Emulsification by high frequency ultrasound using piezoelectric transducer: Formation and stability of emulsifier free emulsion

Emulsifier free emulsion was developed with a new patented technique for food and cosmetic applications. This emulsification process dispersed oil droplets in water without any emulsifier. Emulsions were prepared with different vegetable oil ratios 5%, 10% and 15% (v/v) using high frequency ultrasounds generated by piezoelectric ceramic transducer vibrating at 1.7 MHz. The emulsion was prepared with various emulsification times between 0 and 10 h. Oil droplets size was measured by laser granulometry. The pH variation was monitored; electrophoretic mobility and conductivity variation were measured using Zêtasizer equipment during emulsification process. The results revealed that oil droplets average size decreased significantly (p < 0.05) during the first 6 h of emulsification process and that from 160 to 1 μm for emulsions with 5%, 10% and from 400 to 29 μm for emulsion with 15% of initial oil ratio.For all tested oil ratios, pH measurement showed significant decrease and negative electrophoretic mobility showed the accumulation of OH⁻ at oil/water interface leading to droplets stability in the emulsion. The conductivity of emulsions showed a decrease of the ions quantity in solution, which indicated formation of positive charge layer around OH⁻ structure. They constitute a double ionic layer around oil particles providing emulsion stability. This study showed a strong correlation between turbidity measurement and proportion of emulsified oil.     

Potential-induced sonoelectrochemical graphene nanosheets with vacancies as hydrogen peroxide reduction catalysts and sensors

Defective graphene nanosheets (dGN_4V) with 5-9, 5-8-5, and point defects were synthesised by a sonoelectrochemical method, where a potential of 4 V (vs. Ag/AgCl) was applied to drive the rapid intercalation of phosphate ions between the layers of the graphite foil as a working electrode. In addition to these vacancies, double vacancy defects were also created when the applied potential was increased to 8 V (dGN_8V). The defect density of dGN_8V (2406 μm⁻²) was higher than that of dGN_4V (1786 μm⁻²). Additionally, dGN_8V and dGN_4V were applied as catalysts for the hydrogen peroxide reduction reaction (HPRR). The mass activity of dGN_8V (1.31 × 10⁻² mA·μg⁻¹) was greater than that of dGN_4V (1.17 × 10⁻² mA·μg⁻¹) because of its high electrochemical surface area (ECSA, 1250.89 m²·g⁻¹) and defect density (N_D, 2406 μm⁻²), leading to low charge transfer resistance on the electrocatalytic interface. The ECSA and N_D of dGN_4V were 502.7 m²·g⁻¹ and 1786 μm⁻², respectively. Apart from its remarkable HPRR activity, the cost-effective dGN_8V catalyst also showed potential as an amperometric sensor for the determination of H₂O₂.     

Fabrication of emulsions prepared by rice bran protein hydrolysate and ferulic acid covalent conjugate: Focus on ultrasonic emulsification

The aim of the paper was to investigate the effect of ultrasonic emulsification treatment on the fabrication mechanism and stability of the emulsion. The covalent conjugate made with rice bran protein hydrolysate (RBPH) and ferulic acid (FA) was used as the emulsifier. The effects of high intensity ultrasound (HIU) power with different level (0 W, 150 W, 300 W, 450 W and 600 W) on the stability of emulsion were evaluated. The results showed that ultrasonic emulsification can significantly improve the stability of the emulsions (p < 0.05). The emulsion gained better stability and emulsifying property at 300 W. It was able to fabricate emulsion with smaller particle size, more uniform distribution and higher interfacial protein content. It was confirmed by fluorescent microscopy and cryo-scanning electron microscopy (cryo-SEM) furtherly. And it was also proved that the emulsion treated by proper HIU treatment at 300 W had better storage stability. Excessive HIU treatment (450 W, 600 W) had negative effects on the stability of emulsion. The stability of emulsion (300 W) against different environmental stresses was further explored, which established a theoretical basis for the industrial application of emulsion in food industry.     

