Methacrylated calix[4]arene phosphonic acids as functionalized crosslinker for radical polymerization

We describe the synthesis of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dioxypropylphosphonic acid‐26,28‐dimethacryloyloxy‐calix [4]arene and 5,11,17,23‐tetra‐tert‐butyl‐25‐oxypropylphosphonic acid‐27‐hydroxy‐26,28‐dimethacryloyloxy‐calix[4]arene starting from para‐tert‐butyl‐calix[4]arene. The complete reaction was proved by matrix‐assisted laser desorption ionization time of flight mass spectrometry and nuclear magnetic resonance spectroscopy. The influence of these compounds on the kinetics of the radical polymerization of methyl methacrylate was shown by dilatometry. Furthermore, the adhesive properties of dental adhesives containing these calix[4]arene derivatives were investigated. Copyright © 2012 Society of Chemical Industry     

Modification of poly(propylene) by grafted polyester‐amide‐based dendritic nanostructures with the aim of improving its dyeability

Fiber‐graded poly(propylene) was modified by polyester‐amide‐based dendritic nanostructures with the aim of improving its dyeability. Two different dendritic polymers were used and the dendritic nanostructures were formed in situ via reactive blending with maleic anhydride‐modified poly(propylene). Samples were chosen exploiting a 4‐component mixture design. Thermal, morphological, and rheological characterizations showed domains with different size and distribution were formed and primary properties of the dendritics determined the characteristics of the resulted domains. Morphological parameters were quantified by digital analysis of scanning electron microscope images. Thermal and rheological behavior also demonstrated good agreements with the inferred morphology of the formed dendritic domains. The modified samples were then dyed with dispersed dyestuffs. A variety of substantivities were obtained, and some of the modified samples showed a significant enhancement in dyeing properties. A predictive model was developed for K/S ratio, where K and S are absorption and scattering coefficients of the Kubelka‐Munk one constant theory, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the degree of branching on the glass transition temperature of polyesters

Glass transition temperature dependence on the branching degree can be empirically estimated by excluding additional effects on this parameter as molecular weight distribution, end group interactions or crystallization. In this communication aliphatic–aromatic polyesters with a well defined degree of branching between 0% (linear) and 50% (hyperbranched) are investigated by differential scanning calorimetry. The hydrogen bonding effect of the OH-terminal groups was successfully extracted from the pure branching effect by protection of the end-functionalities. Fractionation of samples with variation of the branching degree and end-functionalities led to series of narrowly distributed molar masses. The dependence of the molecular weight on the glass transition temperature for different branching degrees was calculated and compared for polar and non-polar end groups.     

Arduino-based slider setup for gas–liquid mass transfer investigations: Experiments and CFD simulations

The implementation of traditional sensors is a drawback when investigating mass transfer phenomena within microstructured devices, since they disturb the flow and reactor characteristics. An Arduino based slider setup is developed, which is equipped with a computer-vision system to track gas–liquid slug flow. This setup is combined with an optical analytical method allowing to compare experimental results against CFD simulations and investigate the entire lifetime of a single liquid slug with high spatial and temporal resolution. Volumetric mass transfer coefficients are measured and compared with data from literature and the mass transfer contribution of the liquid film is discussed.     

Short SiC fiber/Ti3SiC2 MAX phase composites: Fabrication and creep evaluation

The compressive creep of silicon carbide fiber reinforced Ti₃SiC₂ MAX phase with both fine and coarse microstructure was investigated in the temperature range of 1000-1300°C. Comparison of only steady-state creep was done to understand the response of fabricated composite materials toward creep deformation. It was demonstrated that the fibers are more effective in reducing the creep rates for the coarse microstructure by an increase in activation energy compared to the variant with a finer microstructure, being partly a result of the enhanced creep rates for the microstructure with larger grain size. Grain boundary sliding along with fiber fracture appears to be the main creep mechanism for most of the tested temperature range. However, there are indications for a changed creep mechanism for the fine microstructure for the lowest testing temperature. Local pores are formed to accommodate differences in strain related to creeping matrix and predominantly elastically deformed fibers during creep. Microstructural analysis was done on the material before and after creep to understand the deformation mechanics.     

