Catalytically Active Hollow Fiber Membranes with Enzyme-Embedded Metal–Organic Framework Coating

Metal–organic frameworks (MOFs) are suitable enzyme immobilization matrices. Reported here is the in situ biomineralization of glucose oxidase (GOD) into MOF crystals (ZIF-8) by interfacial crystallization. This method is effective for the selective coating of porous polyethersulfone microfiltration hollow fibers on the shell side in a straightforward one-step process. MOF layers with a thickness of 8 μm were synthesized, and fluorescence microscopy and a colorimetric protein assay revealed the successful inclusion of GOD into the ZIF-8 layer with an enzyme concentration of 29±3 μg cm⁻². Enzymatic activity tests revealed that 50 % of the enzyme activity is preserved. Continuous enzymatic reactions, by the permeation of β-d -glucose through the GOD@ZIF-8 membranes, showed a 50 % increased activity compared to batch experiments, emphasizing the importance of the convective transport of educts and products to and from the enzymatic active centers.     

Direct Introduction of an Alkylsulfonamido Group on C-sites of Isomeric Dicarba-closo-dodecaboranes: The Influence of Stereochemistry on Inhibitory Activity against the Cancer-Associated Carbonic Anhydrase IX Isoenzyme

Carbonic anhydrase IX (CA IX), a tumor-associated metalloenzyme, represents a validated target for cancer therapy and diagnostics. Herein, we report the inhibition properties of isomeric families of sulfonamidopropyl-dicarba-closo-dodecaboranes group(s) prepared using a new direct five-step synthesis from the corresponding parent cages. The protocol offers a reliable solution for synthesis of singly and doubly substituted dicarba-closo-dodecaboranes with a different geometric position of carbon atoms. The closo-compounds from the ortho- and meta-series were then degraded to corresponding 11-vertex dicarba-nido-undecaborate(1−) anions. All compounds show in vitro enzymatic activity against CA IX in the low nanomolar or subnanomolar range. This is accompanied by clear isomer dependence of the inhibition constant (K_i) and selectivity towards CA IX. Decreasing trends in K_i and selectivity index (S_I) values are observed with increasing separation of the cage carbon atoms. Interactions of compounds with the active sites of CA IX were explored with X-ray crystallography, and eight high-resolution crystal structures uncovered the structural basis of inhibition potency and selectivity.     

Antivitamins B12—Some Inaugural Milestones

The recently delineated structure- and reactivity-based concept of antivitamins B₁₂ has begun to bear fruit by the generation, and study, of a range of such B₁₂-dummies, either vitamin B₁₂-derived, or transition metal analogues that also represent potential antivitamins B₁₂ or specific B₁₂-antimetabolites. As reviewed here, this has opened up new research avenues in organometallic B₁₂-chemistry and bioinorganic coordination chemistry. Exploratory studies with antivitamins B₁₂ have, furthermore, revealed some of their potential, as pharmacologically interesting compounds, for inducing B₁₂-deficiency in a range of organisms, from hospital resistant bacteria to laboratory mice. The derived capacity of antivitamins B₁₂ to induce functional B₁₂-deficiency in mammalian cells and organs also suggest their valuable potential as growth inhibitors of cancerous human and animal cells.     

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This paper presents a framework for incorporating arbitrary implicit multistep schemes into the lattice Boltzmann method. While the temporal discretization of the lattice Boltzmann equation is usually derived using a second-order trapezoidal rule, it appears natural to augment the time discretization by using multistep methods. The effect of incorporating multistep methods into the lattice Boltzmann method is studied in terms of accuracy and stability. Numerical tests for the third-order accurate Adams-Moulton method and the second-order backward differentiation formula show that the temporal order of the method can be increased when the stability properties of multistep methods are considered in accordance with the second Dahlquist barrier.     

“Dial-In” Emission from a Unique Flexible Material with Polarization Tuneable Spectral Intensity

The development of organic photoluminescent materials, which show promising roles as catalysts, sensors, organic light-emitting diodes, logic gates, etc., is a major demand and challenge for the global scientific community. In this context, a photoclick polymerization method is adopted for the growth of a unique photoluminescent three-dimensional (3D) polymer film, E, as a model system that shows emission tunability over the range 350–650 nm against the excitation range 295–425 nm. The DFT analysis of energy calculations and π-stacking supports the spectroscopic observations for the material exhibiting a broad range of emission owing to newly formed chromophoric units within the film. Full polarization spectroscopic Mueller matrix studies were employed to extract and quantify the molecular orientational order of both the ground (excitation) and excited (emission) state anisotropies through a set of newly defined parameters, namely the fluorescence diattenuation and fluorescence polarizance. The information contained in the recorded fluorescence Mueller matrix of the organic polymer material provided a useful way to control the spectral intensity of emission by using pre- and post-selection of polarization states. The observation was based on the assumption that the longer lifetime of the excited dipolar orientation is attributed to the compactness of the film.     

Non‐thermal plasma‐induced apoptosis in yeast Saccharomyces cerevisiae

The effect of non‐thermal plasma generated by the direct current (DC) corona discharge in the mode of transition spark is studied on a yeast Saccharomyces cerevisiae. The exposure to plasma increases production of reactive oxygen species (ROS) in cells, possibly causing the induction of apoptosis. To clarify the mechanism of apoptosis, its induction is tested not only on a wild strain of S. cerevisiae, but also on mutant strains: A deletion mutant Δyca1 without yeast metacaspase proves that in S. cerevisiae the apoptosis occurs partly by the caspase‐independent pathway. A petite strains with mutation in the mitochondria do not show pronounced ROS formation, but in spite of this, apoptosis is detected. Hence, mitochondrial ROS probably do not play an important role in induction of apoptosis.