Sonoelectrochemical hydrogenation of safrole: A reactor design,statistical analysis and computational fluid dynamic approach

In this work, ultrasound-assisted electrocatalytic hydrogenation (US-ECHSA) of safrole was carried out in water medium, using sacrificial anode of nickel. The ultrasonic irradiation was carried out at frequency of 20 kHz ± 500 Hz with a titanium cylindrical horn (MS 73 microtip; Ti-6AI-4V alloy; 3.0 mm diameter). The optimal conditions were analyzed by statistical experimental design (fractional factorial). The influence of the sonoelectrochemical reactor design was also investigated by using computational fluid dynamics as simulation tool. Among the five parameters studied: catalyst type, use of β-cyclodextrin as inverse phase transfer catalyst, sonoelectrochemical reactor design, ultrasound mode and the temperature of the solution, only the last three were significant. The hydrogenation product, dihydrosafrole, reached 94% yield, depending on the experimental conditions applied. Data of computational fluid dynamics showed that a wing shape tube added to the sonoelectrochemical reactor can work as a cooling apparatus, during the electrochemical process. The reactional solution temperature diminishes 14 °C when compared to the four-way-type reactor. Cooper cathode, absence of β-cyclodextrin, four-way-type reactor, ultrasound continuous mode (14 W) and absence of temperature control were the most effective reaction parameters for the safrole hydrogenation using US-ECHSA method. The proposed approach represents an important contribution for understanding the hydrodynamic behavior of sonoelectrochemical reactors designs and, consequently, for the reducing of the experimental costs inherent to the sonoelectrochemical process.     

Synergistic antibacterial effects of ultrasound and thyme essential oils nanoemulsion against Escherichia coli O157:H7

Essential oil nanoemulsions have been proven to have stronger antimicrobial effects compared to the essential oil alone or coarse emulsion. Sonoporation could be the promising candidate to trigger a synergistic effect with thyme essential oil nanoemulsion (TEON) and produce a more effective antibacterial efficacy. Therefore, in this study, the bactericidal effects of ultrasound (US) in combination with TEON treatments against Escherichia coli (E. coli) O157:H7 were investigated. The remarkable synergistic effects of US (20 kHz, 255 W/cm², 9 min) and TEON (0.375 mg/mL) treatments at 22 °C reduced E. coli O157:H7 populations by 7.42 ± 0.27 log CFU/mL.The morphological changes of cells exposed to different treatments were observed by scanning electron microscopy and transmission electron microscopy. The results showed that the synergistic effects of the ultrasound and TEON treatments altered the morphology and interior microstructure of organism cells. Laser scanning confocal microscopy (LSCM) images revealed that the combination treatments of ultrasound and TEON altered the permeability of cell membranes, and this affected the integrity of E. coli O157:H7 cells. This was further indicated by the high amounts of nucleic acids and proteins released from these cells following treatment.The results from this study illustrated the mechanisms of the synergistic effects of sonoporation and TEON treatments and provided valuable information for their potential in food pasteurization.     

A facile and eco-friendly approach for preparation of microkeratin and nanokeratin by ultrasound-assisted enzymatic hydrolysis

Protein is one of the most abundant natural polymeric materials, but only a few studies on nanoproteins have been conducted. In this paper, a novel approach based on ultrasound-assisted enzymatic hydrolysis was employed for the preparation of microkeratin and nanokeratin from wool. The hydrolysis system included a solution containing enzyme (esperase) and reductant (L-cysteine) and treated ultrasonically to remove the scales and amorphous regions within wool. Results showed that the reaction was most effective at 50 °C and pH 7, when incubated for 3 h, followed by sonication for 6 h. The products included spindle-shaped microkeratin (4–7 μm in diameter and 70–120 μm in length) and cone-shaped nanokeratin (50–300 nm in diameter and less than 15 μm in length). Under ultrasonic-assisted conditions, the yields of microkeratin and nanokeratin increased significantly, while the treatment time decreased. Fourier transform infrared spectroscopy (FTIR) showed that the chemical structures of microkeratin and nanokeratin did not change, compared to that of wool. X-ray diffraction (XRD) analysis showed that the microkeratin was mainly composed of α-helical structure, while the β-sheet structure was more prevalent in nanokeratin. The presented method is facile and eco-friendly, thereby paving new pathways for the preparation of microkeratin and nanokeratin.     

