Francine Cazier

Fluorescent Indolizine-β-Cyclodextrin Derivatives for the Detection of Volatile Organic Compounds

This paper presents the synthesis, the structural determination and the sensing capabilities toward Volatile Organic Compounds (VOCs) of a new class of fluorescent indolizine-cyclodextrin sensors. Two different pathways, both involving bipyridinium ylides and 6-amino-b-cyclodextrin, have been used to carry out the synthesis of these sensors. The macrocycle structures were dominantly established by 1H-NMR spectra and systematically studied by molecular modelling (MM3, AM1, AM1-COSMO methods). The sensing capabilities of the sensors were evaluated by emission of fluorescence, during the inclusion of the guest (adamantanol or aromatic derivatives) into the cyclodextrin (CD) host cavity. The host/guest complex formation was investigated by formation constant determinations, using experimental methods, coupled with theoretical calculations of formation energies using a specific docking procedure. Both experimental and theoretical results suggest that some compounds would make very attractive sensors for VOC detection. Some compounds could also be taken into consideration as biological markers.

Organically Modified Silica with Pyrazole-3-carbaldehyde as a New Sorbent for Solid-Liquid Extraction of Heavy Metals

A new chelating matrix, SiNP, has been prepared by immobilizing 1.5-dimethyl-1H-pyrazole-3-carbaldehyde on silica gel modified with 3-aminopropyl-trimethoxysilane. This new chelating material was well characterized by elemental analysis, FT-IR spectroscopy, cross polarization magic angle spinning solid state 13C-NMR, nitrogen adsorption-desorption isotherm, BET surface area, BJH pore size, and scanning electron microscopy (SEM). The new product exhibits good chemical and thermal stability as determined by thermogravimetry curves (TGA). The new prepared material was used as an adsorbent for the solid-phase extraction (SPE) of Pb(II), Cd(II), Cu(II) and Zn(II) from aqueous solutions using a batch method, prior to their determination by flame atomic adsorption spectrometry. The adsorption capacity was investigated using kinetics and pH effects. Common coexisting ions did not interfere with separation and determination.

Metabolization of the Polycyclic Aromatic Hydrocarbon Benzo( A )Pyrene by a Non-White Rot Fungus ( Fusarium Solani ) in a Batch Reactor

To investigate metabolization of benzo[ a ]pyrene (B a P), a high-molecular-weight polycyclic aromatic hydrocarbon consisting of five aromatic rings, by a Deuteromycete Fusarium solani , a culture with [7,10- 14 C]benzo[ a ]pyrene was carried out in a batch fermentor under cometabolic conditions. In spite of drastic culture conditions with a high load of B a P (302 mg in a 1.6 liters), analysis of the growth and substrate depletion kinetics showed a classical pattern. The evolution of 14 CO 2 release demonstrated that B a P mineralization by the non-white rot fungus F. solani occurred rapidly at early stages of fermentation (15 hr) during the germination process. At the end of fermentation, 1.2% of the B a P was evolved as 14 CO 2 and 5.3% was incorporated in biomass. B a P metabolization was also confirmed by isolating metabolic products, extracted from mycelia and identified as 1,6-benzo[ a ]pyrene quinone and 3,6-benzo[ a ]pyrene quinone, by mass and ultraviolet (UV) spectroscopic analyses.

Efficient synthesis of a fluorescent tripod detection system for pesticides by microwave-assisted click chemistry.

A new tripod molecule containing an aromatic core bearing three peracetylated cyclodextrins was synthesized via a microwave-assisted Huisgen 1,3-dipolar cycloaddition and was studied by fluorescence spectroscopy. The photoluminescent properties of complexation phenomena with different pesticides were evaluated in acetonitrile. Fluorescence titrations have been performed to calculate binding constants, sensitivity factors, and limit of detection of the resulting complexes. 2D NMR experiments confirmed the inclusion of pesticide in the hydrophobic cavity of the macrocycle and validated the supramolecular association responsible for the quenching of the fluorescence.

