Enzymatic esterification of glycerol I. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols

Regioisomerically pure 1,3-sn-diacylglycerols are conveniently prepared in high yields (>80%) and in large quantities by enzymatic esterification of glycerol in the presence of various 1,3-selective lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) and a variety of different acyl donors like free fatty acids, fatty acid alkyl esters and vinyl esters. All reactions are carried out in aprotic organic solvents of low water content, namelyn-hexane, diethyl ether or tBuOMe. The creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction media by the adsorption of glycerol onto a solid support prior to use was essential for the success of these transformations. The effects of reaction conditions and the regioselectivities of the lipases on the product yields are described in detail.     

Statistical Analysis of the Intergranular Film Thickness in Silicon Nitride Ceramics

Silicon nitride materials typically reveal thin amorphous intergranular films along grain boundaries, with only the exception of special boundaries. It is known that such grainboundary films strongly affect the high-temperature properties of the bulk material. High-resolution electron microscopy (HREM) was used to study these amorphous films in different Si₃N₄ ceramics. The observed film thicknesses at grain boundaries in these materials varied between 5and 15 Å. It was shown that the grain-boundary film thickness strongly depends on film chemistry. Careful inspections of film-thickness measurements across grain boundaries in a given material suggest that the film widths vary on the order of 1 Å. Therefore, a quantitative evaluation should allow for the determination of the standard deviation of the film thickness. The amorphous film widths along grain boundaries in four materials were measured over the entire length (up to 1 μm) of the grain boundary between two triple points. Forty to fifty data points were evaluated for each boundary, giving a Gaussian-like distribution of the film thickness around a median value, which corresponded well with the film width measured from single HREM micrographs. The accuracy achieved by the statistical method was better than ± 1 Å.     

Alumina Grown during Deposition of Thermal Barrier Coatings on NiCrAlY

The microstructure of Al₂O₃ formed by oxidation of a model NiCrAlY alloy during electron-beam physical vapor deposition of ZrO₂–7.6 mol% YO_1.5 is examined and compared with that formed on the bare substrate. The growth rate, morphology, and chemical composition of the oxide vary among the different constituents of the alloy surface and are further influenced by the O₂ partial pressure and the physical presence of the thermal barrier coating (TBC) layer. These differences, however, are largely limited to the outer oxide layer. The interplay between the TBC and the growing oxide leads to the formation of a fine-grain Al₂O₃–ZrO₂"mixed zone" within the thermally grown oxide. A mechanism is outlined to explain this behavior, based on the dissolution of ZrO₂ in a transient Al₂O₃ structure growing by outward diffusion of Al, and its subsequent reprecipitation when the metastable phase transforms to the stable α-Al₂O₃ form.     

Korrosion von ölgefeuerten Zentralheizungskesseln

Corrosion of oil-fired domestic boilers Depending on the surface temperature of the flue gas side the corrosion of oil fired domestic boilers proceeds either mainly by acid corrosion or by oxygen corrosion:

• – At surface temperatures of 60°C and higher the corrosion mechanism of acid corrosion prevails and the corrosion rates amount to 0.1–0.3 mm/year (values referred to continuous burner operation). The corrosion products consist of soluble iron(II)- and iron(III)sulfates. Higher corrosion rates can be attributed to an appreciable catalytic formation of sulfur trioxide on the corrosion products formed on the convective heating surfaces.
• – At surface temperatures of 40°C the mechanism of oxygen corrosion already dominates and the corrosion rates are about ten times higher (1.5–3 mm/year, referred to continous burner operation). The high portion of ioron oxide hydrates, especially goethit (α-FeOOH), makes the corrosion products difficult to remove.
• – Distinctly reduced service lives are also expected for the so called reduced temperature boilers (“Niedertemperaturkessel”) and low temperature boiers (“Tieftemperaturkessel”): According to the manufacturers these boilers may be operated at boiler water temperatures well below 60°C, as they are equipped with constructive measures to enhance the surface temperature on the flue gas side. However, these measures are only fully effective under stationary conditions.

