On comparison of luminescence properties of La2Zr2O7 and La2Hf2O7 nanoparticles

Unveiling the underlying mechanisms of properties of functional materials, including the luminescence differences among similar pyrochlores A₂B₂O₇, opens new gateways to select proper hosts for various optoelectronic applications by scientists and engineers. For example, although La₂Zr₂O₇ (LZO) and La₂Hf₂O₇ (LHO) pyrochlores have similar chemical compositional and crystallographic structural features, they demonstrate different luminescence properties both before and after doped with Eu³⁺ ions. Based on our earlier work, LHO-based nanophosphors display higher photo- and radioluminescence intensity, higher quantum efficiency, and longer excited state lifetime compared to LZO-based nanophosphors. Moreover, under electronic O²⁻→Zr⁴⁺/Hf⁴⁺ transition excitation at 306 nm, undoped LHO nanoparticles (NPs) have only violet blue emission, whereas LZO NPs show violet blue and red emissions. In this study, we have combined experimental and density functional theory (DFT) based theoretical calculation to explain the observed results. First, we calculated the density of state (DOS) based on DFT and studied the energetics of ionized oxygen vacancies in the band gaps of LZO and LHO theoretically, which explain their underlying luminescence difference. For Eu³⁺-doped NPs, we performed emission intensity and lifetime calculations and found that the LHOE NPs have higher host to dopant energy transfer efficiency than the LZOE NPs (59.3% vs 24.6%), which accounts for the optical performance superiority of the former over the latter. Moreover, by corroborating our experimental data with the DFT calculations, we suggest that the Eu³⁺ doping states in LHO present at exact energy position (both in majority and minority spin components) where oxygen defect states are located unlike those in LZO. Lastly, both the NPs show negligible photobleaching highlighting their potential for bioimaging applications. This current report provides a deeper understanding of the advantages of LHO over LZO as an advanced host for phosphors, scintillators, and fluoroimmunoassays.     

The Effect of Addition of High-Melting Monoacylglycerol and Candelilla Wax on Pea and Faba Bean Protein Foam-Templated Oleogelation

Use of oleogels prepared from hydrocolloids has recently gained considerable attention as an alternative for trans and saturated fats. Lately, pulse proteins such as faba bean protein and pea protein have been successfully used to prepare oleogels using a foam-templated approach. Although the pulse proteins are healthy oleogelators, high oil loss and low quality of cake baked using pulse protein-stabilized oleogels due to its poor rheological properties challenged its use. The present study explored whether the addition of small amount of high-melting monoglyceride (MAG) or candelilla wax (CW) can be used to improve the oil binding capacity, rheological properties, and baking qualities of pulse protein-stabilized oleogels composed of 5% faba bean or pea protein concentrate with 0.25% xanthan gum foams. Different concentrations (0.5–3%) of MAG or CW were dissolved in canola oil at 80 °C, followed by addition into the freeze-dried protein-polysaccharide foams (pH 7) and quickly transferred to a refrigerator to facilitate the formation of oleogels. The crystallized additives were found to be reinforcing the protein foam network in the oleogels. With increase in concentration of CW and MAG, the oil binding capacity, firmness, cohesiveness, and storage moduli of the oleogels were increased. Oleogels with and without MAG or CW were then characterized and tested for their performance as a shortening replacer in model baked cakes. Findings showed improved textural properties of cake upon addition of MAG in the foam-templated oleogels, however, compared to the shortening, negative effect on cake hardness and chewiness was still observed with the oleogels.     

