Impact of defects on the decomposition of chemical warfare agent simulants in Zr-based metal organic frameworks

Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.     

Modeling approaches and performance for estimating personal exposure to household air pollution: A case study in Kenya

This study assessed the performance of modeling approaches to estimate personal exposure in Kenyan homes where cooking fuel combustion contributes substantially to household air pollution (HAP). We measured emissions (PM_2.5, black carbon, CO); household air pollution (PM_2.5, CO); personal exposure (PM_2.5, CO); stove use; and behavioral, socioeconomic, and household environmental characteristics (eg, ventilation and kitchen volume). We then applied various modeling approaches: a single-zone model; indirect exposure models, which combine person-location and area-level measurements; and predictive statistical models, including standard linear regression and ensemble machine learning approaches based on a set of predictors such as fuel type, room volume, and others. The single-zone model was reasonably well-correlated with measured kitchen concentrations of PM_2.5 (R² = 0.45) and CO (R² = 0.45), but lacked precision. The best performing regression model used a combination of survey-based data and physical measurements (R² = 0.76) and a root mean-squared error of 85 µg/m³, and the survey-only-based regression model was able to predict PM2.5 exposures with an R² of 0.51. Of the machine learning algorithms evaluated, extreme gradient boosting performed best, with an R² of 0.57 and RMSE of 98 µg/m³.     

Development and validation of a crisis self‐efficacy index

This study develops a crisis self‐efficacy index to provide a tool for crisis communication researchers and practitioners to understand behavioural aspects of crisis response better. Evaluations of public's crisis self‐efficacy using this index inform strategic message development to protect the public and minimize crisis damages by identifying the public/s most in need of self‐efficacy enhancing interventions. The index also provides practitioners a useful longitudinal index to evaluate progress in crisis preparedness programs and track changes in efficacy. A four‐stage survey index development process using structural equation modelling identifies four underlying constructs of crisis self‐efficacy: action, preventive, achievement and uncertainty management.     

Lupin seed coat as a promising food ingredient: physicochemical,nutritional, antioxidant properties,and effect of genotype and environment

The high proportion of seed coat of legume lupins results in big milling lose during kernel flour production, though the seed coat could be value-added as human food. The physicochemical and nutritional properties and antioxidant capacities of seed coats of six Australian sweet lupin cultivars grown at two locations were evaluated. Results showed that genotype, environment and their interaction were significant for seed coat percentage, proximate composition, dietary fibre content, polyphenols and antioxidant capacities. Strong correlations between seed coat lightness and polyphenol content were found. A comparison using multivariate analysis of the seed coat properties showed clear separation based on growing sites. This study indicates the enormous potential of Australian sweet lupin seed coat as an ‘antioxidant dietary fibre’ food source. The results could also benefit to breed varieties with desirable levels of nutrients and phytochemicals.     

Enhanced dielectric properties of three phase dielectric MWCNTs/BaTiO3/PVDF nanocomposites for energy storage using fused deposition modeling 3D printing

This research studied the effect of fused deposition modeling (FDM) 3D printing on three phase dielectric nanocomposites using poly(vinylidene) fluoride (PVDF), BaTiO₃ (BT), and multiwall carbon nanotubes (CNTs). PVDF polymer and BT ceramics are piezo-, pyro- and di-electric materials extensively used for sensor and energy storage/harvesting applications due to their unique characteristic of dipole polarization. To increase dielectric property, CNTs have been recently utilized for uniform dispersion of BT nanoparticles, ultrahigh polarization density, and local micro-capacitor among matrix. It was proved that 3D printing process provides homogeneous dispersion of nanoparticles, alleviating agglomeration of nanoparticles and reducing micro-crack/voids in matrix which can potentially enhance their dielectric property than traditional methods. In this research, these three-phase nanocomposites are fabricated through FDM 3D printing process and characterized for dielectric property. Increasing both BT and CNT nanoparticles improves dielectric properties, while CNTs have a percolation threshold near 1.7?wt%. The most desirable combination of dielectric constant and loss properties (118 and 0.11 at 1?kHz) is achieved with nanocomposites containing 1.7?wt%-CNT/45?wt%-BT/PVDF. These results provide not only a technique to 3D print dielectric nanocomposites with improved dielectric property but also large-scale electronic device manufacturing possibility with freedom of design, low cost, and faster process.     

