Sonochemical synthesis of hierarchical ZnO nanostructures

This work is about fabrication of ZnO nanostructures (ZnO-NS) via a simple sonochemical method. The chemicals used for the synthesis of various shaped ZnO are Zn salt, sodium hydroxide and ammonia solution without other structure directing agent or surfactant needed. This method is feasible and green, as it does not require high temperature and/or highly toxic chemicals. The shape of the ZnO-NS can be tuned by adjusting the ultrasound energy dissipated via varying the ultrasonication time from 5 to 60 min. It was found that uniform ZnO nanorods with diameter around 50 nm were formed after 15 min of ultrasonication while flowerlike ZnO-NS was formed after 30 min. This method produces high quality ZnO-NS with controllable shapes, uniformity, and purity.     

Ultrasound irradiation promoted enzymatic alcoholysis for synthesis of monoglyceryl phenolic acids in a solvent-free system

Monoglyceryl phenolic acids (MPAs) were known as the natural hydrophilic antioxidants which could be used in different fields such as food, pharmaceutical, cosmetic etc. A novel enzymatic route of MPAs synthesis by the alcoholysis of phenolic acid ethyl esters with glycerol under ultrasound irradiation in solvent free system was developed. Optimization of reaction parameters shows that a high conversion of above 97.4% can be obtained under the following conditions: phenolic acid ethyl esters to glycerol molar ratio of 1:10, with 6% catalyst (Novozym 435), at 60 °C and 200 rpm, with ultrasound input of 250 W, at 20 kHz frequency. Compared to the conventional stirring method, the activation energy for phenolic acid ethyl esters conversion was decreased from 65.0 kJ/mol to 32.1 kJ/mol under ultrasound promotion; the apparent kinetic constant (V_m/K_m) increased above 1.2-folds; the lipase amount decreased to 50%; the time required for the maximum conversion reduced up to 3-folds without damaging the lipase activity, which is the fastest report for enzymatic synthesis of MPAs.     

Preparation of resveratrol-enriched and poor allergic protein peanut sprout from ultrasound treated peanut seeds

Peanut sprout is a kind of high quality natural food which has important effect on health-care. It contains abundant bioactive substances such as resveratrol and lower fat. Naturally, resveratrol occurs in stilbene phytoalexin phenolic compound produced in response to a variety of biotic and abiotic stresses. In this study, the influence of ultrasonic stimulation on the resveratrol accumulate in germinant peanut prepared from three varieties (FH12, FH18, and BS1016) in the dry state before steeping were investigated. All experiments were performed using an ultrasonic cleaner bath operating at three frequencies (28, 45 and 100 kHz) for 20 min at constant temperature 30 °C. The resulted amounts of resveratrol in peanut sprout were increasing by 2.25, 3.34, and 1.71 times compared with the control group of peanut germinated from FH12, FH18, and BS1016, respectively, after 3d with decreasing the amounts of allergic protein. After ultrasound, the germination rate and total sugar content increased slightly while the crude fat decreased and protein remained unchanged. Overall, the study results indicated that ultrasound treatment combined with germination can be an effective method for producing enriched-resveratrol and poor allergic protein peanut sprout as a functional vegetable.     

A sonochemical method for the preparation of cadmium sulfide and cadmium selenide nanoparticles in aqueous solutions

Sonochemistry is a branch of chemistry where sound energy in the form of ultrasound is used to influence the course of reactions. A short-term, local increase in temperature occurs when the solutions and suspensions are irradiated by ultrasound. This happens because the substance absorbs the ultrasound waves. The purpose of this research was the synthesis of CdS and CdSe nanoparticles. We used cadmium sulfate hydrate (CdSO₄·8/3H₂O), elemental S and Se. Aqueous solutions of NaOH, Na₂SO₃ and EDTA were used as the solvents.During the syntheses, we used a direct immersion ultrasound probe by vibracell. The device operates with a constant frequency of 20 kHz, with the possibility to change the amplitude and with it the input of energy to the time unit. The products were characterized by X-ray powder diffraction (XRD), thermal analyses (TGA, SDTA) and TEM analyses.     

