Exploring how changes to the steroidal core alter oleogelation capability in sterol: γ-oryzanol blends.

Oleogels based on sterols such as ß-sitosterol blended with the sterol ester γ-oryzanol are a very interesting class of systems, but there are aspects of their formation and structure that remain elusive. It has previously been shown that a methyl group on the C30 position of the sterol-ester plays an important role in gelation. This work explored the effect that having C30 methyl groups on both the sterol and the sterol-ester had on the gelation process and subsequent gel structure. Lanosterol and saponified γ-oryzanol (which was synthesized as part of this study) were identified as materials of interest, as both feature a methyl group on the C30 position of their steroidal cores. It was observed that both sterols formed gels when blended with γ-oryzanol, and also that lanosterol gelled sunflower oil without the addition of γ-oryzanol. All of these gels were significantly weaker than that formed by ß-sitosterol blended with γ-oryzanol. To explore why, molecular docking simulations along with AFM and SAXS were used to examine these gels on a broad range of length scales. The results suggest that saponified γ-oryzanol-γ-oryzanol gels have a very similar structure to that of ß-sitosterol-γ-oryzanol gels. Lanosterol-γ-oryzanol gels and pure lanosterol gel, however, form with a totally different structure facilitated by the head-to-tail stacking motif exhibited by lanosterol. These results give further evidence that relatively slight changes to the molecular structure of gelators can result in significant differences in subsequent gel properties.

Molecular Interactions behind the Self-Assembly and Microstructure of Mixed Sterol Organogels.

In this work, we have employed docking and atomistic molecular dynamics (MD) simulations supported by complementary experiments using atomic force microscopy, rheology, and spectroscopy to investigate the self-assembled structure of ß-sitosterol and γ-oryzanol molecules into cylindrical tubules in a nonaqueous solvent. Docking models of several phytosterols, including sitosterol, with oryzanol and other sterol esters demonstrate that for systems to form tubules, the phytosterol sterane group must be stacked in a wedge shape with the ester sterane group and a hydrogen bond must form between the hydroxyl group of the phytosterol and the carbonyl group of the ester. MD of the self-assembled structure were initiated with the molecules in a roughly cylindrical configuration, as suggested from previous experimental studies, and the configurations were found to be stable during 50 ns simulations. We performed MD simulations of two tubules in proximity to better understand the aggregation of these fibrils and how the fibrils interact in order to stick together. We found that an interfibril network of noncovalent bonds, in particular van der Waals and π-π contacts, which is formed between the ferulic acid groups of oryzanol through the hydroxyl, methoxy, and aromatic groups, is responsible for the surface-to-surface interactions between fibrils; an observation supported by molecular spectroscopy. We believe that these interactions are of primary importance in creating a strong organogel network.

Supramolecular Amino Acid Based Hydrogels: Probing the Contribution of Additive Molecules using NMR Spectroscopy.

Supramolecular hydrogels are composed of self-assembled solid networks that restrict the flow of water. l-Phenylalanine is the smallest molecule reported to date to form gel networks in water, and it is of particular interest due to its crystalline gel state. Single and multi-component hydrogels of l-phenylalanine are used herein as model materials to develop an NMR-based analytical approach to gain insight into the mechanisms of supramolecular gelation. Structure and composition of the gel fibres were probed using PXRD, solid-state NMR experiments and microscopic techniques. Solution-state NMR studies probed the properties of free gelator molecules in an equilibrium with bound molecules. The dynamics of exchange at the gel/solution interfaces was investigated further using high-resolution magic angle spinning (HR-MAS) and saturation transfer difference (STD) NMR experiments. This approach allowed the identification of which additive molecules contributed in modifying the material properties.

Halogen effects on the solid-state packing of phenylalanine derivatives and the resultant gelation properties.

Phenylalanine is an important amino acid both biologically, essential to human health, and industrially, as a building block of artificial sweeteners. Our interest in this particular amino acid and its derivatives lies with its ability to form gels in a number of solvents. We present here the studies of the influence of halogen addition to the aromatic ring on the gelation properties and we analyse the crystal structures of a number of these materials to elucidate the trends in their behaviour based on the halogen addition to the aromatic group and the interactions that result.