Development of sulphurized SnS thin film solar cells

Thin films of tin sulphide (SnS) have been grown by sulphurization of sputtered tin precursor layers in a closed chamber. The effect of sulphurization temperature (T_s) that varied in the range of 150–450 °C for a fixed sulphurization time of 120 min on SnS film was studied through various characterization techniques. X-ray photoelectron spectroscopy analysis demonstrated the transformation of metallic tin layers into SnS single phase for T_s between 300 °C and 350 °C. The X-ray diffraction measurements indicated that all the grown films had the (111) crystal plane as the preferred orientation and exhibited orthorhombic crystal structure. Raman analysis showed modes at 95 cm⁻¹, 189 cm⁻¹ and 218 cm⁻¹ are related to the A_g mode of SnS. AFM images revealed a granular change in the grain growth with the increase of T_s. The optical energy band gap values were estimated using the transmittance spectra and found to be varied from 1.2 eV to 1.6 eV with T_s. The Hall effect measurements showed that all the films were p-type conducting nature and the layers grown at 350 °C showed a low electrical resistivity of 64 Ω-cm, a net carrier concentration of 2 × 10¹⁶ cm⁻³ and mobility of 41 cm² V⁻¹ s⁻¹. With the use of sprayed Zn_0.76Mg_0.24O as a buffer layer and the sputtered ZnO:Al as window layer, the SnS based thin film solar cell was developed that showed a conversion efficiency of 2.02%.     

Improvement of the emulsifying properties of mixed emulsifiers by optimizing ultrasonic-assisted processing

Optimizing ultrasound (ULD)-assisted flavonoid modification is an important component of enhancing its application potential. In this work, diverse flavonoids, such as quercetin (Que), apigenin (Api), and morin (Mor), were used to modify protein in myofibrillar protein (MP)/cellulose nanocrystal (CN) complexes using ULD-assisted method. Compared with the MP/CNs group, the triiodide contents of MP-Que/CNs, MP-Api/CNs, and MP-Mor/CNs increased by 1175.84%, 479.05%, and 2281.50% respectively. The findings revealed that the actual intensity of ULD was drastically reduced by the molecular weight decrease of these flavonoids. For olive oil emulsions prepared with mixed emulsifiers, the low interfacial diffusion rates (0.03 mN·m·s^−1/2) and weak emulsifying activity (8.33 m²/g) of the MP/CN complexes were significantly improved by the flavonoids after ULD-assisted treatment. Notably, the emulsions prepared using MP-Api/CNs contained smaller oil droplets and exhibited better emulsifying properties, compared to emulsions prepared with MP-Mor/CNs or MP-Que/CNs. This study is essential for ULD-assisted treatment since the processing impact may be increased by choosing the most suitable flavonoid.     

Laccase cross-linking of sonicated α-Lactalbumin improves physical and oxidative stability of CLA oil in water emulsion

α-lactalbumin was modified by ultrasound (US, 20 kHz, 43 ± 3.4 W/cm⁻²) pre-treatments (0, 15, 30 and 60 min) and laccase cross-linking of sonicated α-lactalbumin was used to evaluate the physical and oxidative stability of conjugated linoleic acid (CLA) emulsions. The emulsions prepared with laccase cross-linking US-α-lactalbumin (α-lactalbumin treated with US pre-treatment) and US-α-lactalbumin were scrutinized for oxidative and physical stability at room temperature for two weeks of storage. Laccase cross-linking US-α-lactalbumin (Lac-US-α-lactalbumin) revealed improved physical stability in comparison with US-α-lactalbumin, specified by droplet size, structural morphology, adsorbed protein, emulsifying properties and creaming index. SDS-PAGE analysis showed that there was formation of polymers in Lac-US-α-lactalbumin emulsion. Surface hydrophobicity of Lac-US-α-lactalbumin was higher than that of US-α-lactalbumin, and gradually enhanced with the increase of ultrasound time. More importantly, the measurements of peroxide values and conjugated dienes were used to study the oxidative stability of the CLA emulsions. The Lac-US-α-lactalbumin emulsion proved to be reducing the synthesis of fatty acid hydroperoxides and less conjugated dienes compared to the native and US-α-lactalbumin emulsions. This study revealed that the combination of US pre-treatment and laccase cross-linking might be an effective technique for the modification of CLA emulsions.     