Some of the results were obtained from weight loss measurements on test specimen made from St 35.8 and gray cast iron, that were exposed to the flue gases of an oil fired experimental boiler. Other important results come from field measurements of the sulfuric acid content of about 30 boilers that are in practical use.     

Effect of substrate surface roughness on the adherence of NiCrAlY thermal spray coatings

The adherence of plasma sprayed NiCrAlY bond coats can be improved by an appropriate substrate surface finish. The interface fracture energy for crack propagation along the coating/substrate interface has been measured for different surface roughness by means of a specially designed four-point bending test. An increase of the interface fracture energy of about 15% was observed for a three times higher surface roughness. In addition, four-point bending tests with the coating on the side face of bending specimens were performed to analyze the fracture and spalling behavior of the coatings both under large tensile and compressive substrate deformations.     

Topology optimization of a cantilevered piezoelectric energy harvester using stress norm constraints

Vibrational piezoelectric energy harvesters are devices which convert ambient vibrational energy into electric energy. Here we focus on the common cantilever type in which an elastic beam is sandwiched between two piezoelectric plates. In order to maximize the electric power for a given sinusoidal vibrational excitation, we perform topology optimization of the elastic beam and tip mass by means of the SIMP approach, leaving the piezoelectric plates solid. We are interested in the first and especially second resonance mode. Homogenizing the piezoelectric strain distribution is a common indirect approach increasing the electric performance. The large design space of the topology optimization approach and the linear physical model also allows the maximization of electric performance by maximizing peak bending, resulting in practically infeasible designs. To avoid such problems, we formulate dynamic piezoelectric stress constraints. The obtained result is based on a mechanism which differs significantly from the common designs reported in literature.     

A knowledge-based approach to manage information systems interoperability

Interoperability is a key property of enterprise applications, which is hard to achieve due to the large number of interoperating components and semantic heterogeneity. The inherent complexity of interoperability problems implies that there exists no silver bullet to solve them. Rather, the knowledge about how to solve wicked interoperability problems is hidden in the application cases that expose those problems. The paper addresses the question of how to organise and use method knowledge to resolve interoperability problems. We propose the structure of a knowledge-based system that can deliver situation-specific solutions, called method chunks. Situational Method Engineering promotes modularisation and formalisation of method knowledge in the form of reusable method chunks, which can be combined to compose a situation-specific method. The method chunks are stored in a method chunk repository. In order to cater for management and retrieval, we introduce an Interoperability Classification Framework, which is used to classify and tag method chunks and to assess the project situation in which they are to be used. The classification framework incorporates technical as well as business and organisational aspects of interoperability. This is an important feature as interoperability problems typically are multifaceted spanning multiple aspects. We have applied the approach to analyse an industry case from the insurance sector to identify and classify a set of method chunks.     

Immunoglobulin 1 (IgG1) Fc-glycosylation profiling of anti-citrullinated peptide antibodies from human serum

In several autoimmune disorders, including rheumatoid arthritis (RA), autoantibodies are thought to be the driving force of pathogenicity. Glycosylation of the Fc-part of human Igs is known to modulate biological activity. Hitherto, glycosylation of human IgG-Fc has been analyzed predominantly at the level of total serum IgG, revealing reduced galactosylation in RA. Given the pathogenic relevance of autoantibodies in RA, we wished, in the present study, to address the question whether distinct Fc-glycosylation features are observable at the level of antigen-specific IgG subpopulations. For this purpose, we have developed a method for the microscale purification and Fc-glycosylation analysis of anti-citrullinated peptide antibodies (ACPA). ACPA represent a group of autoantibodies that occur with unique specificity in RA patients. Their presence is associated with increased inflammatory disease activity and rapid joint destruction. Results indicate that ACPA of the IgG1 subclass vary considerably from total serum IgG1 with respect to Fc-galactosylation, with galactosylation being higher on ACPA than on serum IgG1 for some patients, while other patients show higher galactosylation on serum IgG1 than on ACPA. Using this method, studies can be performed on the biological and clinical relevance of ACPA glycosylation within RA patient cohorts.