Chemically and enzymatically catalyzed synthesis of C6–C10 alkyl benzoates

The esterification of benzoic acid with n‐hexanol, n‐octanol, 2‐ethyl hexanol and n‐decanol was investigated in detail. An analysis of the reaction kinetics of esterification in the presence of different commercially available chemical catalysts was carried out. The effects of catalyst type and loading on the reaction rate were studied. Although the considered reaction is bimolecular, it showed a first‐order behavior, and a linear dependence with respect to the catalyst concentration was observed. Hence, a new approach is presented to describe the reaction kinetics accurately over a wide range. The application of biotechnological synthesis applying different enzymes as catalysts offers an interesting alternative besides chemical synthesis. Especially an esterase from Bacillus subtilis immobilized on Sepabeads EC‐EP showed high stability and was applied for 2 days in the synthesis of hexyl benzoate. Nevertheless, the chemical reaction route remains superior with respect to the catalyst activities under the applied conditions, which were 25 kU/g for the chemical reaction and 0.7 kU/g for the best enzymatic conversion.     

Pharmacological Promiscuity: Dependence on Compound Properties and Target Specificity in a Set of Recent Roche Compounds

What parameters determine promiscuity? A compound's potential for promiscuity (pharmacological activity at multiple targets) may be influenced by molecular parameters such as ionization state, lipophilicity, and molecular weight. In an analysis of recent Roche compounds we found that a positive charge is an important determinant for potential promiscuity; aminergic activity was found to be the main reason for overt promiscuity.

     

Influence of Irradiation Temperature on Grafting of Styrene into Poly(tetrafluoroethylene‐co‐hexafluoropropylene) Films

This study concerns with the investigation of the effect of irradiation conditions on grafting of styrene into FEP films by the pre‐irradiation method. EPR spectroscopy was used to characterize the base polymer material regarding the trapped radical species and their concentration. Radiation‐induced changes in the chemical structure were studied by IR spectroscopy. Tensile strength and elongation at break as well as yield of grafting were found to be strongly influenced by irradiation temperature. Main‐chain scissions were identified to be the reason for the deterioration of the mechanical properties after radiation treatment at temperatures below glass transition temperature.

     

Analytical investigation of the composition of plasma-induced functional groups on carbon nanotube sheets

To increase the applicability of carbon nanotubes (CNTs) oxygen-containing functional groups were generated on their widely inert surface by using glow-discharge plasmas. CNT-sheets (bucky papers) produced from the powder-like raw material were used as substrates allowing for a more defined characterization of one and the same surface by different analytical techniques. The plasma composition was analyzed by optical emission spectroscopy. Since the actual composition of the plasma-induced functional groups has still not been completely resolved, we performed an in-depth characterization of the treated samples by X-ray photoelectron (XPS) and Raman spectroscopy as well as electron spin resonance measurements. To overcome limitations of the XPS-analysis in distinguishing between groups featuring nearby binding energies, alcohol-, keto-/aldehyde-, and carboxyl-groups were tagged by derivatization techniques using fluorine-containing reagents (trifluoroaceticanhydride, trifluoromethylphenylhydrazine, and trifluoroethanol). Differential spectra were calculated to enhance the accuracy of the deconvolution of the XPS-spectra. This enabled us to determine dependencies of the plasma parameters, i.e. treatment time, process pressure, and gas composition (mixtures of Ar, O₂, H₂O, and H₂), on the composition of the generated functional groups as well as an up to 6-fold enhancement in derivatizable groups for switching process gas from Ar/O₂ to Ar/H₂O.     

A Silicon Nanocrystal Schottky Junction Solar Cell produced from Colloidal Silicon Nanocrystals

Solution-processed semiconductors are seen as a promising route to reducing the cost of the photovoltaic device manufacture. We are reporting a single-layer Schottky photovoltaic device that was fabricated by spin-coating intrinsic silicon nanocrystals (Si NCs) from colloidal suspension. The thin-film formation process was based on Si NCs without any ligand attachment, exchange, or removal reactions. The Schottky junction device showed a photovoltaic response with a power conversion efficiency of 0.02%, a fill factor of 0.26, short circuit-current density of 0.148 mA/cm², and open-circuit voltage of 0.51 V.     

Modelling of orthogonal cutting processes with the method of smoothed particle hydrodynamics

In the last decades, mesh-free methods for simulating various cutting processes have been used very widely as they can eliminate numerical problems in the simulation of material failure and large plastic deformations. This paper deals with the results from modelling the orthogonal cutting of AISI 1045 steel using smoothed particle hydrodynamics (SPH) method. Moreover, it is determined how the parameters of the SPH solver such as initial smoothing length, initial particle density and coefficient for the timestep increase affect the prediction error for the values of cutting force and chip compression ratio as well as computing time. The optimum values of the SPH solver parameters are determined by minimising an objective function. The best balance between the prediction error of machining variables and computing time is achieved for an initial particle density of 40 μm and a coefficient for the timestep increase of 0.4.     

