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.     

Evidence for Non-Innocence of a β-Diketonate Ligand

β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac⁻) to Cr^II spontaneously affords Cr^III and a reduced β-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β-diketonates as electron reservoirs opens up possibilities for new metal–ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry.     

Azodicarboxylate-Mediated Peptide Cyclisation: Application to Disulfide Bond Formation in Solution and Solid Phase

Cyclic peptides are important molecules, playing key roles in protein architecture, as chemical probes, and increasingly as crucial structural elements of clinically-useful therapeutics. Herein we report methodology using azodicarboxylates as efficient reagents for the facile synthesis of cyclic peptides through a disulfide bridge. The utility of this approach in both solution and solid-phase, and compatibility with common amino acid side chain functionalities is demonstrated, resulting in cyclic peptides in good yield and purity. This approach has significant potential application for synthesis of molecules of biological or therapeutic significance.     

Isotope‐Filtered 4D NMR Spectroscopy for Structure Determination of Humic Substances

Humic substances, the main component of soil organic matter, could form an integral part of green and sustainable solutions to the soil fertility problem. However, their global‐scale application is hindered from both scientific and regulatory perspectives by the lack of understanding of the molecular make‐up of these chromatographically inseparable mixtures containing thousands of molecules. Here we show how multidimensional NMR spectroscopy of isotopically tagged molecules enables structure characterization of humic compounds. We illustrate this approach by identifying major substitution patterns of phenolic aromatic moieties of a peat soil fulvic acid, an operational fraction of humic substances. Our methodology represents a paradigm shift in the use of NMR active tags in structure determination of small molecules in complex mixtures. Unlike previous tagging methodologies that focused on the signals of the tags, we utilize tags to directly probe the identity of the molecules they are attached to.     

Three‐Phase Barker Arrays

A 3‐phase Barker array is a matrix of third roots of unity for which all out‐of‐phase aperiodic autocorrelations have magnitude 0 or 1. The only known truly two‐dimensional 3‐phase Barker arrays have size 2 × 2 or 3 × 3. We use a mixture of combinatorial arguments and algebraic number theory to establish severe restrictions on the size of a 3‐phase Barker array when at least one of its dimensions is divisible by 3. In particular, there exists a double‐exponentially growing arithmetic function T such that no 3‐phase Barker array of size with exists for all . For example, , , and . When both dimensions are divisible by 3, the existence problem is settled completely: if a 3‐phase Barker array of size exists, then .     

Effects of small changes in initial conditions on mixing layer three-dimensionality

Conclusions An experimental study which shows the effects of relatively small changes in the initial conditions on the development of the three-dimensional structure of a plane mixing layer originating from laminar boundary layers has been completed. It was shown that while the exact shapes and positions of the streamwise vortex structures are not the same for the two initial conditions, their overall distribution, reorganization and decay are very similar. The present results imply that while some of the specific details of the streamwise vortex structure may be facility dependent, a relatively strong structure, which produces significant three-dimensionality, should form in all mixing layers originating from laminar boundary layers. After some initial readjustments, the structure will appear in the form of counter-rotating pairs of streamwise vortices which, in the mean, grow with the mixing layer and decay in strength.The present results also serve as a warning that small changes in initial conditions may significantly affect the Reynolds stress distributions in the near-field. The most likely mechanism for this is through the effects of very small changes in initial boundary layer properties on the details (strength and location) of the spanwise vortex roll-up. Despite these relatively large differences in the near-field, both mixing layers attain comparable turbulence structure and growth rates in the far-field. In addition, the behavior of the streamwise vortex structure does not appear to be affected by the differences in the near-field Reynolds stress distributions.     

Pressure-sensitive paint in aerodynamic testing

Pressure-sensitive paint (PSP) is a relatively new aerodynamic measurement tool with the unique capability of providing a field measurement of pressure over a test surface. An introductory review of this technology is presented, which is confined to the application of the PSP method to aircraft development wind tunnel testing. This is at present the primary application area and thus the focus of research on the use of the method, and is the authors' own area of research. Described are PSP fundamentals, the various elements comprising PSP technology, and current limitations and considerations in applying this technology. Experimental results are presented to illustrate the present capability of the method. The few publications currently available on this subject in the open literature are also referenced.