Effect of reaction temperature on the size and morphology of scorodite synthesized using ultrasound irradiation

Synthesis of scorodite (FeAsO₄·2H₂O) using dynamic action agglomeration and the oxidation effect from ultrasound irradiation was investigated. The effect of different reaction temperatures (90, 70, 50, and 30 °C) on the size and morphology of scorodite particles synthesized under O₂ gas flow and ultrasound irradiation was explored because the generation of fine bubbles depends on the solution temperature. At 90 °C, the size of scorodite particles was non-homogeneous (from fine particles (<1 μm) to large particles (>10 μm)). The oxidation–reduction potential (ORP) and yield at 90 °C showed lower values than those at 70 °C. The scorodite particles, including fine and non-homogeneous particles, were generated by a decrease in the oxidation of Fe(II) to Fe(III) and promotion of dissolution caused by the generation of radicals and jet flow from ultrasound irradiation. Using ultrasound irradiation in the synthesis of scorodite at low temperature (30 °C) resulted in the appearance of scorodite peaks in the X-ray diffraction (XRD) pattern after a reaction time of 3 h. The peaks became more intense with a reaction temperature of 50 °C and crystalline scorodite was obtained. Therefore, ultrasound irradiation can enable the synthesis of scorodite at 30 °C as well as the synthesis of large particles (>10 μm) at higher temperature. Oxide radicals and jet flow generated by ultrasound irradiation contributed significantly to the synthesis and crystal growth of scorodite.     

Sustained release formulations of citronella oil nanoemulsion using cavitational techniques

Nanoemulsion synthesis has proven to be an effective way for transportation of immobile, insoluble bioactive compounds. Citronella Oil (lemongrass oil), a natural plant extract, can be used as a mosquito repellent and has less harmful effects compared to its available market counterpart DEET (N, N-Diethyl-meta-toluamide). Nanoemulsion of citronella oil in water was prepared using cavitation-assisted techniques while investigating the effect of system parameters like HLB (Hydrophilic Lipophilic Balance), surfactant concentration, input energy density and mode of power input on emulsion quality. The present work also examines the effect of emulsification on release rate to understand the relationship between droplet size and the release rate. Minimum droplet size (60 nm) of the emulsion was obtained at HLB of 14, S/O¹ ratio of 1.0, ultrasound amplitude of 50% and irradiation time of 5 min. This study revealed that hydrodynamic cavitation-assisted emulsification is more energy efficient compared to ultrasonic emulsification. It was also found that the release rate of nanoemulsion enhanced as the droplet size of emulsion reduced.     

Ultrasound-assisted acid hydrolysis of cellulose to chemical building blocks: Application to furfural synthesis

In this work, the use of ultrasound energy for the production of furanic platforms from cellulose was investigated and the synthesis of furfural was demonstrated. Several systems were evaluated, as ultrasound bath, cup horn and probe, in order to investigate microcrystalline cellulose conversion using simply a diluted acid solution and ultrasound. Several acid mixtures were evaluated for hydrolysis, as diluted solutions of HNO₃, H₂SO₄, HCl and H₂C₂O₄. The influence of the following parameters in the ultrasound-assisted acid hydrolysis (UAAH) were studied: sonication temperature (30 to 70 °C) and ultrasound amplitude (30 to 70% for a cup horn system) for 4 to 8 mol L⁻¹ HNO₃ solutions. For each evaluated condition, the products were identified by ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS), which provide accurate information regarding the products obtained from biomass conversion. The furfural structure was confirmed by nuclear magnetic resonance (¹H and ¹³C NMR) spectroscopy. In addition, cellulosic residues from hydrolysis reaction were characterized using scanning electron microscopy (SEM), which contributed for a better understanding of physical-chemical effects caused by ultrasound. After process optimization, a 4 mol L⁻¹ HNO₃ solution, sonicated for 60 min at 30 °C in a cup horn system at 50% of amplitude, lead to 78% of conversion to furfural. This mild temperature condition combined to the use of a diluted acid solution represents an important contribution for the selective production of chemical building blocks using ultrasound energy.     