Use a Fluorescent Molecular Sensor for the Detection of Pesticides and Herbicides in Water

A fluorescent chemosensor based on modified �-cyclodextrin was used for the detection of pesticides and her- bicides in water. Binding constants, thermodynamic parameters and sensitivity factors were calculated and supported by AM1 semi-empirical method calculation. The results show clearly that a fluorescent chemical sensor based on modified � - cyclodextrin detects quantitatively the presence of pesticides or herbicides and allow a direct analysis of these pollutants as a new method of detection with limits of the order of ppm for the whole of the analytes.

New Amine-Modified Silicas: Synthesis, Characterization and Its Use in the Cu(II)-Removal from Aqueous Solutions

Porous silica has been chemically modified with conjugated phenylamine and phenyldiamine moieties using the homogeneous route. This synthetic route involved the reaction of carbaldehyde derivatives with 3-aminopropyltrimethoxysilane prior to immobilization on the support. The resulting materials have been characterized by elemental analysis, FT-IR, 13 C NMR of the solid state, nitrogen adsorption-desorption isotherm, BET surface area, B.J.H. Pore sizes, thermogravimetry analyser (TGA) curves, X-ray diffraction (XRD) and scanning electron microscope (SEM). The new chelating surfaces exhibit good chemical and thermal stability. The solids were employed as Cu(II) adsorbents from aqueous solutions at room temperature. The effects of pH and adsorption kinetics have been studied using the batch technique. Flame atomic absorption spectrometry was used to determine the Cu(II) concentration in the filtrate after the adsorption process. The results indicate that under the optimum conditions, the maximum adsorption value for Cu(II) was 24.5 mg Cu(II) g −1 modified silica, whereas the adsorption capacity of the unmodified silica was only 1 mg Cu(II) g −1 silica. On the basis of these results, it can be concluded that it is possible to modify chemically silica with amine derivatives and to use the resulting modified porous silica as an effective adsorbent for Cu(II) in aqueous media.

1-(Pyridin-2-yl) Imine Functionalized Silica Gel: Synthesis, Characterization, and Preliminary Use in Metal Ion Extraction

A new silica gel material covalently bonded with 1-(pyridin-2-yl) imine (SiNPn) was synthesized and well characterized by elemental analysis, FT–IR, 13C NMR of the solid state, nitrogen adsorption-desorption isotherm, BET surface area, B.J.H. Pore sizes, thermogravimetry curves (TGA), and scanning electron microscope (SEM). The new chelating surface exhibits good chemical and thermal stability. The adsorption capabilities of this new system towards toxic metal ions (Hg2+, Cd2+, Pb2+, and Zn2+) were investigated using the batch method. The percentage limits of extraction were determined by atomic absorption measurements.

SYNTHESIS OF NEW FLUORESCENT β-CYCLODEXTRIN SENSOR

The synthesis of a new fluorescent sensor incorporating a fluoro pyridine indolizinic unit and a ßcyclodextrin fragment by two different synthetic ways is described.

Cyclophanes or Cyclodextrins: What is the Best Host for Aromatic Volatile Organic Compounds?

The first results of the complexing ability of cyclobis-(paraquat-p-phenylene) as supramolecular host with different aromatic volatile organic compounds are presented. The formation constants of cyclobis(paraquat-p-phenylene) with toluene and halogenobenzenes were determined in aqueous solution by static headspace associated with gas chromatography and compared with the ones obtained by cyclodextrins. The data indicated the formation of 1:1 inclusion compounds in both cases. The results underlined a greater complexation ability for cyclobis(paraquat-p-phenylene) which was confirmed by a theoretical study.

Synthesis and modification of oxetane based oligomers with 3-ethoxypropylamine by focused microwave irradiation

Abstract Synthesis of oligomers was achieved via condensation of several bisphenol sodium salts in water with 3,3′-bis(chloromethyl)oxetane in nitrobenzene under phase transfer catalysis with tetrabutyl ammonium bromide. All proceedings were developed both by classical and under focused microwave irradiation with complete experimental parameters control. The rigid oxetane chain was then opened partially with 3-ethoxypropylamine in order to generate some specific properties. Higher substitution was obtained by microwave activation in the presence of the zinc chloride which is well known to react as microwave absorber.