Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Formal Umpolung Addition of Phosphites to 2-Azaaryl Ketones under Chiral Brønsted Base Catalysis: Enantioselective Protonation Utilizing [1,2]-Phospha-Brook Rearrangement

The formal enantioselective umpolung addition of dialkyl phosphites to 2-azaaryl ketones was developed under Brønsted base catalysis. The reaction involves the enantioselective protonation of the transient α-oxygenated (2-azaaryl)methyl anion generated through the 1,2-addition of the anion of dialkyl phosphite to the 2-azaaryl ketone and the subsequent [1,2]-phospha-Brook rearrangement. A chiral bis(guanidino)iminophosphorane organosuperbase efficiently catalyzed the reaction to provide enantio-enriched phosphates in high yields with good to high enantioselectivities. This is a rare example of the catalytic enantioselective protonation of transient carbanions other than enolates, constructing a trisubstituted stereogenic center α to 2-azaarenes.     

Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

A study of 3D radial density adapted trajectories for sodium imaging

Sodium imaging typically employs ultrashort echo time radial, density adapted and cones trajectories to capture the rapidly decaying short T2 signal. The present study considers the parameter choices involved in the use of these trajectories in terms of their impact on the resolution and signal to noise ratio. Many parameters have a strong effect on these image properties, particularly the number of spokes which impacts voxel size. The present article develops an understanding of the trade-offs involved and how to choose optimal (or at least reasonable) parameter values. This has a practical role in designing clinical protocols for imaging sodium.     

Maximum cross-correlated kurtosis-based unsaturated stochastic resonance and its application to bearing fault diagnosis

Considering the random impulses of mechanical noise and the limitations involved while identifying mechanical fault impulse signals via traditional measurement indices of signal-to-noise ratio, which require the characteristic frequency to be known in advance, this study proposes an adaptive unsaturated stochastic resonance method employing maximum cross-correlated kurtosis as the signal detection index. The proposed method combines the features of a cross-correlated coefficient to indicate periodic fault transients and those of spectrum kurtosis to locate these transients in the frequency domain. Actual vibration signals collected from motor and gear bearings subjected to heavy noise are used to demonstrate the effectiveness of the proposed method. Through a coarse tree-based machine learning method, the proposed method is verified to be more suitable for explaining the periodic impulse components of bearing signals, as compared to the ensemble empirical mode decomposition denoising method and unsaturated stochastic resonance using the kurtosis-intercorrelation index.     

Intracranial vessel wall imaging framework – Data acquisition,processing, and visualization

ObjectiveAssessment of vessel walls is an integral part in diagnosis and disease monitoring of vascular diseases such as vasculitis. Vessel wall imaging (VWI), in particular of intracranial arteries, is the domain of Magnetic Resonance Imaging (MRI) – but still remains a challenge. The tortuous anatomy of intracranial arteries and the need for high resolution within clinically acceptable scan times require special technical conditions regarding the hardware and software environments.Materials and methodsIn this work a dedicated framework for intracranial VWI is presented offering an optimized, black-blood 3D T1-weighted post-contrast Compressed Sensing (CS)-accelerated MRI sequence prototype combined with dedicated 3D-GUI supported post-processing tool for the CPR visualization of tortuous arbitrary vessel structures.ResultsUsing CS accelerated MRI sequence, the scanning time for high-resolution 3D black-blood CS-space data could be reduced to under 10 min. These data are adequate for a further processing to extract straightened visualizations (curved planar reformats – CPR). First patient data sets could be acquired in clinical environment.ConclusionA highly versatile framework for VWI visualization was demonstrated utilizing a post-processing tool to extract CPR reformats from high-resolution 3D black-blood CS-SPACE data, enabling simplified and optimized assessment of intracranial arteries in intracranial vascular disorders, especially in suspected intracranial vasculitis, by stretching their tortuous course. The processing time from about 15–20 min per patient (data acquisition and further processing) allows the integration into clinical routine.     

Surfactant self-assembly structures and multilayer formation at the solid-solution interface induces by electrolyte,polymers and proteins

Recent developments in the study of the formation of self-assembled surfactant structures and multilayers at the solid-solution interface are presented. It covers a wide range of phenomena, but in this review the main focus is on the surface structures formed from dilute solution in the presence of electrolyte and in more concentrated solutions. Their formation under those conditions are set in the wider context of the more extensive observations of their occurrence in more complex polymer-surfactant mixtures. Although the sequential adsorption methods using layer-by-layer approaches are more well established for polyelectrolytes and their associated mixtures, the main emphasis is on the self-assembly. The opportunities to manipulate wetting properties and to generate enhanced wetting characteristics are discussed. The potential applications, modifying wetting behaviour, efficient near surface reservoir for enhanced and prolonged delivery of active components, and for the development of a range of smart functionalised surfaces are highlighted.