Oxidation of the reduced (pink) phosphate-free bovine spleen acid phosphatase with 1.5 mol HzOz or sodium peroxodisulfate/mol, in the presence of Mes or Bistris pH 5, leads to a species with an absorption maximum at 558 nm. Addition of acetate or oxidation in the presence of acetate buffer engenders a species with a maximum at 550 nm. Addition of phosphate to both species shifts the maximum immediately to 540 nm; this is the species also found after preparation from the spleen. The assumption that these species represent strongly bidentatebinding hydroxo, acetato and phosphato complexes of the Fe(II1)-Fe(II1) system is supported by replacement reactions with other ligating oxoanions followed by their typical spectral shifts. These oxoanion complexes cannot be dissociated by gel filtration; this is possible only after reduction to the Fe(I1)-Fe(II1) system. The oxidized species without EPR signals below g values of 2 still reveals 5% activity which cannot be reduced to zero even in the presence of higher concentrations of peroxodisulfate. The pH optimum of the reaction with a-naphthyl phosphate shifts from 5.9 to 5.3 in the oxidized species.The apparent pK values around 4.5 as derived from the pH dependence of activity, of the EPR spectra, and the spectral shifts of the phosphate-saturated reduced and oxidized species are assigned to an aquo/hydroxo equilibrium at the Fe(Il1) or an equilibrium, where the phosphato ligand is replaced by a hydroxo ligand. A reaction mechanism is proposed in which a hydroxo ligand at the chromophoric Fe(II1) attacks the phosphoric acid ester group only when that is monoprotonated and pre-oriented by electrostatic interaction with the nonchromophoric metal ion. Binding and inhibition studies with the oxoanions indicate that they compete with the catalytically active hydroxo group of the reduced and oxidized enzyme with nearly the same inhibition constants. Catalysis is not affected by the oxoanions which replace the additional p-hydroxo ligand in the 558-nmabsorbing Fe(II1)-Fe(II1) species. In contrast to hemerythrin and ribonucleotide reductase, a binuclear iron center is proposed for the purple acid phosphatase, which is bridged by a carboxylato and two aquo/hydroxo groups, but without a p-0x0 bridge.Mammalian purple tartrate-resistant acid phosphatases (PAP) [l, 21 have been isolated from porcine uterus [3], bovine spleen [4, 51, rat spleen [6] and rat bone [7]. They are glycoproteins [4-81 with molecular masses of 35 kDa with a monomeric peptide structure. The chain of the bovine enzyme seems to be split into two nonidentical subunits [5]

Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH3, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH3, are summarized. The electrical response to NH3 obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed.

The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia.

In application as a thermal barrier coating (TBC), partially stabilized zirconia (Zr) approaches some limits of performance. To further enhance the efficiency of gas turbines, higher temperature capability and a longer lifetime of the coating are needed for the next generation of TBCs. This paper presents the development of new materials and concepts for application as TBC. Materials whose compositions have the pyrochlore structure or doped Zr are presented in contrast with new concepts like nanolayers between the top and bond coat, metal-glass composites, and double-layer structures. In the last concept, the new compositions are used in a combination with Zr, as a double, multi, or graded layer coating. In this case, the benefits of Zr will be combined with the promising properties of the new top coating. In the case of metal-glass composites, the paper will be focused on the influences of different plasma spraying processes on the microstructure. The performance of all these different coating systems has been evaluated by burner rig tests. The results will be presented and discussed.

Recently, a novel method emerged to determine the oxygen storage degree of three way catalysts (TWC) by a microwave-based method. Up to now, this method has been investigated only in lab-scale reactors or under steady state conditions. This work expands those initial studies. A TWC-coated gasoline particulate filter was investigated in a dynamic engine test bench simulating a typical European driving cycle (NEDC). It could be shown that both the oxygen storage degree and the soot loading can be monitored directly, but not simultaneously due to their competitive effects. Under normal driving conditions, no soot accumulation was observed, related to the low raw emissions and the catalytic coating of the filter. For the first time, the quality factor of the cavity resonator in addition to the resonance frequency was used, with the benefit of less cross sensitivity to inconstant temperature and water. Therefore, a temperature dependent calibration of the microwave signal was created and applied to monitor the oxidation state in transient driving cycles. The microwave measurement mirrors the oxidation state determined by lambda probes and can be highly beneficial in start-stop phases (where lambda-probes do not work) and to determine the oxygen storage capacity (OSC) without unnecessary emissions.