Ultrasonic energy input influence οn the production of sub-micron o/w emulsions containing whey protein and common stabilizers

Ultrasonication may be a cost-effective emulsion formation technique, but its impact on emulsion final structure and droplet size needs to be further investigated. Olive oil emulsions (20 wt%) were formulated (pH ～ 7) using whey protein (3 wt%), three kinds of hydrocolloids (0.1–0.5 wt%) and two different emulsification energy inputs (single- and two-stage, methods A and B, respectively). Formula and energy input effects on emulsion performance are discussed. Emulsions stability was evaluated over a 10-day storage period at 5 °C recording the turbidity profiles of the emulsions. Optical micrographs, droplet size and viscosity values were also obtained. A differential scanning calorimetric (DSC) multiple cool–heat cyclic method (40 to ?40 °C) was performed to examine stability via crystallization phenomena of the dispersed phase.Ultrasonication energy input duplication from 11 kJ to 25 kJ (method B) resulted in stable emulsions production (reduction of back scattering values, dBS ～ 1% after 10 days of storage) at 0.5 wt% concentration of any of the stabilizers used. At lower gum amount samples became unstable due to depletion flocculation phenomena, regardless of emulsification energy input used. High energy input during ultrasonic emulsification also resulted in sub-micron oil-droplets emulsions (D₅₀ = 0.615 μm compared to D₅₀ = 1.3 μm using method A) with narrower particle size distribution and in viscosity reduction.DSC experiments revealed no presence of bulk oil formation, suggesting stability for XG 0.5 wt% emulsions prepared by both methods. Reduced enthalpy values found when method B was applied suggesting structural modifications produced by extensive ultrasonication. Change of ultrasonication conditions results in significant changes of oil droplet size and stability of the produced emulsions.     

Effect of ultrasonic pretreatment on the emulsification properties of Clanis Bilineata Tingtauica Mell protein

Clanis Bilineata Tingtauica Mell Protein (CBTMP) is a naturally high-quality insect protein resource, while its poor emulsification has limited its application in food industry. In order to change the present situation, in this research, the ultrasonic pretreatment (0 W, 200 W, 400 W, 600 W, and 800 W) method was used to improve the emulsification properties of CBTMP. Results indicated that ultrasound treatment especially at 400 W could significantly change the particle sizes, further increase the content of sulfhydryl group and surface hydrophobicity. The emulsification properties of emulsions were enhanced (from 4.16 ± 1.07 m²/g to 27.62 ± 2.20 m²/g) by sonicated CBTMP solution. Moreover, the physical stability of the emulsions to salt stress and centrifugation treatment was also promoted. Additionally, rheology revealed that a stronger network was formed at 400 W and all samples exhibited frequency-dependent and amplitude-dependent properties. The experiment demonstrated that ultrasound pretreatment was an effective means to improve the emulsification properties of CBTMP and it could provide a promising perspective for the application of CBTMP in food industry.     