Effect of ultrasound frequency on antioxidant activity,total phenolic and anthocyanin content of red raspberry puree

Ultrasound in the 20–1000 kHz range show unique propagation characteristics in fluid media and possess energy that can break down fruit matrices to facilitate the extraction of valuable bioactive compounds. Red raspberries carry significant amounts of specific antioxidants, including ellagitannins and anthocyanins that are important for human health. The objective of this study was to investigate the effects of ultrasound frequencies associated with cavitation (20 kHz) and microstreaming (490 and 986 kHz) on total antioxidant activity (AOA), total phenolics content (TPC), and total monomeric anthocyanin content (ACY) of red raspberry puree prepared from crushed berries. The pureed fruit was subjected to high-intensity (20 kHz) and higher frequency-low intensity (490 and 986 kHz) ultrasound for 30 min. The temperature of treated purees increased to a maximum of 56 °C with 986 kHz. Sonication at 20 and 490 kHz significantly (p < 0.05) affected the AOA, ACY, and TPC of red raspberry puree, while 986 kHz had no significant effect on ACY and AOA (p < 0.05). In all cases, ultrasound treatment had significant and positive effect on at least one of the measured parameters up to 30 min. Sonication beyond 10 min (and up to 30 min) using 20 kHz either produced no change or caused a drop in AOA and ACY. However, for 986 and 20 kHz, TPC, increased by 10% and 9.5%, respectively after 30 min (p < 0.05) compared to the control. At 20 kHz, AOA and ACY increased by 17.3% and 12.6% after 10 min. It was demonstrated that 20 kHz ultrasound treatment, when limited to 10 min, was the most effective for extraction of bioactive compounds in red raspberry compared to 490 and 986 kHz although the effect could be similar at the higher frequencies if different amplitudes are used.     

Sonochemical modification of carbon nanotubes for enhanced nanocomposite performance

Multi-walled carbon nanotubes (CNTs) have been treated using 20 kHz ultrasound in combination with dilute nitric and sulfuric acids at much lower concentrations than previously reported. The measurements revealed an optimum set of sonication conditions (in this case 30 min at 12 W cm⁻²) exists to overcome aggregation of the nanotubes and to allow efficient dispersion in ethanol or in chitosan. Transmission electron microscopy and Raman spectroscopy suggested the removal of amorphous material and reduction of the CNT diameter as well as modifications to their defect structures. The surface oxidation was determined by FTIR spectroscopy. At longer times or higher ultrasound intensities, degradation such as nanotube shortening and additional defect generation in the graphitic network occurred and the benefits of using ultrasound decreased. The modified CNTs were used as fillers for chitosan films and gave a tenfold increase in tensile strength and integrity of the films. The methodology was combined with sonochemical generation of gold or iron oxide nanoparticles to produce a range of functional membranes for catalytic reductive hydrogenation or dye degradation under conditions that are more environmentally benign than those previously used. Our results further add to the usefulness of sonochemistry as a valuable tool in preparative materials chemistry but also illustrate the crucial importance of careful control over the experimental conditions if optimum results are to be obtained.     

Ultrasound irradiation based in-situ synthesis of star-like Tragacanth gum/zinc oxide nanoparticles on cotton fabric

Application of natural biopolymers for green and safe synthesis of zinc oxide nanoparticles on the textiles is a novel and interesting approach. The present study offers the use of natural biopolymer, Tragacanth gum, as the reducing, stabilizing and binding agent for in-situ synthesis of zinc oxide nanoparticles on the cotton fabric. Ultrasonic irradiation leads to clean and easy synthesis of zinc oxide nanoparticles in short-time at low-temperature. FESEM/EDX, XRD, FT-IR spectroscopy, DSC, photocatalytic activities and antimicrobial assay are used to characterize Tragacanth gum/zinc oxide nanoparticles coated cotton fabric. The analysis confirmed synthesis of star-like zinc oxide nanoparticles with hexagonal wurtzite structure on the cotton fabric with the average particle size of 62 nm. The finished cotton fabric showed a good photocatalytic activity on degradation of methylene blue and 100% antimicrobial properties with inhibition zone of 3.3 ± 0.1, 3.1 ± 0.1 and 3.0 ± 0.1 mm against Staphylococcus aureus, Escherichia coli and Candida albicans.     

