CuI and H2O2 Inactivate and FeII Inhibits [Fe]‐Hydrogenase at Very Low Concentrations

[Fe]‐Hydrogenase (Hmd) catalyzes reversible hydride transfer from H₂. It harbors an iron‐guanylylpyridinol as a cofactor with an Fe^II that is ligated to one thiolate, two COs, one acyl‐C, one pyridinol‐N, and solvent. Here, we report that Cu^I and H₂O₂ inactivate Hmd (half‐maximal rates at 1 μM Cu^I and 20 μM H₂O₂) and that Fe^II inhibits the enzyme with very high affinity (K_i=40 nM ). Infrared and EPR studies together with competitive inhibition studies with isocyanide indicated that Cu^I exerts its inhibitory effect most probably by binding to the active site iron‐thiolate ligand. Using the same methods, it was found that H₂O₂ binds to the active‐site iron at the solvent‐binding site and oxidizes Fe^II to Fe^III. Also it was shown that Fe^II reversibly binds away from the active site iron, with binding being competitive to the organic hydride acceptor; this inhibition is specific for Fe^II and is reminiscent of that for the [FeFe]‐hydrogenase second iron, which specifically interacts with H₂.     

PGSS-drying: Mechanisms and modeling

Micronization of polyethylene glycol from aqueous solutions has been successfully performed with particles from gas-saturated solutions (PGSS)-drying process, producing spherical PEG particles with average particle size of 10 μm and residual water content below 1 wt%. Based on experimental results, an analysis of the fundamentals of the process has been developed, discussing mass and energy balances, phase equilibrium conditions, mass transfer rates and atomization mechanisms. Some discrepancies between experimentally observed moisture concentration in powder and calculations based on the mass balance and the phase equilibrium have been observed, which have been attributed to the kinetic evolution of pressure and temperature along the expansion path. The static mixer used to saturate the solution with CO₂ has been analyzed with phase equilibrium and mass transfer calculations, concluding that a significant fraction of water is extracted to the gas phase already in the static mixer, and high CO₂ concentrations are achieved in the liquid due to the high solubility of CO₂ in PEG. All experimental trends of variation of particle size with process parameters can be explained considering a flash-boiling atomization mechanism dependant on the concentration of CO₂ in the solution after the static mixer.     

The effect of water temperature on the adsorption equilibrium of dissolved organic matter and atrazine on granular activated carbon

The influence of water temperature on the adsorption of natural dissolved organic matter (DOM) on activated carbon has not been investigated intensively yet. In this study, batch experiments with granular activated carbon (GAC) have been carried out at three temperatures (5 degrees C, 20 degrees C, 35 degrees C) using a humic acid model water and different types of surface water (lake, river, canal). Furthermore, the adsorption of an anthropogenic contaminant, atrazine, was quantified in the absence and presence of DOM. The results indicate a significant influence of water temperature on the adsorption equilibrium of DOM and atrazine. Contrary to expectations, DOM and atrazine adsorption in surface water tends to be increased with increasing water temperature, whereas the extent of this effect is dependent on the type and concentration of DOM. Furthermore, the temperature effect on atrazine adsorption is controlled by competition of DOM and atrazine on adsorption sites. Some assumptions are proposed and discussed for explaining the temperature effects observed in the batch studies.     

APPLICATION OF CONCENTRATED SOLAR RADIATION TO HIGH TEMPERATURE DETOXIFICATION AND RECYCLING PROCESSES OF HAZARDOUS WASTES

In many cases, hazardous wastes are subject to thermal treatment at elevated temperatures. Some types of wastes do not have a sufficient calorific value to cover the heat demand of the high temperature process. For thermal treatment of e.g. filter residues, dusts, sulfuric acid, aluminium dross, foundry sand, or waste water, supplementary energy supply is needed. The specific energy demand ranges from 0.5 to 2.5 kWh/kg (2–10 MJ/kg). An important aim of process optimisation is the reduction of (fossil) energy consumption and exhaust gas flow. Concentrated solar energy promises advantages when applied to high energy consuming waste treatment processes with regard to substitute fossil or electric energy consumption, to reduce CO₂ emissions, and exhaust gas flow. In parallel to conceptional studies, a solar-heated rotary kiln mini-plant has been designed and constructed for tests in the DLR solar furnace. The tests will give indications of boundary conditions for solar thermal treatment or conversion of selected hazardous materials.     

Effective Formal Reduction of Linear Differential Systems

In this paper we present a new method for the formal reduction of linear differential systems. We generalize classical results and concepts and obtain new characterizations of existing notions. Our main result is a generalization of the classical Splitting Lemma. This leads to an algorithm for computing formal invariants and solutions in a more efficient way. Received: March 9, 1999; revised version: September 2, 1999     

Modeling of a semi-hermetic CO2 reciprocating compressor including lubrication submodels for piston rings and bearings

A comprehensive model for a semi-hermetic CO₂ reciprocating compressor is presented. This comprehensive model is composed of three main sub-models simulating the geometry and kinematics, the compression process, and frictional power loss. Valve and leakage sub-models are included in the compression process model. The frictional power loss model includes the friction at the bearings and between the piston ring and cylinder wall. The predicted results of the comprehensive model are validated using external compressor performance measurements of compressor input power and mass flow rate. The mass flow rate and compressor input power are predicted to within 4.03% and 6.43% mean absolute error, respectively, compared to the experimental datum. Additionally, a parametric study is presented which investigates compressor performance as a function of the stroke-to-bore ratio.     

Preparation of Ring-Shaped Thermoelectric Legs from PbTe Powders for Tubular Thermoelectric Modules

Waste heat recovery—for example, in automotive applications—is a major field for thermoelectric research and future application. Commercially available thermoelectric modules are based on planar structures, whereas tubular modules may have advantages for integration and performance in the field of automotive waste heat recovery. One major drawback of tubular generator designs is the necessity for ring-shaped legs made from thermoelectric material. Cutting these geometries from sintered tablets leads to considerable loss of thermoelectric material and therefore high cost. Direct sintering of ring-shaped legs or tubes of thermoelectric material is a solution to this problem. However, sintering such rings with high homogeneity and density faces some difficulties related to the mechanical properties of typical thermoelectric materials such as lead telluride (PbTe)—particularly brittleness and high coefficient of thermal expansion. This work shows a process for production of thermoelectric rings made of p- and n-doped PbTe. Long tubes of PbTe have been sintered in a current-assisted sintering process with specially designed sintering molds, coated with a diffusion barrier, and finally cut into ring-shaped slices. To demonstrate the technology, a tubular thermoelectric module has been assembled using these PbTe rings.     

Produktivitätssteigerung durch integrierte Produktionstechnik und Verfahrens-Know-how

Increasing Productivity through Integrated Production Engineering and Processing Expertise The future of production engineering is interdisciplinary. Between product innovation and product marketing there lies a design process which has to be optimised and which is interdisciplinary in character. The design process has to satisfy the demands of global markets on chemical products, which lead, for example, to shorter and shorter product life cycles, and to demands for low production costs, high and consistent product quality, and faster market launches.