Ultrasound-homogenization-assisted extraction of polyphenols from coconut mesocarp: Optimization study

Coconut pericarp (shell fiber (mesocarp) and shell (endocarp)), the main by-product of coconut production, is often discarded and causing serious environmental pollution. To make better use of coconut pericarp, the extraction process of polyphenols from coconut mesocarp (CM) carefully studied by screening seven solvent systems, optimizing the assisted ultrasonic process by response surface methodology, and comparing the four processes of Ultrasound-Assisted Extraction (UAE), Homogenization-Assisted Extraction (HAE), Homogenization-Ultrasound-Assisted Extraction (HUAE), and Ultrasound-Homogenization-Assisted Extraction (UHAE). The UAE and HAE are considered to be the main methods for efficient extraction of natural active ingredients. The former effectively destroys the cell wall structure and promotes the intermolecular diffusion based on the cavitation, thermal and mechanical effect of ultrasonic, while the latter breaks the material based on strong shear force between the rotor and stator. Their combinations (HUAE and UHAE) enhance the damage to the cell wall of raw materials and improve the extraction efficiency by the synergistic effect. The results showed that using 60% acetone (V : V) as extraction solvent, solid-liquid ratio of 1:5 g mL⁻¹, ultrasonic temperature of 80 ℃, ultrasonic time of 80 min, ultrasonic power of 225 W, and then homogenizing at 10,000 rpm for 10 min, the total flavonoid content of CM reached the maximum value of 551.99 ± 12.69 mg Rutin g⁻¹ dry weight (dw), while the total phenolic content reached the maximum value of 289.48 ± 4.41 mg GAE g⁻¹ dw at 10,000 rpm for 5 min, which may be related to the oxidative degradation of polyphenols caused by the increase of polyphenol oxidase with the extension of homogenization time. This study provides a technical guarantee for the further utilization of phenolic substances in CM.     

Converting of the 2D graphene to its 3D by chicken red blood cells as sheets separator for construction supercapacitor electrode

Here, we report on a facile green and scalable method for the fabrication of porous 3D graphene as a well-known carbon-based material used in many energy storage devices. Chicken red blood cells were used as sheets spacer and heteroatom sources in the construction of 3D graphene. First, the red blood cells were separated from the blood and mixed with graphene oxide. Then, the mixture was freeze-dried and carbonized at 700 °C. The resulted 3D graphene containing heteroatoms was used as a supercapacitor electrode modifier on a glassy carbon electrode and tested with various electrochemical techniques. The supercapacitor electrode showed a specific capacitance of 330 F g⁻¹ at a current density of 1 A g⁻¹, maximum power density of 1958 W kg⁻¹, and maximum energy density of 85 Wh kg⁻¹. Furthermore, the supercapacitive performances were tested in a two-electrode symmetrical system which exhibited a specific capacitance of 238 F g⁻¹ for 1 A g⁻¹. It also showed a power density of 2200 W kg⁻¹ and an appreciable energy density of 160 Wh kg⁻¹. The excellent electrochemical behavior of 3D graphene indicates the promising abilities of the composite for other applications such as biosensors, batteries, electrocatalysts, etc.     

Combining high intensity ultrasound and experimental design to improve carotenoid extraction efficiency from Buriti (Mauritia flexuosa)

Buriti (Mauritia flexuosa L.) is a significant source of carotenoids, but these compounds have been extracted using laborious and low-effective methods. The present work evaluated the high-intensity ultrasound combined with a chemometric approach to developing an optimal extraction method of carotenoids from buriti pulp. The multivariate optimization was carried out through two steps. First, a simplex-lattice mixture design was used to optimize the extractor solution finding higher extraction yield (903 ± 21 µg g⁻¹) with the acetone:ethanol (75/25) mixture. After, sample mass (80 mg) and sonication time (30 min) were optimized applying central composite design (CCD) which provided a 14% improvement in the extraction method yield. So, the total carotenoid content (TCC) with optimal extraction conditions was 1026 ± 13 µg g⁻¹ which is almost twice the yield of methods known in the literature for buriti. The RP-HPLC-DAD analysis revealed that the carotenoids are gently extracted and β-carotene is the major compound in the extracts. To confirm the accuracy, buriti samples spiked with β-carotene standard and the developed method showed recovery >84% and precision <6.5%. Furthermore, the optimized ultrasound-assisted extraction (UAE) method was applied to other samples (tomato, guava, carrot, mango, acerola, papaya, and pumpkin) and presented a yield to 5.5-fold higher when compared to the reported methods indicating high robustness. Based on results, the UAE method developed has demonstrated feasibility and reliability for the study of carotenoids in buriti pulp as well as in other plant matrices with high biological relevance.     

