Detection of volatile organic compounds using porphyrin derivatives.

Seven different porphyrin compounds have been investigated as colorimetric gas sensors for a wide range of volatile organic compounds. The porphyrins examined were the free base and Mg, Sn, Zn, Au, Co, and Mn derivatives of 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine. Chloroform solutions of these materials were prepared and changes in their absorption spectra induced by exposure to various organic compounds measured. The porphyrins that showed strong responses in solution were selected, and Langmuir-Blodgett films were prepared and exposed to the corresponding analytes. This was done to determine whether they are useful materials for solid state thin film colorimetric vapor sensors. Porphyrins that readily coordinate extra ligands are shown to be suitable materials for colorimetric volatile organic compound detectors. However, porphyrins that already have bound axial ligands when synthesized only show a sensor response to those analytes that can substitute these axial ligands. The Co porphyrin displays a considerably larger response than the other porphyrins investigated which is attributed to a switch between Co(II) and Co(III) resulting in a large spectral change.

A solution concentration dependent transition from self-stratification to lateral phase separation in spin-cast PS:d-PMMA thin films.

Thin films with a rich variety of different nano-scale morphologies have been produced by spin casting solutions of various concentrations of PS:d-PMMA blends from toluene solutions. During the spin casting process specular reflectivity and off-specular scattering data were recorded and ex situ optical and atomic force microscopy, neutron reflectivity and ellipsometry have all been used to characterise the film morphologies. We show that it is possible to selectively control the film morphology by altering the solution concentration used. Low polymer concentration solutions favour the formation of flat in-plane phase-separated bi-layers, with a d-PMMA-rich layer underneath a PS-rich layer. At intermediate concentrations the films formed consist of an in-plane phase-separated bi-layer with an undulating interface and also have some secondary phase-separated pockets rich in d-PMMA in the PS-rich layer and vice versa. Using high concentration solutions results in laterally phase-separated regions with sharp interfaces. As with the intermediate concentrations, secondary phase separation was also observed, especially at the top surface.

Alkylamine sensing using langmuir-blodgett films of n-alkyl-N-phenylamide-substituted zinc porphyrins.

Two porphyrin compounds, zinc(II) 5,10,15,20-tetrakis(3,5,5-trimethyl- N-phenylhexanamide)porphyrin and zinc(II) 5,10,15,20-tetrakis(2,2-dimethyl- N-phenylpropanamide)porphyrin, have been investigated as possible candidates for the detection of alkylamines. UV-visible spectroscopy has shown that their solution absorption spectra are significantly modified upon interaction with a range of organic analytes, including acetic acid, butanone, ethylacetate, hexanethiol, octanal, octanol, alkylamines, and trimethylphosphite. Large spectral changes are observed for the family of alkylamines as a result of the specific affinity between zinc and the amine moiety. Langmuir-Blodgett (LB) films of the porphyrins have been fabricated in order to assess their solid-state sensing capability toward amines. The surface pressure-area (Pi- A) isotherms reveal a clear three-phase Langmuir film behavior and show that these monolayer films may be compressed to a relatively high surface pressure ( approximately 40-50 mN m (-1)). The isotherm data alongside molecular modeling suggest a relatively flat orientation of the porphyrin rings of both compounds: that is, a mutually parallel alignment of the plane of the porphyrin ring and that of the water surface. LB films deposited at 15 mN m (-1) have been exposed to alkylamine vapor (carried by N 2). A red shift and increase in intensity of the Soret band absorbance is observed which can be reversed by flowing pure N 2 over the gently heated sample (60 degrees C) after exposure. Primary amines were expected to invoke the greatest sensing response due to (i) their larger association constants with these porphyrins compared to secondary and tertiary amines and (ii) the ease of diffusion of amines which is expected to follow the order primary > secondary > tertiary due to the steric hindrance arising from the bulky secondary and tertiary amines. However, the magnitude of the absorbance change is largest for exposure to the secondary amines, dipropylamine and dibutylamine, for both porphyrins, compared to primary and tertiary amines. This trend follows that observed when the amines were added to solutions of the porphyrins. The rate of response of the porphyrin LB films falls as the molecular weight of the diffusing alkylamine increases. Furthermore, a greater rate of response is observed for the phenylhexanamide porphyrin compared to the phenylpropanamide porphyrin due to its lower molecular density within the LB film and therefore more porous structure.

Experimental and simulational study of the operation conditions for a high transmission mass filter.

The operation conditions of a double pulsed field mass filter were studied using both experiment and simulation. The mass filter consists of two pairs of parallel plates and operates on the time-of-flight principle. The study showed that the ions' beam deflection angle is a critical factor in optimizing the mass filter transmission efficiency. This angle is dependent on the accelerating voltage, ion mass, and horizontal velocity of the ions. The optimum operating conditions for the mass filter were found and used to study the mass distribution of palladium ions produced by a magnetron sputtering source. The study shows that this mass filter is suitable for technological applications because of its high transmission and wide mass range.