Prof Tony Cafolla

The design and performance of a ruggedised dissolved oxygen (DO) probe, which is based on phase fluorometric detection of the quenched fluorescence of an oxygen-sensitive ruthenium complex, is reported. The complex is entrapped in a porous hydrophobic sol–gel matrix that has been optimised for this application. The LED excitation and photodiode detection are employed in a dipstick probe configuration, with the oxygen-sensitive film coated on a disposable PMMA disc, which in turn is designed to guide light into the film by total internal reflection. A key element of the design is the common mode rejection of phase between the signal and reference channels, requiring careful selection of the relevant optoelectronic components. The advantages of the phase fluorometric approach over intensity measurement are highlighted. The phase detection electronics exhibits excellent long-term stability with a temperature coefficient of 0.00087. The sensor response exhibits excellent signal-to-noise ratio (SNR) and reversibility and has been corrected for both temperature and pressure. The limit of detection (LOD) is typically 0.15 hPa or 6 ppb. The sensor has many potential applications but it has been designed primarily for application in waste-water monitoring.

Oxygen binding and cleavage are important for both molecular recognition and catalysis. Mn-based porphyrins in particular are used as catalysts for the epoxidation of alkenes, and in this study the homolytic cleavage of O₂ by a surface-supported monolayer of Mn porphyrins on Ag(111) is demonstrated by scanning tunneling microscopy, X-ray absorption, and X-ray photoemission. As deposited, {5,10,15,20-tetraphenylporphyrinato}Mn(III)Cl (MnClTPP) adopts a saddle conformation with the average plane of its macrocycle parallel to the substrate and the axial Cl ligand pointing upward, away from the substrate. The adsorption of MnClTPP on Ag(111) is accompanied by a reduction of the Mn oxidation state from Mn(III) to Mn(II) due to charge transfer between the substrate and the molecule. Annealing the Mn(II)ClTPP monolayer up to 510 K causes the chlorine ligands to desorb from the porphyrins while leaving the monolayer intact. The Mn(II)TPP is stabilized by the surface acting as an axial ligand for the metal center. Exposure of the Mn(II)TPP/Ag(111) system to molecular oxygen results in the dissociation of O₂ and forms pairs of Mn(III)OTPP molecules on the surface. Annealing at 445 K reduces the Mn(III)OTPP complex back to Mn(II)TPP/Ag(111). The activation energies for Cl and O removal were found to be 0.35 ± 0.02 eV and 0.26 ± 0.03 eV, respectively.

The modification of cyclo-olefin polymer Zeonor by plasma-enhanced chemical vapor deposition to form a silica-like surface and evaluation of its application for lateral flow bioassays applications are discussed in this study. The SiO_x layer was extensively characterized using contact angle measurements, atomic force microscopy, and Fourier transform infrared spectroscopy in attenuated total internal reflectance mode where the presence of a uniform SiO_x film was clearly identified. The SiO_x modification resulted in a surface with enhanced wettability and excellent fluidic properties when combined with a hot-embossed micropillar capillary fill-based substrate. The SiO_x surface also had the ability to accelerate the clotting of human plasma, which may have application in certain types of blood coagulation assays.