Effect of microwave sintering on the properties of copper oxide doped Y-TZP ceramics

The effect of various amounts of copper oxide (CuO) up to 1?wt% on the densification behaviour and mechanical properties of 3?mol% yttria-tetragonal zirconia polycrystal (Y-TZP) were studied by using microwave (MW) sintering method. The MW sintering was performed at temperatures between 1100?°C and 1400?°C, with a heating rate of 30?°C/min. and holding time of 5?min. The beneficial effect of MW in enhancing densification was also compared for the undoped and 0.2?wt% CuO-doped Y-TZP when subjected to conventional sintering (CS) method. The results showed that significant enhancement in the relative density and Vickers hardness were observed for the undoped Y-TZP when MW-sintered between 1100?°C and 1250?°C. It was revealed that the 0.2?wt% CuO-doped Y-TZP and MW sintered at 1250–1300?°C could attain ≥?99.8% of theoretical density, Vickers hardness of about 14.4?GPa, fracture toughness of 7.8 MPam^1/2 and exhibited fine equiaxed tetragonal grain size of below 0.25?µm. In contrast, the addition of 1?wt% CuO was detrimental and the samples exhibited about 50% monoclinic phase upon sintering coupled with poor bulk density and mechanical properties. The study also revealed that the addition of 0.2?wt% CuO and subjected to conventional sintering produced similar densification as that obtained for microwave sintering, thus indicating that the dopant played a more significant role than the sintering method.     

Formation and Degradation of Beta-casomorphins in Dairy Processing

Milk proteins including casein are sources of peptides with bioactivity. One of these peptides is beta-casomorphin (BCM) which belongs to a group of opioid peptides formed from β-casein variants. Beta-casomorphin 7 (BCM7) has been demonstrated to be enzymatically released from the A1 or B β-casein variant. Epidemiological evidence suggests the peptide BCM 7 is a risk factor for development of human diseases, including increased risk of type 1 diabetes and cardiovascular diseases but this has not been thoroughly substantiated by research studies. High performance liquid chromatography coupled to UV-Vis and mass spectrometry detection as well as enzyme–linked immunosorbent assay (ELISA) has been used to analyze BCMs in dairy products. BCMs have been detected in raw cow's milk and human milk and a variety of commercial cheeses, but their presence has yet to be confirmed in commercial yoghurts. The finding that BCMs are present in cheese suggests they could also form in yoghurt, but be degraded during yoghurt processing. Whether BCMs do form in yoghurt and the amount of BCM forming or degrading at different processing steps needs further investigation and possibly will depend on the heat treatment and fermentation process used, but it remains an intriguing unknown.     

Increased Uptake of Chelated Copper Ions by Lolium perenne Attributed to Amplified Membrane and Endodermal Damage

The contributions of mechanisms by which chelators influence metal translocation to plant shoot tissues are analyzed using a combination of numerical modelling and physical experiments. The model distinguishes between apoplastic and symplastic pathways of water and solute movement. It also includes the barrier effects of the endodermis and plasma membrane. Simulations are used to assess transport pathways for free and chelated metals, identifying mechanisms involved in chelate-enhanced phytoextraction. Hypothesized transport mechanisms and parameters specific to amendment treatments are estimated, with simulated results compared to experimental data. Parameter values for each amendment treatment are estimated based on literature and experimental values, and used for model calibration and simulation of amendment influences on solute transport pathways and mechanisms. Modeling indicates that chelation alters the pathways for Cu transport. For free ions, Cu transport to leaf tissue can be described using purely apoplastic or transcellular pathways. For strong chelators (ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA)), transport by the purely apoplastic pathway is insufficient to represent measured Cu transport to leaf tissue. Consistent with experimental observations, increased membrane permeability is required for simulating translocation in EDTA and DTPA treatments. Increasing the membrane permeability is key to enhancing phytoextraction efficiency.     

In situ measurements of human cough aerosol hygroscopicity

The airborne dynamics of respiratory droplets, and the transmission routes of pathogens embedded within them, are governed primarily by the diameter of the particles. These particles are composed of the fluid which lines the respiratory tract, and is primarily mucins and salts, which will interact with the atmosphere and evaporate to reach an equilibrium diameter. Measuring organic volume fraction (OVF) of cough aerosol has proved challenging due to large variability and low material volume produced after coughing. Here, the diametric hygroscopic growth factors (GF) of the cough aerosol produced by healthy participants were measured in situ using a rotating aerosol suspension chamber and a humidification tandem differential mobility analyser. Using hygroscopicity models, it was estimated that the average OVF in the evaporated cough aerosol was 0.88 ± 0.07 and the average GF at 90% relative humidity (RH) was 1.31 ± 0.03. To reach equilibrium in dry air the droplets will reduce in diameter by a factor of approximately 2.8 with an evaporation factor of 0.36 ± 0.05. Hysteresis was observed in cough aerosol at RH = ∼35% and RH = ∼65% for efflorescence and deliquescence, respectively, and may depend on the OVF. The same behaviour and GF were observed in nebulized bovine bronchoalveolar lavage fluid.