Biosynthesis of gold nanoparticles by Aspergillum sp. WL-Au for degradation of aromatic pollutants

A simple method for synthesis of gold nanoparticles (AuNPs) using Aspergillum sp. WL-Au was presented in this study. According to UV–vis spectra and transmission electron microscopy images, the shape and size of AuNPs were affected by different parameters, including buffer solution, pH, biomass and HAuCl₄ concentrations. Phosphate sodium buffer was more suitable for extracellular synthesis of AuNPs, and the optimal conditions for AuNPs synthesis were pH 7.0, biomass 100 mg/mL and HAuCl₄ 3 mM, leading to the production of spherical and pseudo-spherical nanoparticles. The biosynthesized AuNPs possessed excellent catalytic activities for the reduction of 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, o-nitroaniline and m-nitroaniline in the presence of NaBH₄, and the catalytic rate constants were calculated to be 6.3×10⁻³ s⁻¹, 5.5×10⁻³ s⁻¹, 10.6×10⁻³ s⁻¹, 8.4×10⁻³ s⁻¹ and 13.8×10⁻³ s⁻¹, respectively. The AuNPs were also able to catalyze the decolorization of various azo dyes (e.g. Cationic Red X-GRL, Acid Orange II and Acid scarlet GR) using NaBH₄ as the reductant, and the decolorization rates reached 91.0–96.4% within 7 min. The present study should provide a potential candidate for green synthesis of AuNPs, which could serve as efficient catalysts for aromatic pollutants degradation.     

Measurement of Ar(I) and Ar(II) transition probabilities in LTE ARC plasmas

The transition probabilities of two Ar(I) lines and one Ar(II) line have been measured in emission on wall-stabilized argon arc plasmas (0·5×10⁵?p, Nm^-2?3×10⁵; 10,000?T, K?20,000; 10²²?N_e, m^-3?5×10²³) using the “method of best fit (MBF)”. The results (without line-wing correction) are for Ar(I) at 714·7 nm, A_nm=5·66×10⁵ s^-1±5%; for Ar(I) at 430·0 nm, A_nm=3·40×10⁵ s^-1±5%; for Ar(II) at 480·6 nm, A_nm=8·82×10⁷ s^-1±7%. These values were not influenced by deviations from LTE, which have been observed at electron number densities n_e?10²³ m^-3. The small uncertainties were achieved after careful corrections of different sources of error.     

Reactions of hydrazine with the amidogen radical and atomic hydrogen

The rate coefficient k₁ for NH₂ + N₂H₄ was measured to be (5.4 ± 0.4) × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ at 296 K. NH₂ was generated by pulsed laser photolysis of NH₃ at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N₂H₄ in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k₁ = 6.3 × 10⁻²³ T^3.44 exp(+289 K/T) cm³ molecule⁻¹ s⁻¹. The minor channel for H + N₂H₄ forming NH₂ + NH₃ was characterized computationally as well, to yield 5.0 × 10⁻¹⁹ T^2.07 exp(-4032 K/T) cm³ molecule⁻¹ s⁻¹. These results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.     

Ultrasonic assisted synthesis of Ni3(VO4)2-reduced graphene oxide nanocomposite for potential use in electrochemical energy storage