Lab-Scale Microreactor Plant for the Study of Methylations with Liquid Chloromethane

Chloromethane is an important reagent for methylations in the process industry. However, as a gas suspected of causing cancer, it is rarely used at laboratory scale. Therefore, a setup is presented here for studies in a laboratory under safe and reproducible conditions. The use of a microreactor guarantees high heat transfer rates and a low holdup of the reagent. As a proof-of-concept, the reaction of chloromethane with the secondary amine morpholine in aqueous solution is investigated. By applying elevated pressures, a liquid-liquid system with enhanced solubility of chloromethane in the aqueous phase is accessible.     

Investigations on Selectivity of Gas-Liquid Reactions in Capillaries

Biocatalysis offers a broad spectrum of possible ecological and economic advantages over conventional chemical catalysis processes, e.g., lower energy consumption and high enantio selectivity. The focus of this work is on gas-liquid reactions. These are of great importance in the chemical and biochemical industry and subject of current research since they are often limited by mass transfer or show low selectivity. Different suitable biocatalytically gas-liquid reaction systems were tested in capillary reactor designs in order to obtain information about the interaction between reaction and fluid mechanics. Furthermore, an optical measuring method was established. The experiments were performed in batch mode in a glass beaker with a flow cuvette for UV/Vis measurement of product concentration.     

Der Schnellstart in die digitale Lehre unter Corona-Randbedingungen

The corona lockdown and campus closure of the TU Dortmund University led to a fully digital summer semester 2020 of the Faculty of Biochemical and Chemical Engineering. Completely digital? No! This article gives examples of different digital courses. From the perspective of the Dean of Studies, experiences and personal reflections on this unusual semester until July 2020 are presented. After a short introduction, measures for digital teaching with the gradual partial opening are described. Especially the exchange of experiences together with the students' feedback brought interesting results and experiences with digital tools. The lessons learned are outlined together with recommendations for different digital tools and an outlook on upcoming semesters.     

EGFR-Binding Peptides: From Computational Design towards Tumor-Targeting of Adeno-Associated Virus Capsids

The epidermal growth factor receptor (EGFR) plays a central role in the progression of many solid tumors. We used this validated target to analyze the de novo design of EGFR-binding peptides and their application for the delivery of complex payloads via rational design of a viral vector. Peptides were computationally designed to interact with the EGFR dimerization interface. Two new peptides and a reference (EDA peptide) were chemically synthesized, and their binding ability characterized. Presentation of these peptides in each of the 60 capsid proteins of recombinant adeno-associated viruses (rAAV) via a genetic based loop insertion enabled targeting of EGFR overexpressing tumor cell lines. Furthermore, tissue distribution and tumor xenograft specificity were analyzed with systemic injection in chicken egg chorioallantoic membrane (CAM) assays. Complex correlations between the targeting of the synthetic peptides and the viral vectors to cells and in ovo were observed. Overall, these data demonstrate the potential of computational design in combination with rational capsid modification for viral vector targeting opening new avenues for viral vector delivery and specifically suicide gene therapy.     

Rather the Rule than the Exception: Non-Convex Pareto Sets and their Navigation in Distillation Processes

Novel algorithms for adaptive approximation and interactive navigation of Pareto sets are applied to various homogeneous distillation processes with recycle streams within an industrial flowsheet simulator. The adaptive approximation scheme shows that the Pareto set consists of both convex and non-convex regions when the product purities are maximised while minimising the total heat duties. It is illustrated how such Pareto sets can be navigated interactively using a ray tracing technique. Our results suggest that the occurrence of non-convex regions in the Pareto sets is due to recycle streams in the flowsheets and is therefore the rule rather than the exception in multi-objective optimisation of flowsheet simulations in chemical engineering.