Effect of Long-Term Forest Fertilization on Scots Pine Xylem Quality and Wood Borer Performance

We tested whether changes in long-term nutrient availability would affect the xylem quality and characteristics of Scots pine trees as a food source for the larvae of the xylophagous wood borer Hylotrupes bajulus L. (Cerambycidae). We looked for an effect of host plant growth and xylem structural traits on H. bajulus larval performance, and looked for delayed effects of long-term forest fertilization on xylem chemical quality. In general, larval performance was dependent on larval developmental stage. However, the growth of larvae also varied with host plant quality (increases in the concentration of nitrogen and carbon-based secondary compounds of xylem were correlated with a decrease in the larval growth rate). The greater annual growth of trees reduced tracheid length and correlated positively with second-instar H. bajulus growth rate. This is consistent with the hypothesis that intrinsic growth patterns of host plants influence the development of the xylophagous wood borer H. bajulus.     

Liquid flow texture analysis in trickle bed reactors using high-resolution gamma ray tomography

Trickle bed reactor performance and safety may suffer from radial and axial liquid maldistribution and thus from non-uniform utilization of the catalyst packing. Therefore, experimental analysis and fluid dynamic simulation of liquid–gas flow in trickle bed reactors is an important topic in chemical engineering. In the present study for the first time a truly high-resolution gamma ray tomography technique was applied to the quantitative analysis of the liquid flow texture in a laboratory cold flow trickle bed reactor of 90 mm diameter. The objective of this study was to present the comparative analysis of the liquid flow dynamics for two different initial liquid distributions and two different types of reactor configurations. Thus, the hydrodynamic behavior of a glass bead packing was compared to a porous Al₂O₃ catalyst particle packing using inlet flow from a commercial spray nozzle (uniform initial liquid distribution) and inlet flow from a central point source (strongly non-uniform initial liquid distribution), respectively. The column was operated in downflow mode at a gas flow rate of 180 L h⁻¹ and at liquid flow rates of 15 and 25 L h⁻¹.     

Analysis and specification of the crash behaviour of plastics/metal-hybrid composites by experimental and numerical methods

Plastics materials are nowadays used in many structural applications for the substitution of metals with respect to weight reduction. In order to utilize the high freedom of design and the light-weight potential of plastics materials in crash-relevant structural parts, so-called hybrid composites which combine the high rigidity and strength of steel with the advantages of plastics materials are investigated in the outlined research. Thereby, the joining of both materials as well as the design by means of numerical methods such as the finite element analysis (FEA) are challenges which have to be met. A new approach in joining is based on the modified arc welding process where metal pin structures are formed in one working step and subsequently welded onto the surface. The pins are formed with ball-shaped, cylindrical or spiky ends and produced directly from the welding wire without requiring additional pre-fabricated components such as studs or similar. This allows the small-scale surface structuring of metal components that can be adapted optimally for a form fit on the respective plastics structure. Subsequently, injection molding is used for the application of the plastics material onto the pin-structured metal part in order to generate a positive fit between metal and plastics in an intrinsic joining process. An additional joining process, which is carried out after injection molding, is not required. Within the framework of the research presented, comprehensive mechanical tests are presented to illustrate the suitability of pin-structured metal-hybrid composites in crash applications. In comparison to structures which are in particular exposed to static loads and therefore designed to exhibit maximum component strength, crash applications are designed to fail in a continuous process to achieve maximum energy consumption. The outlined research illustrates the enhanced failure behavior of pin-structured plastics/metal-hybrid composites and the increased energy consumption under impact loading. Moreover, a comparison between pin structuring and laser structuring with regard to the obtainable mechanical properties under impact loading is given. Concluding, the current potential and weak points in the simulation of plastics/metal-hybrid structures using FEA is presented and discussed.     

Selective Oxidation of Propene with Air to Propylene Oxide,a Case Study of Autoxidation Versus Catalytic Oxidation with AMM-Catalysts

The formation of propylene oxide from propene by direct oxidation with air has been studied with a series of new microporous amorphous catalysts containing isolated active sites. Although the materials showed good activities as heterogeneous oxidation catalysts, the formation of acroleine dominated in the gas phase. Oxidation selectivities of the various catalysts are reported. Significant PO-formation was only observed under reaction conditions involving pressures larger 5 bar. Promoting effects of solvents or additives like acetaldehyde could be excluded. Best results were observed in continuous gas phase flow experiments. All catalysts studied proved detrimental to the PO-yield and control experiments pointed to catalyst free autoxidation conditions. A factorial design followed by an optimization of the reaction conditions provided PO-selectivities of 60 % at propene conversion of 11.4 % (T = 290 °C; pressure = 25 bar; propene content = 75 %; total feed = 39.5 ml/min) at continuous reaction conditions. By passivating the inner reactor surfaces with gold, a PO-selectivity of 62.8 % at a propene conversion of 15.1 % could be obtained, indicating, that autoxidation of propene may become a serious contender in the search for improved production processes. This work is a case study of attempted catalyzed selective oxidation with air illustrating potential pitfalls and misleading interpretations.