In the present study, Ni₃(VO₄)₂-reduced graphene oxide (NV/RGO) nanocomposite was synthesized for energy storage purpose. To this end, a mixture containing RGO nanosheets, Ni (CH₃COOH)₂ and Na₃VO₄ mixture was prepared under probe-type ultrasonic irradiation with frequency of 20 KHz and the optimized power of 100 W. The Raman and energy-dispersive X-ray spectroscopies confirmed the presence of RGO nanosheets, nickel and vanadium elements in the NV/RGO, respectively. In addition, field emission-scanning electron microscopy (FESEM) data showed the formation of the NV nanoparticles on the RGO nanosheets. NV/RGO nanocomposite was pasted on nickel foam (NF) and its performance was investigated in energy storage using a three-electrode cell containing 6 M KOH. In cyclic voltammogram of NV/RGO/NF, redox peaks for Ni (II)/Ni (III) with intensities higher than that for NV/NF were observed which confirms the synergistic effect of RGO on the performance of NV. Chronopotentiometry data revealed that the NV/RGO/NF electrode exhibits high capacity of 117.22 mA h g⁻¹ at 2 A g⁻¹. Electrochemical impedance spectroscopy also demonstrated an improvement in the electrical conductivity and electrochemical behavior of NV/RGO/NF nanocomposite compared to the RGO/NF and NV/NF. Furthermore, NV/RGO/NF electrode reserved about 88% of its initial capacity after 1000th potential cycle at 50 mV s⁻¹. Overall, the results of our study suggest that the NV/RGO nanocomposite prepared in the presence of ultrasonic irradiation might be regarded as a suitable active material for energy storage systems.     

Structuring functional mayonnaise incorporated with Himalayan walnut oil Pickering emulsions by ultrasound assisted emulsification

Nowadays Pickering emulsions have attracted immense attention due to their enhanced stability and numerous food applications. In this context, the present study was aimed to introduce Pickering emulsions stabilized by soy protein isolate (SPI)-maltodextrin (MD)-pectin complex incorporated with Himalayan walnut oil (HWO) for development of novel mayonnaise by ultrasound assisted emulsification. The functional mayonnaise was characterised for its stability, structural, textural, rheological and morphological properties. The rheological and microstructure measurements indicated that use of SPI-pectin HWO emulsions had a viscoelastic solid behaviour (G′ > G″) with highly interconnected gel-like network structure leading to diffused oil droplet distribution. An increase in particle size diameter (1.86–5.09 µm) and hardness values (43.16–69.08 N) was seen with increase in the SPI-pectin wall material concentration. A significant reduction in whiteness (L* value) from 91.12 to 53.52 was noted during storage for encapsulated samples. Mayonnaise formulations containing encapsulated HWO depicted significantly lower peroxide value (2.65 meqO₂/kg) after extended storage period in comparison to free oil (8.33 meqO₂/kg). FTIR analysis of mayonnaise formulations depicted successful complexation of HWO with SPI-MD-pectin matrix. These findings would be of immense importance in designing of Pickering emulsions stabilized by protein-polysaccharide particles with aim of delivering nutraceuticals associated with myriad health benefits.     

Effect of high-intensity ultrasound on the physicochemical properties,microstructure, and stability of soy protein isolate-pectin emulsion

In this study, an emulsion stabilized by soy protein isolate (SPI)-pectin (PC) complexes was prepared to investigate the effects of high-intensity ultrasound (HIU) treatment (150–600 W) on the physicochemical properties, microstructure, and stability of emulsions. The results found that the emulsion treated at 450 W showed the best emulsion stability index (ESI) (25.18 ± 1.24 min), the lowest particle size (559.82 ± 3.17 nm), the largest ζ-potential absolute value (16.39 ± 0.18 mV), and the highest adsorbed protein content (27.31%). Confocal laser scanning microscopy (CLSM) and atomic force microscopy (AFM) revealed that the emulsion aggregation was significantly improved by ultrasound treatment, and the average roughness value (Rq) was the smallest (10.3 nm) at 450 W. Additionally, HIU treatment reduced the interfacial tension and apparent viscosity of the emulsion. Thermal stability was best when the emulsion was treated at 450 W, D₄₃ was minimal (907.95 ± 31.72 nm), and emulsion separation also improved. Consequently, the creaming index (CI) was significantly decreased compared to the untreated sample, indicating that the storage stability of the emulsion was enhanced.     