Thermosonication as a potential quality enhancement technique of apple juice

Enzymatic browning and microbial growth lead to quality losses in apple products. In the present study, fresh apple juice was thermosonicated using ultrasound in-bath (25 kHz, 30 min, 0.06 W cm⁻³) and ultrasound with-probe sonicator (20 kHz, 5 and 10 min, 0.30 W cm⁻³) at 20, 40 and 60 °C for inactivation of enzymes (polyphenolase, peroxidase and pectinmethylesterase) and microflora (total plate count, yeast and mold). Additionally, ascorbic acid, total phenolics, flavonoids, flavonols, pH, titratable acidity, ^°Brix and color values influenced by thermosonication were investigated. The highest inactivation of enzymes was obtained in ultrasound with-probe at 60 °C for 10 min, and the microbial population was completely inactivated at 60 °C. The retention of ascorbic acid, total phenolics, flavonoids and flavonols were significantly higher in ultrasound with-probe than ultrasound in-bath at 60 °C. These results indicated the usefulness of thermosonication for apple juice processing at low temperature, for enhanced inactivation of enzymes and microorganisms.     

Effect of ultrasound-assisted freezing on the physico-chemical properties and volatile compounds of red radish

Power ultrasound, which can enhance nucleation rate and crystal growth rate, can also affect the physico-chemical properties of immersion frozen products. In this study, the influence of slow freezing (SF), immersion freezing (IF) and ultrasound-assisted freezing (UAF) on physico-chemical properties and volatile compounds of red radish was investigated. Results showed that ultrasound application significantly improved the freezing rate; the freezing time of ultrasound application at 0.26 W/cm² was shorten by 14% and 90%, compared to IF and SF, respectively. UAF products showed significant (p < 0.05) reduction in drip loss and phytonutrients (anthocyanins, vitamin C and phenolics) loss. Compared to SF products, IF and UAF products showed better textural preservation and higher calcium content. The radish tissues exhibited better cellular structures under ultrasonic power intensities of 0.17 and 0.26 W/cm² with less cell separation and disruption. Volatile compound data revealed that radish aromatic profile was also affected in the freezing process.     

Development and validation of an efficient ultrasound assisted extraction of phenolic compounds from flax (Linum usitatissimum L.) seeds

Flaxseed accumulates in its seedcoat a macromolecular complex composed of lignan (secoisolariciresinol diglucoside, SDG), flavonol (herbacetin diglucoside, HDG) and hydroxycinnamic acids (p-couramic, caffeic and ferulic acid glucosides). Their antioxidant and/or cancer chemopreventive properties support their interest in human health and therefore, the demand for their extraction. In the present study, ultrasound-assisted extraction (UAE) of flaxseed phenolic compounds was investigated. Scanning Electron Microscopy imaging and histochemical analysis revealed the deep alteration of the seedcoat ultrastructure and the release of the mucilage following ultrasound treatment. Therefore, this method was found to be very efficient for the reduction of mucilage entrapment of flaxseed phenolics. The optimal conditions for UAE phenolic compounds extraction from flaxseeds were found to be: water as solvent supplemented with 0.2 N of sodium hydroxide for alkaline hydrolysis of the SDG–HMG complex, an extraction time of 60 min at a temperature of 25 °C and an ultrasound frequency of 30 kHz. Under these optimized and validated conditions, highest yields of SDG, HDG and hydroxycinnamic acid glucosides were detected in comparison to other published methods. Therefore, the procedure presented herein is a valuable method for efficient extraction and quantification of the main flaxseed phenolics. Moreover, this UAE is of particular interest within the context of green chemistry in terms of reducing energy consumption and valuation of flaxseed cakes as by-products resulting from the production of flax oil.     

