Binding of cadmium,copper, and zinc to humic substances originating from municipal solid waste compost

The application of municipal solid waste (MSW) compost increases both the trace metal loading and the organic matter in the soil. To characterize the quality and metal-binding capacity of the compost OM, we extracted humic acid (HA) and fulvic acid (FA) from mature MSW compost and analyzed them for elemental composition, acid-titratable functional groups, total metal content, and structural components (by ¹³C NMR). HA constituted 67% of all extracted humic substances and differed significantly from HAs of cultivated lands: The compost HA exhibited smaller molecular size, a higher N content, and lower aromaticity due to large amounts of saturated aliphatic components. Metal complexation studies of the extracted HA and FA were performed by equilibrium dialysis titration. The complexing capacity (CC) was highest for Cu: CC_HA = 3357 and CC_FA = 5221 μmol Cu g⁻¹ of dissolved organic carbon (DOC) at pH 5. Zn and Cd were bound (at pH 7) in smaller concentrations: CC_HA(Zn) = 2167, CC_FA(Zn) = 2809, CC_HA(Cd) = 2386, and CC_FA(Cd) = 2468 μmol metal g⁻¹ of DOC. Stability constants for binding on the strongest sites (pK_int) were determined as pK_intHA = 6.6 and pK_intFA = 7.3 for Cu at pH 5; and pK_intHA = 8.0 and pK_intFA = 6.4 for Cd at pH 7. Since these measured parameters fall within the ranges of values obtained for soil humic substances, we conclude that in soils with little organic matter, compost addition will significantly increase the amount of highly reactive organic complexing agents for trace metals in the soil.     

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.     

Burn Rate Models for Gun Propellants

In the past, Vieille's law and minor modifications of it described sufficiently the linear burning rate of gun propellants which governs the design of charges by interior ballistic simulations. Recent developments to increase the performance led to new gun concepts and innovative propellants. These are the electrothermal‐chemical gun, porous and foamed charges as well as formulations exhibiting a temperature independent burning. Vieille's law cannot fully meet experimental results in these cases. Approaches based on the heat flow equation in the solid energetic material give simplified formulas to extend the validity. These burning rate models have the ability to describe the experimentally determined burning behavior at least in a simplified or qualitative way. More sophisticated methods consider complex geometrical structures in the solid or take into account the actual progress in phase behavior and reaction kinetics of heterogeneous combustion. The dependence of the burning rate on initial temperature, on phase transitions, porous structure and gaseous reactions can be described.     

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.     

Structure Formation of Integral Asymmetric Composite Membranes of Polystyrene‐block‐Poly(2‐vinylpyridine) on a Nonwoven

The formation of an integral asymmetric membrane composed of a cylinder‐forming polystyrene‐block‐poly(2‐vinylpyridine) on a nonwoven by using solvent casting followed by solvent/nonsolvent exchange (phase inversion) is reported for the first time. The influence of parameters such as solvent composition, evaporation time of the solution‐cast block copolymer film before phase inversion, and immersion bath temperature is demonstrated. The optimized membranes are characterized in terms of stimuli‐responsive water flux properties. The morphologies of the membranes as well as of the bulk of the block copolymer are imaged by scanning force microscopy, scanning electron microscopy, and transmission electron microscopy.

     

Effect of Silica‐Coated Poly(butyl methacrylate)‐block‐poly(methyl methacrylate) Double‐Shell Particles on the Mechanical Properties of PMMA Composites

Silica nanoparticles with an average diameter of 12 nm are grafted with PBMA‐b‐PMMA double shells through typical sequential ATRP from bromoisobutyrate initiators anchored at the silica surface using an epoxysilane. A commercially available PMMA homopolymer is used for the preparation of composites with unmodified, silane‐modified and double‐shell‐modified silica particles. Good mechanical properties are obtained for silica double shell containing systems. The silica content in double shell particle systems is varied from 0 to 2.5 wt%. A significant improvement in impact properties is observed. The surface‐modified silica particles are characterized by ATR‐FTIR, NMR, GPC, and thermal analyses. TEM analysis is used to analyze the nature of dispersion of particles in the composites.

     

Ice Crystal Growth in Sucrose Solutions Containing Kappa- and Iota-Carrageenans

Measurements of ice recrystallization inhibition (IRI) and thermal hysteresis (TH) activities of kappa (κ)- and iota (ι)-carrageenans were carried out to examine whether they can be novel cryoprotectants or not. IRI measurements indicate that both carrageenans reduce recrystallization in sucrose solution, but that the IRI activity of κ-carregeenan is higher than that of ι-carrageenan. TH measurements indicate that κ- and ι-carrageenans do not exhibit TH activity. TH activity measurements of antifreeze glycoprotein (AFGP) in the presence of κ-carregeenan demonstrate that this carregeenan neither influences the TH activity of AFGP nor the shape of the ice crystals. The round ice crystal shape transformed into an angular and elongated shape in the presence of both carregeenans.     

The Rise of Retinal Organoids for Vision Research

Retinal degenerative diseases lead to irreversible blindness. Decades of research into the cellular and molecular mechanisms of retinal diseases, using either animal models or human cell-derived 2D systems, facilitated the development of several therapeutic interventions. Recently, human stem cell-derived 3D retinal organoids have been developed. These self-organizing 3D organ systems have shown to recapitulate the in vivo human retinogenesis resulting in morphological and functionally similar retinal cell types in vitro. In less than a decade, retinal organoids have assisted in modeling several retinal diseases that were rather difficult to mimic in rodent models. Retinal organoids are also considered as a photoreceptor source for cell transplantation therapies to counteract blindness. Here, we highlight the development and field’s improvements of retinal organoids and discuss their application aspects as human disease models, pharmaceutical testbeds, and cell sources for transplantations.     

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