Gelation Landscape Engineering Using a Multi-Reaction Supramolecular Hydrogelator System.

Simultaneous control of the kinetics and thermodynamics of two different types of covalent chemistry allows pathway selectivity in the formation of hydrogelating molecules from a complex reaction network. This can lead to a range of hydrogel materials with vastly different properties, starting from a set of simple starting compounds and reaction conditions. Chemical reaction between a trialdehyde and the tuberculosis drug isoniazid can form one, two, or three hydrazone connectivity products, meaning kinetic gelation pathways can be addressed. Simultaneously, thermodynamics control the formation of either a keto or an enol tautomer of the products, again resulting in vastly different materials. Overall, this shows that careful navigation of a reaction landscape using both kinetic and thermodynamic selectivity can be used to control material selection from a complex reaction network.

Photocontrol over cucurbit[8]uril complexes: stoichiometry and supramolecular polymers.

Herein we report the photocontrol of cucurbit[8]uril (CB[8])-mediated supramolecular polymerization of azobenzene-containing monomers. The CB[8] polymers were characterized both in solution and in the solid state. These host-guest complexes can be reversibly switched between highly thermostable photostationary states. Moreover, a remarkable stabilization of Z-azobenzene was achieved by CB[8] complexation, allowing for structural characterization in the solid state.

Ultrasound-assisted construction of halogen-bonded nanosized cocrystals that exhibit thermosensitive luminescence.

Multi-component organic nanocrystals that are comprised of two or more supramolecular building blocks can be used to extend the design and assembly scope of solid molecular materials. Herein, we report the use of ultrasonication to prepare halogen-bonded stilbene-based nano-cocrystals that exhibit different photoemission properties, including one- and two-phonon emission and fluorescence lifetimes, relative to those of macrodimensional crystals. The structural transformation from nano-cocrystals into nanocrystals upon heating results in a luminescence red-shift from greenish blue to yellow. The temperature-dependent ratiometric luminescence may allow such nano-cocrystals to be used as fluorescent sensors and thermosensitive materials.

Use of in situ atomic force microscopy to follow phase changes at crystal surfaces in real time.

AFM of cocrystals: Atomic force microscopy can be used to observe phase changes at crystal surfaces where the transformation is accompanied by a change in the spacing between layers of molecules. The conversion of a metastable polymorph of the caffeine-glutaric acid cocrystal into the thermodynamically stable form was analyzed continuously in situ using intermittent-contact-mode atomic force microscopy.

Recovery Of Zinc from Scrap Steel Using Zinc-Bromine Battery Technology.

Secondary production of steel is known to significantly decrease the CO2 emissions of steelmaking, but only 40 % of steel is produced through recycling, which is made difficult by contamination of scrap resources with nonferrous metals and nonmetal debris. These contaminants include zinc, towards which blast furnace and electric arc systems have a low tolerance (<0.02 wt %). In this work, clean and efficient recovery of zinc from the surface of steel substrates was investigated using a custom-made low-cost membrane-free non-flow zinc-bromine battery (ZBB) that enabled rapid and straightforward integration and removal of steel substrates. The electrical performance of the cell was characterized by charge-discharge profiles, and zinc removal and recovery onto electrodes was characterized by using scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). Upon discharging, the cell efficiently removed >99.9 wt % zinc from steel surfaces. On recharging the cell, zinc was re-electroplated onto a carbon foam electrode in an easily recoverable form and with high purity. The process was repeated over 30 cycles to demonstrate robustness. The work shows the importance of the cutoff voltage upon discharging: if less than 0.5 V, the cell co-extracted iron into the electrolyte solution, affecting cell durability and zinc purity. A two-stage process for recovering zinc from scrap steel is proposed, illustrating how ZBB technology could enable efficient and clean recovery of zinc from complex scrap steel resources in the steel industry.

The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides.

1,2,6-Thiadiazines treated with visible light and 3O2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce 1O2 and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.

Pressure-induced enhancement of magnetic-ordering temperature in an organic radical to 70 K: a magnetostructural correlation.

