Structural insights into peptide self-assembly using photo-induced crosslinking experiments and discontinuous molecular dynamics

Determining the structure of the (oligomeric) intermediates that form during the self-assembly of amyloidogenic peptides is challenging because of their heterogeneous and dynamic nature. Thus, there is need for methodology to analyze the underlying molecular structure of these transient species. In this work, a combination of fluorescence quenching, photo-induced crosslinking (PIC) and molecular dynamics simulation was used to study the assembly of a synthetic amyloid-forming peptide, Aβ_16-22. A PIC amino acid containing a trifluormethyldiazirine (TFMD) group—Fmoc(TFMD)Phe—was incorporated into the sequence (Aβ*_16–22). Electrospray ionization ion-mobility spectrometry mass-spectrometry (ESI-IMS-MS) analysis of the PIC products confirmed that Aβ*_16–22 forms assemblies with the monomers arranged as anti-parallel, in-register β-strands at all time points during the aggregation assay. The assembly process was also monitored separately using fluorescence quenching to profile the fibril assembly reaction. The molecular picture resulting from discontinuous molecule dynamics simulations showed that Aβ_16-22 assembles through a single-step nucleation into a β-sheet fibril in agreement with these experimental observations. This study provides detailed structural insights into the Aβ_16-22 self-assembly processes, paving the way to explore the self-assembly mechanism of larger, more complex peptides, including those whose aggregation is responsible for human disease.     

Investigating measurements of fine particle (PM2.5) emissions from the cooking of meals and mitigating exposure using a cooker hood

There is growing awareness that indoor exposure to particulate matter with diameter ≤ 2.5 μm (PM_2.5) is associated with an increased risk of adverse health effects. Cooking is a key indoor source of PM_2.5 and an activity conducted daily in most homes. Population scale models can predict occupant exposures to PM_2.5, but these predictions are sensitive to the emission rates used. Reported emission rates are highly variable and are typically for the cooking of single ingredients and not full meals. Accordingly, there is a need to assess PM_2.5 emissions from the cooking of complete meals. Mean PM_2.5 emission rates and source strengths were measured for four complete meals. Temporal PM_2.5 concentrations and particle size distributions were recorded using an optical particle counter (OPC), and gravimetric sampling was used to determine calibration factors. Mean emission rates and source strengths varied between 0.54—3.7 mg/min and 15—68 mg, respectively, with 95% confidence. Using a cooker hood (apparent capture efficiency > 90%) and frying in non‐stick pans were found to significantly reduce emissions. OPC calibration factors varied between 1.5 and 5.0 showing that a single value cannot be used for all meals and that gravimetric sampling is necessary when measuring PM_2.5 concentrations in kitchens.     

Surface structure and quenching effects in BiFeO3-BaTiO3 ceramics

The structure and properties of Mn-doped 0.67BiFeO₃-0.33BaTiO₃ ceramics are systematically investigated with respect to the effects of annealing prior to rapid cooling by quenching in air. Air-quenching induces a change in crystal structure from pseudo-cubic to rhombohedral, with higher quenching temperatures leading to an increased rhombohedral distortion. These structural changes are correlated with the appearance of more well-defined ferroelectric domain configurations. It is shown that the surface preparation procedures for XRD measurements can induce significant changes in the peak profiles, indicating differences in crystal structure between the surface and bulk regions. Frequency dispersion in the temperature-dependent relative permittivity for the as-sintered sample is significantly reduced after quenching, accompanied by enhancement of the Curie point and improved temperature-stability of piezoelectric properties. It is proposed that the formation of defect clusters by A-site cation diffusion during cooling is circumvented by quenching, leading to the observed modification of structural distortion and ferroelectric properties.     

Hydrogen storage performance of methyl-substituted mesoporous silica with tailored textural characteristics

Journal of Porous Materials - The present study reports a systematic analysis of morphology and hydrogen sorption capacity of mesoporous organic-inorganic silica prepared by varying the silica...     

