Electromodified NiFe Alloys as Electrocatalysts for Water Oxidation: Mechanistic Implications of Time-Resolved UV/Vis Tracking of Oxidation State Changes.

Facile electromodification of metallic NiFe alloys leads to a series of NiFe oxyhydroxide surface films with excellent electrocatalytic performance in alkaline water oxidation. During cyclic voltammetry and after sudden potential jumps between noncatalytic and catalytic potentials, Ni oxidation/reduction was tracked with millisecond time resolution by a UV/Vis reflectance signal. Optimal catalysis at intermediate Ni/Fe ratios is explained by two opposing trends for increasing Fe content: a) pronounced slowdown of the Ni2+ /Ni3+ oxidation step and b) increased reactivity of the most oxidized catalyst state detectable at catalytic potentials. This state may involve an equilibrium between Ni4+ ions and Ni2+ ions with neighboring ligand holes, possibly in the form of bound peroxides.

Methanol from CO2 by organo-cocatalysis: CO2 capture and hydrogenation in one process step.

Carbon dioxide chemically bound to alcohol-amines was hydrogenated to methanol under retrieval of these industrially used CO2 capturing reagents. The energetics of the process can be seen as a partial cancellation of the exothermic heat of reaction of the hydrogenation with the endothermic one of the CO2 release from the capturing reagent. The process provides a means to significantly improve the energy efficiency of CO2 to methanol conversions.

Degradation of selected (bio-)surfactants by bacterial cultures monitored by calorimetric methods.

The subjects of the article are investigations concerning the ability of both Rhodococcus opacus 1CP and mixed bacterial cultures to use selected surfactants as sole carbon and energy source. In a comparative manner the biosurfactants rhamnolipid, sophorolipid and trehalose tetraester, and the synthetic surfactant Tween 80 were examined. Particular emphasis was put on a combinatorial approach to determine quantitatively the degree of surfactant degradation by applying calorimetry, thermodynamic calculations and mass spectrometry, HPLC as well as determination of biomass. The pure bacterial strain R. opacus was only able to metabolize a part of the synthetic surfactant Tween 80, whereas the mixed bacterial cultures degraded all of the applied surfactants. Exclusive for the biosurfactant rhamnolipid a complete microbial degradation could be demonstrated. In the case of the other surfactants only primary degradation was observed.

Calorimetric investigations into the starvation response of Pseudomonas putida growing on phenol and glucose.

AIMS: To investigate the stress response during nutrient deprivation, particularly with regard to the application of phenol as growth substrate of Pseudomonas putida with calorimetric measurements as a new method. METHODS AND RESULTS: The online and noninvasive measurement of the thermal power P(0) permits the detection of microbial activity during the starvation period. While the results of the investigations with phenol reveal a significant loss of activity as a function of the temporal nutrient dosage, only a small loss of activity was detected by using glucose. Microbiological methods (colony forming units (CFU) and activity of catechol-2,3-dioxygenase) showed a loss of the enzyme activity at a constant CFU. The introduction of a simple decay parameter k(D) in the kinetic description of the growth process on phenol was sufficient for the successful kinetic modelling. CONCLUSIONS: The combination of calorimetric measurements and the determination of the enzymatic activity proved the loss of activity of Ps. putida during the deprivation of the substrate phenol. SIGNIFICANCE AND IMPACT OF THE STUDY: The initial heat power (P(0)) proves to be a suitable parameter for the characterization of the physiological state of the culture and can be used for the regulation of nutrient supply in biotechnological process development.