Performance Evaluation and Biodegradation Study of Polyvinyl Chloride Films with Castor Oil-based Plasticizer

In the present study, a renewable resource-based plasticizer was synthesized by the lipase-catalyzed esterification reaction of furfuryl alcohol (FA) and castor oil fatty acid (COFA). The resultant ester (FA-COFA ester) was used as secondary plasticizers to the polyvinyl chloride (PVC) films. The PVC films were formulated using the combination of a conventional plasticizer di-butyl phthalate (DBP) and FA-COFA ester as a secondary plasticizer at different concentrations. Films were characterized by X-ray diffraction analysis, scanning electron microscopy, thermal analysis, mechanical performance, and migration stability. A biodegradability study of the PVC films showed increased degradability with increasing concentration of the FA-COFA ester in the PVC film. The study showed that ester of FA and COFA could be a substitute of DBP by as much as 80% of the total plasticizer with improved elongation and tensile properties, and such a kind of sustainable resource-based PVC blend films could be used as a good packaging material with biodegradable property.     

Self-Assembly and Neurotoxicity of β-Amyloid (21–40) Peptide Fragment: The Regulatory Role of GxxxG Motifs

The three GxxxG repeating motifs from the C-terminal region of β-amyloid (Aβ) peptide play a significant role in regulating the aggregation kinetics of the peptide. Mutation of these glycine residues to leucine greatly accelerates the fibrillation process but generates a varied toxicity profile. Using an array of biophysical techniques, we demonstrated the uniqueness of the composite glycine residues in these structural repeats. We used solvent relaxation NMR spectroscopy to investigate the role played by the surrounding water molecules in determining the corresponding aggregation pathway. Notably, the conformational changes induced by Gly³³ and Gly³⁷ mutations result in significantly decreased toxicity in a neuronal cell line. Our results indicate that G³³xxxG³⁷ is the primary motif responsible for Aβ neurotoxicity, hence providing a direct structure–function correlation. Targeting this motif, therefore, can be a promising strategy to prevent neuronal cell death associated with Alzheimer's and other related diseases, such as type II diabetes and Parkinson's.     

Electron microscopy of shock deformation in alumina

Shock recovered samples of a coarse grain (10 μm), high density (>99.9% theoretical) alumina from asymmetric impact tests conducted at 6.5 GPa (e.g. 3.2 times its Hugoniot Elastic Limit) in a single stage gas gun and characterized by X-ray diffractometry, scanning and field emission scanning electron microscopy, and transmission electron microscopy showed prolific presence of reduced crystallite size, higher average microstrain, grain localized micro/nano-scale deformations, micro-cleavages, grain-boundary microcracks, micro-wing crack formation, extensive shear induced deformations and fractures localized at grains, grain boundaries and triple grain junctions, grain localized entanglement of dislocations and their pile up impeded at grain boundaries. A new qualitative model based on micro-shear and micro-twist induced deformation and fracture in single and/or multiple planes in suitably oriented grain and/or grain assembly was developed to explain the experimentally observed damage evolution process.     

Enzymatic alcoholysis reaction of soy phospholipids

Lipase-catalyzed alcoholysis of soy phospholipids was investigated to simultaneously make lysophospholipids and fatty acid esters of individual alcohols. Alcoholysis was carried out by stirring a mixture of soy phospholipids and individual alcohols in equimolar proportions with 10% (by weight of reactants) Mucor miehei lipase at 55°C for 24 h. The products were isolated by column chromatography after removal of the lipase. Lysophospholipids (in 69–78% molar yield) were obtained from soy phospholipids, and the yield of esters of various alcohols also conformed nearly with theoretical yields.     

Preferential oxidation of linolenic acid compared to linoleic acid in the liver of catfish (Heteropneustes fossilis andClarias batrachus)

The fate of [1-¹⁴C] linoleic acid and [1-¹⁴C] linolenic acid in the liver slices and also in the liver tissues of live carnivorous catfish,Heteropneustes fossilis andClarias batrachus, was studied. Incorporation of the fatty acids into different lipid classes in the live fish differed greatly from the tissue slices, indicating certain physiological control operative in vivo. The extent of desaturation and chain elongation of linoleic and linolenic acids into long-chain polyunsaturated fatty acids was low. Linolenic acid was oxidized (thus labeling the saturated fatty acid with liberated¹⁴C-acetyl-CoA) in preference to linoleic acid, and this oxidation also seemed to be under physiological control since both of the fatty acids were poorly oxidized in the tissue slices and in the killed fish. These fish can therefore recognize the difference in the acyl chain structures of linoleate and linolenate. The higher oxidation of liolenic acid and poor capacity for its conversion to longer chain, highly unsaturated derivatives indicates a higher demand for the dietary supply of these essential fatty acids in these two species.     

