Liquid flow and phase holdup—measurement and CFD modeling for two-and three-phase bubble columns

Bubble columns are an important class of contacting devices in chemical industry and biotechnology. Their simple setup makes them ideal reactors for two- and three-phase operations such as fermentations or heterogeneous catalysis. Still, design and operation of these reactors is subject to widely empirical scale-up strategies. With recent advances in the development of measurement techniques, a more detailed approach to the development of optimized reactors for specific operations should become possible. This report is based on detailed measurements of local dispersed phase holdups in a pilot plant-sized bubble column operated at high superficial gas velocities and solid holdups. It deals with the influence of superficial gas velocity, solid loading and sparger geometry on measured and computed liquid flow velocities and holdup distributions. Liquid velocity measurements have been performed using the electrodiffusion method, modeling calculations have been carried out using the computational fluid dynamics (CFD) code CFX-4.3. Measurement results presented here give an insight into the development of liquid circulation and fluctuating velocity distribution depending on superficial gas velocity, solid loading and sparger geometry. CFD results implementing a multi-fluid model with k-ε turbulence and special momentum exchange terms for direct gas-solid interactions show that, even on standard PC workstations, this kind of computations can deliver qualitatively reasonable agreement with measurements.     

New polymer syntheses: 59. Homo-and copolyesters of 4-(4′-hydrophenoxy)benzoic acid

The homopolyester of 4-(4′-hydroxyphenoxy)benzoic acid (poly(4-HPBA)), was prepared under two different reaction conditions and compared with a sample provided by another research group. Depending on the synthetic route, different melting points, d.s.c. traces and crystal lattices were found. However, after repeated heating and cooling, one thermodynamically stable modification with a melting point of 370–375°C can be obtained. Copolyesters of 4-hydroxybenzoic acid and 4-(4′-hydroxyphenoxy)benzoic acid were prepared with various molar ratios either in the melt (condensation in bulk) or in solution. These copolyesters were characterized by elemental analyses, ¹H n.m.r. spectroscopy, d.s.c. measurements, wide-angle X-ray scattering measurements at various temperatures, and optical microscopy. Whereas copolyesters prepared in solution do not melt below 500°C, those prepared by polycondensation in bulk show melting points down to approximately 260°C and form a nematic melt.     

7-(Dialkylamino)coumarin-4-yl]methyl-Caged Compounds as Ultrafast and Effective Long-Wavelength Phototriggers of 8-Bromo-Substituted Cyclic Nucleotides

[7-(Dimethylamino)coumarin-4-yl]methyl (DMACM) and [7-(diethylamino)coumarin-4-yl]methyl (DEACM) esters of 8-bromoadenosine 3',5'-cyclic monophosphate (8-Br-cAMP) and 8-bromoguanosine 3',5'-cyclic monophosphate (8-Br-cGMP) are described as novel caged compounds for 8-bromo-substituted cyclic nucleotides. Synthesis is accomplished by treatment of the free acids of the cyclic nucleotides with the corresponding 7(dialkylamino)-substituted 4(diazomethyl)coumarins. Irradiation of the DMACM- and DEACM-caged cyclic nucleotides with UV light stimulates the release of the cyclic nucleotides within roughly a nanosecond. The new caged compounds are resistant to hydrolysis in aqueous buffers and exhibit long-wavelength absorption properties with maxima at 400 nm, high extinction coefficients, and high quantum yields (0.15-0.31). Their favorable properties render these compounds the most efficient and rapid phototriggers of 8-bromo-substituted cyclic nucleotides known. The usefulness of the compounds for physiological studies under nondamaging light conditions was examined in HEK293 cells expressing the alpha subunit of the cyclic-nucleotide-gated (CNG) channel of cone photoreceptors (CNGA3) and of olfactory neurons (CNGA2) by using confocal laser scanning microscopy and the patch clamp technique.     

mRNA openers and closers: modulating AU-rich element-controlled mRNA stability by a molecular switch in mRNA secondary structure