Solubility study and intensification of extraction of phenolic and anthocyanin compounds from Oryza sativa L. ‘Violet Nori’

Oryza sativa L. ‘Violet Nori’ is an Italian cultivar of spontaneous growing aromatic purple rice which is particularly rich in polyphenolic compounds, especially anthocyanins, conferring it an excellent antioxidant capacity. The present study aimed at increasing the extraction yields of its antioxidant compounds with green strategies and it is divided into two steps. The first step concerned a solubility study of the targeted polyphenols in different ethanol:water mixtures by means of a theoretical prediction method, using the simulation program COSMO-RS, and the subsequently confirmation of the computational results by practical experiments. Once the best extraction mixture was identified, the second step of the work was performed, with the purpose of intensifying the extraction yield. Therefore, various innovative green extraction techniques, including ultrasound, using both the probe system and the ultrasonic bath, bead milling, microwave and accelerated solvent extractions were tested and compared to conventional maceration.Results, expressed in terms of total phenolic and total monomeric anthocyanin contents, showed that the best extracting solvent for ‘Violet Nori’ rice was the mixture ethanol:water (60:40 v/v), being COSMO-RS computational predictions in good correlation with the experimental results. Moreover, the most efficient techniques to extract the antioxidant compounds resulted to be both ultrasound-assisted extraction probe and bead milling, that in only 5 min got the same extractive efficiency obtained after 3 h of conventional maceration.     

Ultrasound irradiation effect on morphological and adsorptive properties of a nanoscale 3D Zn-coordination polymer and derived oxide

In this work, Zn-based coordination polymer [Zn₂(1,3-bdc)bzim₂]_n was successfully synthesized by the sonochemical method using a 13 mm probe-type ultrasound operating at 20 kHz and amplitudes of 30, 40 and 50% corresponding to an acoustic power of 5.5, 8.6, and 10.3 W, respectively. Additionally, a sample was prepared by the slow-diffusion method for comparison. The samples were characterized by FTIR, PXRD, SEM, and BET techniques. The influence of the time and sonication amplitude on the yield of the reaction, crystallite size, and morphology were also studied. It was found that the sonochemical method provided the desired product in 83.9% within 20 min of sonication using the highest level of sonication amplitude. Moreover, this approach resulted in regular, controlled morphology, smaller particles, and higher surface area of the Zn-sample and derived oxide, than the slow diffusion method. The samples prepared by different methodologies were tested for the adsorption of BTEX (benzene, toluene, ethylbenzene, and xylenes) components in six different systems, and the uptakes were quantified by ¹³C NMR spectroscopy. Both samples showed excellent adsorption of benzene, 119.8 mmol/g, and 88.1 mmol/g, for the coordination polymers prepared via the sonochemical and slow-diffusion methods, respectively, corresponding to 63.9%, and 46.9%. These results are in agreement with the non-polar surface of these samples.     

Inactivation of foodborne pathogens based on synergistic effects of ultrasound and natural compounds during fresh produce washing

Ultrasound has potential to be used for disinfection, and its antimicrobial effectiveness can be enhanced in presence of natural compounds. In this study, we compared the antimicrobial effects of ultrasound at 20 kHz (US 20 kHz) or 1 MHz (US 1 MHz) in combination with carvacrol, citral, cinnamic acid, geraniol, gallic acid, lactic acid, or limonene against E. coli K12 and Listeria innocua at a constant power density in water. Compared to the cumulative effect of the individual treatments, the combined treatment of US 1 MHz and 10 mM citral generated >1.5 log CFU/mL additional inactivation of E. coli K12. Similarly, combined treatments of US 1 MHz and 2 mM carvacrol (30 min), US 20 kHz and 2 mM carvacrol, 10 mM citral, or 5 mM geraniol (15 min) generated >0.5–2.0 log CFU/mL additional inactivation in L. innocua. The synergistic effect of citral, as a presentative compound, and US 20 kHz treatment was determined to be a result of enhanced dispersion of insoluble citral droplets in combination with physical impact on bacterial membrane structures, whereas the inactivation by US 1 MHz was likely due to generation of oxidative stress within the bacteria. Combined ultrasound and citral treatments improved the bacterial inactivation in simulated wash water in presence of organic matter or during washing of inoculated blueberries but only additive antimicrobial effects were observed. Findings in this study will be useful to enhance fresh produce safety and shelf-life and design other alternative ultrasound based sanitation processes.     

Standing wave-assisted acoustic droplet vaporization for single and dual payload release in acoustically-responsive scaffolds

An ultrasound standing wave field (SWF) has been utilized in many biomedical applications. Here, we demonstrate how a SWF can enhance drug release using acoustic droplet vaporization (ADV) in an acoustically-responsive scaffold (ARS). ARSs are composite fibrin hydrogels containing payload-carrying, monodispersed perfluorocarbon (PFC) emulsions and have been used to stimulate regenerative processes such as angiogenesis. Elevated amplitudes in the SWF significantly enhanced payload release from ARSs containing dextran-loaded emulsions (nominal diameter: 6 μm) compared to the -SWF condition, both at sub- and suprathreshold excitation pressures. At 2.5 MHz and 4 MPa peak rarefactional pressure, the cumulative percentage of payload released from ARSs reached 84.1 ± 5.4% and 66.1 ± 4.4% under + SWF and -SWF conditions, respectively, on day 10. A strategy for generating a SWF for an in situ ARS is also presented. For dual-payload release studies, bi-layer ARSs containing a different payload within each layer were exposed to temporally staggered ADV at 3.25 MHz (day 0) and 8.6 MHz (day 4). Sequential payload release was demonstrated using dextran payloads as well as two growth factors relevant to angiogenesis: basic fibroblast growth factor (bFGF) and platelet-derived growth factor BB (PDGF-BB). In addition, bubble growth and fibrin degradation were characterized in the ARSs under +SWF and -SWF conditions. These results highlight the utility of a SWF for modulating single and dual payload release from an ARS and can be used in future therapeutic studies.     