Power ultrasound as a pretreatment to convective drying of mulberry (Morus alba L.) leaves: Impact on drying kinetics and selected quality properties

The effect of ultrasound pretreatment prior to convective drying on drying kinetics and selected quality properties of mulberry leaves was investigated in this study. Ultrasound pretreatment was carried out at 25.2–117.6 W/L for 5–15 min in a continuous mode. After sonication, mulberry leaves were dried in a hot-air convective dryer at 60 °C. The results revealed that ultrasound pretreatment not only affected the weight of mulberry leaves, it also enhanced the convective drying kinetics and reduced total energy consumption. The drying kinetics was modeled using a diffusion model considering external resistance and effective diffusion coefficient D_e and mass transfer coefficient h_m were identified. Both D_e and h_m during convective drying increased with the increase of acoustic energy density (AED) and ultrasound duration. However, D_e and h_m increased slowly at high AED levels. Furthermore, ultrasound pretreatment had a more profound influence on internal mass transfer resistance than on external mass transfer resistance during drying according to Sherwood numbers. Regarding the quality properties, the color, antioxidant activity and contents of several bioactive compounds of dried mulberry leaves pretreated by ultrasound at 63.0 W/L for 10 min were similar to that of mulberry leaves without any pretreatments. Overall, ultrasound pretreatment is effective to shorten the subsequent drying time of mulberry leaves without damaging the quality of final product.     

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 h to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.     

Kinetic modeling of ultrasound-assisted extraction of phenolic compounds from grape marc: Influence of acoustic energy density and temperature

The effects of acoustic energy density (6.8–47.4 W/L) and temperature (20–50 °C) on the extraction yields of total phenolics and tartaric esters during ultrasound-assisted extraction from grape marc were investigated in this study. The ultrasound treatment was performed in a 25-kHz ultrasound bath system and the 50% aqueous ethanol was used as the solvent. The initial extraction rate and final extraction yield increased with the increase of acoustic energy density and temperature. The two site kinetic model was used to simulate the kinetics of extraction process and the diffusion model based on the Fick’s second law was employed to determine the effective diffusion coefficient of phenolics in grape marc. Both models gave satisfactory quality of data fit. The diffusion process was divided into one fast stage and one slow stage and the diffusion coefficients in both stages were calculated. Within the current experimental range, the diffusion coefficients of total phenolics and tartaric esters for both diffusion stages increased with acoustic energy density. Meanwhile, the rise of temperature also resulted in the increase of diffusion coefficients of phenolics except the diffusion coefficient of total phenolics in the fast stage, the value of which being the highest at 40 °C. Moreover, an empirical equation was suggested to correlate the effective diffusion coefficient of phenolics in grape marc with acoustic energy density and temperature. In addition, the performance comparison of ultrasound-assisted extraction and convention methods demonstrates that ultrasound is an effective and promising technology to extract bioactive substances from grape marc.     

Green ultrasound-assisted extraction of carotenoids based on the bio-refinery concept using sunflower oil as an alternative solvent

A green, inexpensive and easy-to-use method for carotenoids extraction from fresh carrots assisted by ultrasound was designed in this work. Sunflower oil was applied as a substitute to organic solvents in this green ultrasound-assisted extraction (UAE): a process which is in line with green extraction and bio-refinery concepts. The processing procedure of this original UAE was first compared with conventional solvent extraction (CSE) using hexane as solvent. Moreover, the UAE optimal conditions for the subsequent comparison were optimized using response surface methodology (RSM) and ultra performance liquid chromatography – diode array detector – mass spectroscopy (UPLC–DAD–MS). The results showed that the UAE using sunflower as solvent has obtained its highest β-carotene yield (334.75 mg/l) in 20 min only, while CSE using hexane as solvent obtained a similar yield (321.35 mg/l) in 60 min. The green UAE performed under optimal extraction conditions (carrot to oil ratio of 2:10, ultrasonic intensity of 22.5 W cm^?2, temperature of 40 °C and sonication time of 20 min) gave the best yield of β-carotene.     