Approximately 3 000 genes are regulated in a time-, tissue-, and stimulus-dependent manner by degradation or stabilization of their mRNAs. The process is mediated by interaction of AU-rich elements (AREs) in the mRNA's 3'-untranslated regions with trans-acting factors. AU-rich element-controlled genes of fundamentally different functional relevance depend for their activation on one positive regulator, HuR. Here we present a methodology to exploit this central regulatory process for specific manipulation of AU-rich element-controlled gene expression at the mRNA level. With a combination of single-molecule spectroscopy, computational biology, and molecular and cellular biochemistry, we show that mRNA recognition by HuR is dependent on the presentation of the sequence motif NNUUNNUUU in single-stranded conformation. The presentation of the HuR binding site in the mRNA secondary structure appears to act analogously to a regulatory on/off switch that specifically controls HuR access to mRNAs in cis. Based on this finding we present a methodology for manipulating ARE mRNA levels by actuating this conformational switch specifically in a target mRNA. Computationally designed oligonucleotides (openers) enhance the NNUUNNUUU accessibility by rearranging the mRNA conformation. Thereby they increase in vitro and endogenous HuR-mRNA complex formation which leads to specific mRNA stabilization (as demonstrated for TNFalpha and IL-2, respectively). Induced HuR binding both inside and outside the AU-rich element promotes functional IL-2 mRNA stabilization. This opener-induced mRNA stabilization mimics the endogenous IL-2 response to CD28 stimulation in human primary T-cells. We therefore propose that controlled modulation of the AU-rich element conformation by mRNA openers or closers allows message stabilization or destabilization in cis to be specifically triggered. The described methodology might provide a means for studying distinct pathways in a complex cellular network at the node of mRNA stability control. It allows ARE gene expression to be potentially silenced or boosted. This will be of particular value for drug-target validation, allowing the diseased phenotype to ameliorate or deteriorate. Finally, the mRNA openers provide a rational starting point for target-specific mRNA stability assays to screen for low-molecular-weight compounds acting as inhibitors or activators of an mRNA structure rearrangement.     

Retinal Cell Death Caused by Sodium Iodate Involves Multiple Caspase-Dependent and Caspase-Independent Cell-Death Pathways

Herein, we have investigated retinal cell-death pathways in response to the retina toxin sodium iodate (NaIO₃) both in vivo and in vitro. C57/BL6 mice were treated with a single intravenous injection of NaIO₃ (35 mg/kg). Morphological changes in the retina post NaIO₃ injection in comparison to untreated controls were assessed using electron microscopy. Cell death was determined by TdT-mediated dUTP-biotin nick end labeling (TUNEL) staining. The activation of caspases and calpain was measured using immunohistochemistry. Additionally, cytotoxicity and apoptosis in retinal pigment epithelial (RPE) cells, primary retinal cells, and the cone photoreceptor (PRC) cell line 661W were assessed in vitro after NaIO₃ treatment using the ApoToxGlo™ assay. The 7-AAD/Annexin-V staining was performed and necrostatin (Nec-1) was administered to the NaIO₃-treated cells to confirm the results. In vivo, degenerating RPE cells displayed a rounded shape and retracted microvilli, whereas PRCs featured apoptotic nuclei. Caspase and calpain activity was significantly upregulated in retinal sections and protein samples from NaIO₃-treated animals. In vitro, NaIO₃ induced necrosis in RPE cells and apoptosis in PRCs. Furthermore, Nec-1 significantly decreased NaIO₃-induced RPE cell death, but had no rescue effect on treated PRCs. In summary, several different cell-death pathways are activated in retinal cells as a result of NaIO₃.     