Fragmentation and film growth in supersonic nanoaggregate aerosol deposition

Aerosol deposition with gas phase-synthesized chain-like nanoaggregates can yield dense coatings from the impaction of particles on a substrate; however, dense coating formation is not well understood. Here, we study coating consolidation at the single nanoaggregate level. Flame spray pyrolysis-made tin oxide nanoaggregates are mobility (size) filtered, accelerated through a de Laval nozzle, and impacted on alumina substrates. TEM images obtained from low velocity collection and supersonic deposition are compared via quantitative image analysis, which reveals that upon supersonic impact nanoaggregates fragment into smaller aggregates. This suggests that fragmentation is a key step in producing coatings denser than the depositing nanoaggregates themselves. We supplement experiments with detailed particle trajectory calculations, which show that the impact energies per atom during nanoaggregate deposition are below 0.2 eV/molecule. These results suggest that fragmentation can only occur at locations where nanoaggregates bonded by van der Waals and capillary interactions.     

Modification of LLDPE using esterified styrene maleic anhydride copolymer: Study of its properties and environmental degradability

Linear low‐density polyethylene (LLDPE) was blended with decanol‐esterified styrene maleic anhydride copolymer (MDESMA) with an aim to enhance the environmental degradability of polyethylenes. Styrene‐maleic anhydride copolymer (SMA) was synthesized by precipitation polymerization, using benzoyl peroxide (BPO) as initiator. SMA was esterified with a long‐chain monoalcohol, n‐decanol, using methyl ethyl ketone (MEK) as solvent at 80°C to obtain monoesterified styrene‐maleic anhydride (MDESMA). Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA) were performed to characterize SMA and MDESMA. IR spectra of MDESMA showed a decrease in intensity of peak responsible for carbonyl absorption of a five‐membered ring anhydride group along with broadening of carboxyl O? H stretching peak. TGA showed two‐stage degradation for SMA and MDESMA. LLDPE was blended with MDESMA in single‐screw extruder and blends were characterized thermally by DSC and TGA. A single endothermic melting peak of LLDPE/MDESMA blend was observed. Films of the blends, formed by compression molding, showed an increase in modulus of elasticity but a decrease in elongation at break with increasing concentration of MDESMA. LLDPE/MDESMA blend compositions when kept in phosphate/citric acid buffer solution (pH ～ 8) showed initial weight gain because of water absorption and subsequently loss in weight due to dissolution of soluble component of blends. Film samples of blends kept for soil burial also showed similar behavior. Contact‐angle measurement of film samples of the blends showed an increase in value on soil burial, indicating degradation/dissolution of MDESMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 102–108, 2004     

Effect of steam environment on severe core damage behaviour for VVER-1000 with the ASTEC V1 code

Severe accident studies for very low frequency events for VVER-1000 (V320) are carried out to estimate in-vessel damage progression under steam-rich and starved conditions. The analyses with code ASTEC, jointly developed by IRSN (France) and GRS, Germany), have shown the influence of steam environment on core heat-up followed by material relocation, hydrogen production, vessel failure and aerosol generation along with release to containment. Hydro-accumulator injection for studied transients also gives rise to a steam-rich environment enhancing the material oxidation depending on the injection time and period. The generated information along with PSA-Level 2 is helpful to decide Plant Damage State (PDS) and fruitfully develop accident management strategies for the plant.