Assessment of the beneficial combination of electrochemical and ultrasonic activation of compounds originating from biomass

The electro-oxidation of organic molecules at the anode with simultaneous generation of hydrogen at the cathode in electrosynthesis reactors is considered as a promising and efficient process for the co-production of hydrogen and bio-sourced value-added chemicals. In this study and for the first time, we investigated the electro-oxidation of glucose and methylglucoside in 0.1 mol L⁻¹ NaOH on polycrystalline Pt (real surface area = 14.5 ± 0.5 cm², roughness ≈ 5) in the potential range [0; +1.20 V vs. rhe] under silent and ultrasonic (bath, 45 kHz, P_acous = 11.20 W) conditions. A series of linear sweep voltammograms, chronoamperograms and high-performance liquid chronoamperograms were generated. It was found that higher current densities were obtained under ultrasonic conditions over the potential range of +0.25 V to +1.10 V vs. rhe, indicating that higher oxidation rates were provided under ultrasonication. It was observed that the desorption of species from the Pt surface in the medium potential region was favoured, allowing free catalytic Pt sites for further adsorption and oxidation of reactants; and in the high potential region, high peak current densities in the presence of ultrasound was due to enhanced mass transport of the electroactive species from the bulk electrolyte to the Pt-polycrystalline electrode surface. HPLC studies confirmed that higher electrochemical activity was obtained in the presence of ultrasound than in the absence. In our conditions, it was also found that low frequency ultrasound did not change the selectivity of the glucose and methylglucoside electro-oxidation reactions but instead, a significant increase in the rate of conversion was observed.     

Intensified dissolution of uranium from graphite substrate using ultrasound

Decontamination of graphite structural elements and recovery of uranium is crucial for waste minimization and recycle of nuclear fuel elements. Feasibility of intensified dissolution of uranium-impregnated graphite substrate using ultrasound has been studied with objective of establishing the effect of operating parameters and the kinetics of sonocatalytic dissolution of uranium in nitric acid. The effect of operating frequency and acoustic intensity as well as the acid concentration and temperature on the dissolution of metal has been elucidated. It was observed that at lower acid concentrations (6 M–8 M), the dissolution ratio increases by 15% on increasing the bath temperature from 45 to 70 °C. At higher acid concentration (>10 M), the increase was only around 5–7% for a similar change in temperature. With 12 M HNO₃, pitting was also observed on the graphite surface along with erosion due to high local reaction rates in the presence of ultrasound. For higher frequency of applied ultrasound, lower dissolution rate of uranium was observed though it also leads to high rates of erosion of the substrate. It was thus established that suitable optimization of frequency is required based on the nature of the substrate and the choice of recycling it. The dissolution rate was also demonstrated to increase with acoustic intensity till it reaches to the maximum at the observed optimum (1.2 W/cm² at 33 kHz). Comparison with silent conditions revealed that enhanced rate was obtained due to the use of ultrasound under optimum conditions. The work has demonstrated the effective application of ultrasound for intensifying the extent of dissolution of metal.     

Localized enzymolysis and sonochemically modified sunflower protein: Physical,functional and structure attributes

Impacts of localized enzymolysis and sonication on physical, techno-functional, and structure attributes of sunflower meal protein (SMP) and its hydrolysate (SMPH) were studied. SMP was subjected to enzymolysis (using alcalase) to prepare SMPH with various degrees of hydrolysis (6–24% DH). Enzymolysis decreased colour lightness, turbidity, and particle size of unsonicated and sonicated SMP, while it increased the absolute values of zeta potential (P < 0.05). Sonication improved oil absorption capacity and dispersibility over unsonicated samples. Contrarily, sonicated preparations showed a decrease in water holding capacity. Intrinsic fluorescence and FTIR spectral analyses suggested that SMPH had more movable/flexible secondary structures than SMP. Moreover, the changes in sulfhydryl clusters and disulfide linkages following sonication demonstrated limited unfolding of SMP and SMPH structure and decrease in intermolecular interactions. SDS-PAGE profile exhibited significant reduction in molecular weight (MW) of sonicated SMP, whereas did not display differences between unsonicated and sonicated SMPH. From further MW analysis, SMPH was categorized with high proportion of small-sized peptides ≤ 3 kDa fractions, which increased from 78.64 to 93.01% (control) and from 82.3 to 93.88% (sonication) with enzymolysis (6–24DH). Localized enzymolysis and sonication can be utilised to modify the physical and conformational attributes of SMP and SMPH, which could enhance their functionalities and broaden the utilisation area in food industry.