Intensification of extraction of curcumin from Curcuma amada using ultrasound assisted approach: Effect of different operating parameters

Curcumin, a dietary phytochemical, has been extracted from rhizomes of Curcuma amada using ultrasound assisted extraction (UAE) and the results compared with the conventional extraction approach to establish the process intensification benefits. The effect of operating parameters such as type of solvent, extraction time, extraction temperature, solid to solvent ratio, particle size and ultrasonic power on the extraction yield have been investigated in details for the approach UAE. The maximum extraction yield as 72% was obtained in 1 h under optimized conditions of 35 °C temperature, solid to solvent ratio of 1:25, particle size of 0.09 mm, ultrasonic power of 250 W and ultrasound frequency of 22 kHz with ethanol as the solvent. The obtained yield was significantly higher as compared to the batch extraction where only about 62% yield was achieved in 8 h of treatment. Peleg’s model was used to describe the kinetics of UAE and the model showed a good agreement with the experimental results. Overall, ultrasound has been established to be a green process for extraction of curcumin with benefits of reduction in time as compared to batch extraction and the operating temperature as compared to Soxhlet extraction.     

Intensification of heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction using ultrasound: Understanding effect of operating parameters

Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is a significant reaction for obtaining industrially important products. The current research work deals with intensification of reaction of 4-bromoanisole and phenylboronic acid catalyzed with 5 wt% Pd/C (5% by weight Pd supported on C available as commercial catalyst) using ultrasound and more importantly, without use of any additional phase transfer catalyst. Heterogeneous catalyst has been selected in the present work so as to harness the benefits of easy separation and the possible limitations of heterogeneous operation are minimized by introducing ultrasonic irradiations. The effect of operating parameters such as ultrasound power, temperature, catalyst loading and molar ratio on the progress of reaction has been investigated. It has been observed that an optimum power, temperature and catalyst loading exist for maximum benefits whereas higher molar ratio was found to be favourable for the progress of the reaction. Also, the use of ultrasound reduced the reaction time from 70 min required in conventional approach to only 35 min under conditions of frequency of 22 kHz, power dissipation of 40 W and catalyst loading as 1.5 mol% (refers to total quantum of catalyst used in the work) in ethanol-water system under ambient conditions. The work also demonstrated successful results at ten times higher volume as compared to the normally used volumes in the case of simple ultrasonic horn. Overall, the work has successfully demonstrated process intensification benefits obtained due to the use of ultrasound for heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction.     

Sonosynthesis of gold nanoparticles from a geranium leaf extract

A rapid in situ biosynthesis of gold nanoparticles (AuNPs) is proposed in which a geranium (Pelargonium zonale) leaf extract was used as a non-toxic reducing and stabilizing agent in a sonocatalysis process based on high-power ultrasound. The synthesis process took only 3.5 min in aqueous solution under ambient conditions. The stability of the nanoparticles was studied by UV–Vis absorption spectroscopy with reference to the surface plasmon resonance (SPR) band. AuNPs have an average lifetime of about 8 weeks at 4 °C in the absence of light. The morphology and crystalline phase of the gold nanoparticles were characterized by transmission electron microscopy (TEM). The composition of the nanoparticles was evaluated by electron diffraction and X-ray energy dispersive spectroscopy (EDS). A total of 80% of the gold nanoparticles obtained in this way have a diameter in the range 8–20 nm, with an average size of 12 ± 3 nm. Fourier transform infrared spectroscopy (FTIR) indicated the presence of biomolecules that could be responsible for reducing and capping the biosynthesized gold nanoparticles. A hypothesis concerning the type of organic molecules involved in this process is also given. Experimental design linked to the simplex method was used to optimize the experimental conditions for this green synthesis route. To the best of our knowledge, this is the first time that a high-power ultrasound-based sonocatalytic process and experimental design coupled to a simplex optimization process has been used in the biosynthesis of AuNPs.