The formation and properties of Sialon-ZrN composites produced by reaction bonding combined with post gas-pressure sintering

Sialon-ZrN composites have been fabricated by a combination of reaction bonding and post-gas-pressure sintering. Composites with different amount of ZrN were post sintered at 1600, 1700 and 1800?°C under a nitrogen pressure of 0.7?MPa for 6?h. The results showed that mass loss due to decomposition increased with increasing sintering temperature. The mass loss at 1600 and 1700?°C was comparable, and below 3% even for the highest ZrN content of 50?wt%, but ranged between 6% and 9% for samples post sintered at 1800?°C with 10–50?wt% ZrN. Composites sintered at 1700?°C had the highest relative density (> 97%) and lowest open porosity (< 2%), and this was independent of ZrN content. The incorporation of the ZrN particles was observed to have an effect on the mechanical properties of the composites. The highest hardness (16.05?±?0.17?GPa) was observed for the composite sintered at 1700?°C with 20?wt% ZrN but decreased with higher ZrN contents, due to a weak bonding between the ZrN particles and the Sialon matrix. The fracture toughness showed a continuous increase with increasing ZrN content, due to the effect of the weak bonding on toughening mechanisms such as crack branching, crack deflection and crack bridging. The highest fracture toughness (5.35?±?0.18?MPa?m^1/2) was observed for the composited sintered at 1700?°C with 50?wt% ZrN.     

Novel insights on the impact of top water on Steam‐Assisted Gravity Drainage in a point bar reservoir

As efforts are made to efficiently exploit and recover bitumen resources in Canada, increasingly more complex reservoirs in the Athabasca area continue to challenge the application of Steam‐Assisted Gravity Drainage (SAGD) technology. Several studies have been done to investigate the impact of heterogeneities/complexities such as shale barriers, lean zones, and top and bottom water on the performance of the SAGD process. However, the literature is deficient for point bar deposits with top water zones, a common occurrence in oil sands systems. This study, by using thermal reservoir simulation, examines SAGD performance in a point bar deposit reservoir where an overlying top water and an inclined heterolithic strata (IHS) is present. The results show that where the top water is unconfined and steam injection pressure is higher than that of the top water zone, there is a loss of thermal energy, but the top water does not impact steam chamber development. At steam injection pressure lower than that of the top water zone, top water continuously drains into the reservoir and constrains the size of the chamber. However, the IHS zone helps to delay drainage of the top water into the chamber when steam is injected at underbalanced conditions. Finally, under proper steam injection pressure conditions, top water production can be considerably delayed.     

Design of a Cost‐Reduced Flexible Plant for Supercritical Fluid‐Assisted Applications

A novel batch plant for supercritical CO₂ applications is proposed which is not equipped with expensive components, such as high‐pressure pumps, making it particularly suitable for bench‐scale use. For the first time, the use of a hanging scale is suggested to weigh the amount of CO₂ required for the experiment and the use of the thermodynamics to reach the working conditions. The rig is able to cover different applications, e.g., aerogel drying, impregnation, and extraction, showing high flexibility. An approximate cost analysis has been performed considering as a reference a 150‐mL vessel. It has been calculated that both the setup and running costs are considerably lower than the common batch and semicontinuous rigs.     

Computational Analysis of the Solid-State and Solvation Properties of Carbamazepine in Relation to its Polymorphism

The solvent-dependent polymorphism of the active pharmaceutical ingredient (API) carbamazepine is interpreted from calculations of the solid-state and API-solvent intermolecular interactions. These simulations suggested that apolar solute-solute interactions could be disrupted by apolar solvents. In contrast, the polar solute-solute interactions were found to be easily disrupted by polar and protic solvents. This is consistent with experimental observations that the crystallization of the metastable form II is more dominant in apolar solvents. The Mercury program remains the gold standard in terms of usability; however, further expansion into more complex simulation techniques could make this package of even greater use in pharmaceutical manufacturing workflows.