Thin film calixresorcinarene membranes for chemical sensing.

Novel applications for calix[4]recorcinarene (C[4]RA) sensing membranes have been investigated. A comprehensive deposition study was carried out, encompassing casting, spin coating and Langmuir Blodgett (LB) deposition. The spin coating thickness depended on the angular velocity w, following the description of d = c.wx with coefficients of x - 0.44 and - 0.48 for concentrations of 1 mg/ml and 2mg/ml respectively. The analysis of the LB deposited films established a thickness of 0.95 nm for a monolayer. Furthermore the C[4]RA, was successfully employed as a deposition matrix for a non surface active polymer, poly-ortho-methoxy aniline (POMA), which can otherwise not be deposited by LB. The composite film showed good homogeneity and based on thickness and UV measurements a structural model for it was developed, in which two polymer strands aligned themselves per C[4]RA layer, resulting in a monolayer thickness of 2.1 - 2.2 nm.The response of the C[4]RA and the composite membranes to a variety of organic and inorganic gaseous pollutants was investigated by Surface Plasmon Resonance studies, conductivity and capacitance measurements and UV spectroscopic studies. The integration of cast films into the gate of a charge flow transistor, is the first application of pure calixarenes in a conduction based sensor. The turn on response of the transistor is modulated by a variety of organic vapours, at the saturation vapour pressure, showing selectivity between polar and non-polar solvents, i.e. chloroform, methanol, acetone and hexane, with no cross sensitivity to water vapour. The modulation lies within factors of 45 for CHCI3 and 13 for CH3OH. The conductivity increase is partially attributed to micro-condensation of the vapours inside the micro-porous membrane. A successful application of this implementation as an explosion guard sensor for acetone is demonstrated.Gold electrodes with and without C[4]RA LB films have been characterised using impedance spectroscopy and cyclic voltammography. The modification of the gold electrodes by the C[4]RA film changes their constant phase element impedance, givenby 1/(w.Q)" with w being the angular velocity. The observed values were from Q =0.725-10 -5 Farad and n = 0.87 to Q = 0.828-10-6 Farad and n = 0.82. Organic analyteslike, chloroform and acetone in water can be successfully detected with these electrodes. It is shown by cyclic voltammetry, that the permeability of the C[4]RA LB films is modulated by the organic solvents.