbonyl species , 1987 .

[32]  S. Shinkai,et al.  Saccharide Sensing with Molecular Receptors Based on Boronic Acid , 1996 .

[33]  Q. Guo,et al.  Regression Analysis for the Host–Guest Interaction of β-Cyclodextrin with Mono- and 1,4-Disubstituted Benzenes , 1999 .

[34]  P. Polster,et al.  A novel class of calcium-entry blockers: the 1[[4-(aminoalkoxy)phenyl]sulfonyl]indolizines. , 1992, Journal of medicinal chemistry.

[35]  G. Garçon,et al.  SYNTHESIS OF NEW FLUORESCENT β-CYCLODEXTRIN SENSOR , 2005 .