Fabrication of bilayer emulsion by ultrasonic emulsification: Effects of chitosan on the interfacial stability of emulsion

In this study, the stable system of bilayer emulsion was fabricated by ultrasonic emulsification. The effect of chitosan (CS) addition (0.05 %-0.4 %, w/v) at pH 5.0 on the stability of rice bran protein hydrolysate-ferulic acid (RBPH-FA) monolayer emulsion was investigated. It was found that the addition of CS (0.3 %) could form a stable bilayer emulsion. The droplet size was 3.38 μm and the absolute ζ-potential value was 31.52 mV. The bilayer emulsion had better storage stability, oxidation stability and environmental stabilities than the monolayer emulsion. The results of in vitro simulations revealed the bilayer emulsion was able to deliver the β-carotene to the small intestine digestive stage stably and the bioaccessibility was increased from 22.34 % to 61.36 % compared with the monolayer emulsion. The research confirmed that the bilayer emulsion prepared by ultrasonic emulsification can be used for the delivery of hydrophobic functional component β-carotene.     

Oxygen diffusion and surface exchange studies on (La0.75Sr0.25)0.95Cr0.5Mn0.5O3−δ

Oxygen tracer diffusion coefficient (D^⁎) and surface exchange coefficient (k^⁎) have been measured for (La_0.75Sr_0.25)_0.95Cr_0.5Mn_0.5O_3−δ using isotopic exchange and depth profiling by secondary ion mass spectrometry technique as a function of temperature (700–1000 °C) in dry oxygen and in a water vapour-forming gas mixture. The typical values of D^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 4 × 10^− 10 cm² s^− 1 and 3 × 10^− 8 cm² s^− 1 respectively, whereas the values of k^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 5 × 10^− 8 cm s^− 1 and 4 × 10^− 8 cm s^− 1 respectively. The apparent activation energies for D^⁎ in oxidising and reducing conditions are 0.8 eV and 1.9 eV respectively.     

Ultrasonic assisted water-in-oil emulsions encapsulating macro-molecular polysaccharide chitosan: Influence of molecular properties,emulsion viscosity and their stability

An ultrasonic technique was applied to formulation of two-phase water-in-paraffin oil emulsions loading a high-molecular polysaccharide chitosan (CS) and stabilized by an oil-soluble surfactant (Span80) at different operational conditions. The influence of chitosan molecular properties, phase volume ratio (φ_w), Span80 volume fraction (φ_s) and ultrasonic processing parameters were systemically investigated on the basis of mean droplet diameter (MDD) and polydispersity index (PDI) of emulsions. It was observed that the molecular weight (M_w) of CS was an important influential factor to MDD due to the non-Newtonian properties of CS solution varying with M_w. The minimum MDD of 198.5 nm with PDI of 0.326 was obtained with ultrasonic amplitude of 32% for 15 min at an optimum φ_w of 35%, φ_s of 8%, probe position of 2.2 cm to the top of emulsion, while CS with M_w of 400 kDa and deacetylation degree of 84.6% was used. The rise of emulsion viscosity and the reduction of negative zeta potential at φ_w increasing from 5% to 35% were beneficial to obtain finer droplets and more uniform distribution of emulsions, and emulsion viscosity could be represented as a monotonically-decreasing power function of MDD at the same φ_w. FTIR analysis indicated that the molecular structure of paraffin oil was unaffected during ultrasonication. Moreover, the emulsions exhibited a good stability at 4 °C with a slight phase separation at 25 °C after 24 h of storage. By analyzing the evolution of MDD, PDI and sedimentation index (SI) with time, coalescence model showed better fitting results as comparison to Ostwald ripening model, which demonstrated that the coalescence or flocculation was the dominant destabilizing mechanism for such W/O emulsions encapsulating CS. This study may provide a valuable contribution for the application of a non-Newtonian macromolecule solution as dispersed phase to generate nano-size W/O emulsions via ultrasound, and widen knowledge and interest of such emulsions in the functional biomaterial field.