The structure of the canted antiferromagnet ß-p-NCC(6)F(4)CNSSN (1) was determined from synchrotron powder-diffraction studies in the pressure range 0-21.6 kbar. Radical 1 crystallizes in the orthorhombic space group Fdd2, but undergoes an asymmetric contraction of the unit-cell size with increasing pressure. At the molecular level, this contraction of the unit cell is simultaneously accommodated by: 1) an increase in twist angle between aryl and heterocyclic rings; and 2) a shortening of the intermolecular S···N contacts, which propagate the magnetic-exchange pathway. DFT calculations based on the structures in this pressure range revealed an increase in the magnetic-exchange interaction (J) with increasing pressure, and an excellent correlation was observed between J and the magnetic-ordering temperature, which increased from 36 K at ambient pressure up to 70 K at 16 kbar.

On crystal versus fiber formation in dipeptide hydrogelator systems.

Naphthalene dipeptides have been shown to be useful low-molecular-weight gelators. Here we have used a library to explore the relationship between the dipeptide sequence and the hydrogelation efficiency. A number of the naphthalene dipeptides are crystallizable from water, enabling us to investigate the comparison between the gel/fiber phase and the crystal phase. We succeeded in crystallizing one example directly from the gel phase. Using X-ray crystallography, molecular modeling, and X-ray fiber diffraction, we show that the molecular packing of this crystal structure differs from the structure of the gel/fiber phase. Although the crystal structures may provide important insights into stabilizing interactions, our analysis indicates a rearrangement of structural packing within the fibers. These observations are consistent with the fibrillar interactions and interatomic separations promoting 1D assembly whereas in the crystals the peptides are aligned along multiple axes, allowing 3D growth. This observation has an impact on the use of crystal structures to determine supramolecular synthons for gelators.

In situ X-ray structural studies of a flexible host responding to incremental gas loading.

Crystallographic pressure-lapse snapshots of a porous material responding to gas loading were used to investigate the stepwise uptake of carbon dioxide and acetylene molecules into discrete confined spaces. Based on the data, a qualitative statistical mechanical model was devised that reproduces even subtle features in the experimental gas sorption isotherms.

COVID-19-related anosmia.

On average, 47% of patients with COVID-19 self-report an olfactory disorder, although the inaccuracy of self-reporting means this figure may be higher.

Vocal cord dysfunction after pediatric cardiac surgery: A prospective implementation study.

Objective: To determine the incidence, outcomes, and evaluate diagnostic modalities for postoperative vocal cord dysfunction (VCD) following cardiothoracic surgery in children. Methods: A prospective mixed-methods study using principles of implementation science was completed. All patients undergoing surgery involving the aortic arch, ductus, or ligamentum arteriosum and vascular rings from September 2019 to December 2020 were enrolled. Patients underwent speech pathology assessment, laryngeal ultrasound, and flexible direct laryngoscopy. Results: Ninety-five patients were eligible for inclusion. The incidence of VCD ranged from 18% to 56% and varied according to procedure group. VCD occurred in 42% of neonates. Repair of hypoplastic aortic arch was associated with increased risk of VCD (57%; P = .002). There was no significant difference in duration of intubation, pediatric intensive care unit stay, or hospital stay. Forty percent children were able to achieve full oral feeding. Children with VCD were more likely to require nasogastric supplementary feeding at discharge (60% vs 36%; P = .044). Sixty-eight percent of patients demonstrated complete resolution of VCD at a median of 97 days postoperatively. Laryngeal ultrasound and speech pathology assessment combined had a sensitivity of 91% in comparison to flexible direct laryngoscopy. Conclusions: VCD occurred in one-third and resolved in two-thirds of patients at a median of 3 months following cardiac surgery. Aortic arch repair carried the highest risk of VCD. VCD adversely influenced feeding. Forty percent of patients achieved full oral feeding before discharge. VCD did not delay intensive care unit or hospital discharge. Speech pathology assessment and laryngeal ultrasound combined was reliable for diagnosis in most patients and was more patient friendly than flexible direct laryngoscopy.