A compact photomicroreactor design for kinetic studies of gas‐liquid photocatalytic transformations

A compact photomicroreactor assembly consisting of a capillary microreactor and small‐scale light emitting diodes was developed for the study of reaction kinetics in the gas‐liquid photocatalytic oxidation of thiophenol to phenyl disulfide within Taylor flow. The importance of photons was convincingly shown by a suction phenomenon due to the fast consumption of oxygen. Mass transfer limitations were evaluated and an operational zone without mass transfer effects was chosen to study reaction kinetics. Effects of photocatalyst loading and light sources on the reaction performance were investigated. Reaction kinetic analysis was performed to obtain reaction orders with respect to both thiophenol and oxygen based on heterogeneous and homogeneous experimental results, respectively. The Hatta number further indicated elimination of mass transfer limitations. Reaction rate constants at different photocatalyst loadings and different photon flux were calculated. Furthermore, the advantages of this photomicroreactor assembly for studying gas‐liquid photocatalytic reaction kinetics were demonstrated as compared with batch reactors. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2215–2227, 2015     

Production of Particle‐Stabilized Nonspherical Emulsion Drops in Simple Shear Flow

Nonspherical drops are of interest in the formation of microcapsules in life sciences like food, pharmacy, and cosmetics, agro and fine chemicals as well as material sciences. Out of many systems, particle‐stabilized emulsion drops, so‐called Pickering emulsions, exhibit an interesting formulation. Systems with Pickering particles applied in an excess amount were investigated. During deformation, the particles fully covered the enlarged drop interfaces and prevented its relaxation to a spherical drop shape. Nonspherical drops could be produced in simple shear flow using an adequate process routine. The production in a simple device is a promising high‐throughput alternative to microfluidic devices.     

Characterization of Biomimetic Cofactors According to Stability,Redox Potentials,and Enzymatic Conversion by NADH Oxidase from Lactobacillus pentosus

Oxidoreductases are attractive biocatalysts that convert achiral substrates into products of higher value, but they are also for the most part dependent on nicotinamide cofactors. Recently, biomimetic nicotinamide derivatives have received attention as less costly alternatives to natural cofactors. However, recycling of biomimetics is still challenging because there are only limited opportunities. Here, we have characterized various biomimetic cofactors with regard to stability and redox potentials to find the best alternative to natural cofactors. Further, the cofactor spectrum of NADH oxidase from Lactobacillus pentosus (LpNox) could be expanded, and the enzymatic activity was also compared to activities with different small‐molecule catalysts. As a result, we succeeded in identifying several strategies for regeneration of oxidized biomimetics.     

Kinetic study of hydrogen peroxide decomposition at high temperatures and concentrations in two capillary microreactors

On the background of the direct adipic acid synthesis from cyclohexene and H₂O₂, a kinetic model was derived for the H₂O₂ decomposition catalyzed by sodium tungstate at high H₂O₂ concentrations and high temperatures. A perfluoroalkoxy (PFA) and a stainless steel micro‐flow capillary match commonly used microreactor materials. In the PFA capillary, the decomposition of hydrogen peroxide increased with residence time, reaction temperature and catalyst loading. The reaction order with respect to hydrogen peroxide and sodium tungstate was zero and one, respectively. Simulated data fit well with experimental data in the PFA capillary. While showing a similar trend as that in the PFA capillary, the stainless steel capillary exhibited much higher reaction rates. The steel surface participated in the decomposition process as a heterogeneous catalyst. Key influencing factors of the H₂O₂ decomposition provided some clues on the reaction mechanism of the adipic acid synthesis and its process optimization. © 2016 American Institute of Chemical Engineers AIChE J, 63: 689–697, 2017     

Entwicklung einer kontinuierlichen Mikrowellen‐Vakuumtrocknungsanlage mit hexagonalem Verfahrensraum

A continuous microwave vacuum drying processor with a hexagonal cross‐section of the cavity was constructed. Due to the geometry of the cavity and the continuous movement of the product, homogeneous microwave power absorption of the product can be favored. By the expansion and simultaneous dehydration of non‐expanded, starch‐based extrudates, the applicability of the constructed processor could be shown.