Sabine Achmann

Metal-Organic Frameworks for Sensing Applications in the Gas Phase

Several metal-organic framework (MOF) materials were under investigated to test their applicability as sensor materials for impedimetric gas sensors. The materials were tested in a temperature range of 120 °C - 240 °C with varying concentrations of O2, CO2, C3H8, NO, H2, ethanol and methanol in the gas atmosphere and under different test gas humidity conditions. Different sensor configurations were studied in a frequency range of 1 Hz -1 MHz and time-continuous measurements were performed at 1 Hz. The materials did not show any impedance response to O2, CO2, C3H8, NO, or H2 in the gas atmospheres, although for some materials a significant impedance decrease was induced by a change of the ethanol or methanol concentration in the gas phase. Moreover, pronounced promising and reversible changes in the electric properties of a special MOF material were monitored under varying humidity, with a linear response curve at 120 °C. Further investigations were carried out with differently doped MOF materials of this class, to evaluate the influence of special dopants on the sensor effect.

Direct detection of formaldehyde in air by a novel NAD+- and glutathione-independent formaldehyde dehydrogenase-based biosensor.

An amperometric enzyme-based sensor-system for the direct detection of formaldehyde in air is under investigation. The biosensor is based on a native bacterial NAD(+)- and glutathione-independent formaldehyde dehydrogenase as biorecognition element. The enzyme was isolated from Hyphomicrobium zavarzinii strain ZV 580, grown on methylamine hydrochloride in a fed-batch process. The sensor depends on the enzymatic conversion of the analyte to formic acid. Released electrons are detected in an amperometric measurement at 0.2V vs. Ag/AgCl reference electrode by means of a redox-mediator. To optimize the sensing device, Ca(2+) and pyrroloquinoline quinone (PQQ) were added to the buffer solution as reconstitutional substances. At this stage, the sensor shows linear response in the tested ppm-range with a sensitivity of 0.39 microA/ppm. The signal is highly reproducible with respect to sensitivity and base line signal. Reproducibility of sensitivity is more than 90% within the same bacterial batch and even when enzyme of different bacterial batches is used.

Direct monitoring of organic vapours with amperometric enzyme gas sensors.

In this study, amperometric enzyme gas sensors for direct monitoring of organic vapours (formaldehyde, ethanol and phenol) are presented using exemplarily different sensing strategies: NADH detection, H(2)O(2) detection and direct substrate recycling, respectively. The presented sensor configurations allow the selective, continuous, online monitoring of organic vapours without prior accumulation or sampling of the analyte. The gaseous samples are provided as headspace above aqueous solutions. The concentration in the gas phase was calculated from the concentration in solution at room temperature according to the respective Henry constants given in the literature. The enzymes employed are NAD-dependent formaldehyde dehydrogenase [EC 1.2.1.46] from Pseudomonas putida, alcohol oxidase [EC 1.1.3.13] from Pichia pastoris, and tyrosinase [EC 1.14.18.1] from mushroom. The gas diffusion working electrodes used in the sensors are based on a porous, hydrophobic PTFE membrane (exposed geometric electrode area: 1.77 cm(2)) covered with a porous layer of gold, platinum or graphite/Teflon. Detection limit, sensitivity, and measuring range are 34 microM (6.5 ppb), 117 nA/mM, and 0.46-66.4 mM for formaldehyde, 9.9 microM (55 ppb), 3.43 microA/mM, and 0.1-30 mM for ethanol, and 0.89 microM (0.36 ppb), 2.4 microA/mM, and 0.01-1 mM for phenol, respectively. Further sensor characteristics such as response time and stability are also determined: t(90%) (formaldehyde: 4.5 min; ethanol: 69 s; phenol: 27 min), stability at permanent exposure (formaldehyde: 63%, 15 h @ 2.62 mM; ethanol: 86%, 18 @ 1 mM; phenol: 86%, 16.5 h @ 0.1 M).