Sonochemistry, an almost a century old technique was predominantly employed in the cleaning and extraction processes but this tool has now slowly gained tremendous attention in the synthesis of nanoparticles (NPs) where particles of sub-micron have been produced with great stability. Following this, ultrasonication techniques have been largely employed in graphene synthesis and its dispersion in various solvents which would conventionally take days and offers poor yield. Ultrasonic irradiation allows the production of thin-layered graphene oxide (GO) and reduced graphene oxide (RGO) of up to 1nm thickness and can be produced in single layers. With ultrasonic treatment, reactions were made easy whereby graphite can be directly exfoliated to graphene layers. Oxidation to GO can also be carried out within minutes and reduction to RGO is possible without the use of any reducing agents. In addition, various geometry of graphene can be produced such as scrolled graphene, sponge or foam graphene, smooth as well as those with rough edges, each serving its own unique purpose in various applications such as supercapacitor, catalysis, biomedical, etc. In ultrasonic-assisted reaction, deposition of metal NPs on graphene was more homogeneous with custom-made patterns such as core-shell formation, discs, clusters and specific deposition at the edges of graphene sheets. Graphene derivatives with the aid of ultrasonication are the perfect catalyst for various organic reactions as well as an excellent adsorbent. Reactions which used to take hours and days were significantly reduced to minutes with exceedingly high yields. In a more recent approach, sonophotocatalysis was employed for the combined effect of sonication and photocatalysis of metal deposited graphene. The system was highly efficient in organic dye adsorption. This review provides detailed fundamental concepts of ultrasonochemistry for the synthesis of graphene, its dispersion, exfoliation as well as its functionalization, with great emphasis only based on recent publications. Necessary parameters of sonication such as frequency, power input, sonication time, type of sonication as well as temperature and dual-frequency sonication are discussed in great length to provide an overview of the resultant graphene products.
Sugarcane juice (Saccharum officinarum) is a proven nutritious beverage with high levels of antioxidants, polyphenols, and other beneficial nutrients. It has recently gained consumer interest due to its high nutritional profile and alkaline nature. Still, high polyphenolic and sugar content start the fermentation in juice, resulting in dark coloration. Lately, some novel techniques have been introduced to extend shelf life and improve the nutritional value of sugarcane juice. The introduction of such processing technologies is beneficial over conventional processes and essential for producing chemical-free, high-quality, fresh juices. The synergistic impact of these novel technologies is also advantageous for preserving sugarcane juice. In literature, novel thermal, non-thermal and hurdle technologies have been executed to preserve sugarcane juice. These technologies include high hydrostatic pressure (HHP), ultrasound (US), pulsed electric field (PEF), ultraviolet irradiation (UV), ohmic heating (OH), microwave (MW), microfludization and ozone treatment. This review manifests the impact of novel thermal, non-thermal, and synergistic technologies on sugarcane juice processing and preservation characteristics. Non-thermal techniques have been successfully proved effective and showed better results than novel thermal treatments. Because they reduced microbial load and retained nutritional content, while thermal treatments degraded nutrients and flavor of sugarcane juice. Among non-thermal treatments, HHP is the most efficient technique for the preservation of sugarcane juice while OH is preferable in thermal techniques due to less nutritional loss.
The ion exchange constant, KXBr (for the case of cetyltrimethylammonium bromide, CTABr, in this study) is a method dependant characterization of ion exchange process by counterions, X and Br with different relative binding ratios. In this report, the ion exchange constant, KXBr values for micelle systems irradiated under 2 min of sonication at 120 W power using a probe sonicator with 1 cm tip were determined to be 85.2, 125.6 and 122.4 when X = o-, m- and p-chlorobenzoates, respectively. The values were quantified using a semiempirical kinetic method coupled with Pseudophase Micellar model, and later compared to the same system in the absence of sonication. The sonication was found to amplify the KXBr values by ~ 13-fold for X = o-chlorobenzoate and ~ 2.5-fold for X = m- and p-chlorobenzoates. This is due to the improvement of ion exchange process by the oscillation of bubbles generated by acoustic cavitation. An active ion exchange process indicates better stabilization of the micelle aggregational structure by the penetration of the introduced counterions, X into the micelle Stern layer leading to the growth of the micelle. This is supported by the remarkable increase in the viscosity of the micelle system by > 7-fold for X = o-chlorobenzoate and by > 2-folds for X = m- and p-chlorobenzoates. Sonication was also found to induce maximum viscoelasticity at lower concentration ratio of [CTABr]:[X]. The ability of ultrasound to induce micelle growth and exhibiting viscoelasticity at lower concentration of counterionic additive will be very useful in technologies where viscoelastic solution is desired such as in oil drilling and centralized heating and cooling system.
In this study, high-frequency ultrasound wave (1.8 MHz) at low intensity was applied to improve activated sludge settleability at high MLSS concentration. The effect of irradiation intensity, sonication mode, MLSS concentration and sample volume on the physical characteristics of sludge in a pilot scale settling column were investigated for optimizing the conditions. The obtained results showed that high-frequency ultrasound decreased the height of sludge (44%) and effluent turbidity (82.2%) and increased sludge settling velocity about 3 times at high biomass concentration. Irradiation intensity of 0.4 w/cm2 and sonication mode with interval times of 10 s showed the best results on the performance of the system at MLSS concentration of 8000 mg/L with a sample volume of 3 L.
The nonsteroidal anti-inflammatory drug sodium diclofenac (DC) is an emerging water pollutant which resists conventional wastewater treatments. Here the sonophotocatalytic degradation of DC was carried out using micrometric TiO2 (both pristine and Ag-decorated), UV-A irradiation and 20 kHz pulsed ultrasound. Sonophotocatalytic tests were compared with photolysis, sonolysis, sonophotolysis, sonocatalysis and photocatalysis data performed in the same conditions. A synergy index of over 2 was determined for tests with pristine TiO2, while values close to 1.3 were observed for Ag-TiO2. Reaction intermediates were studied by HPLC-MS, showing degradation mechanisms activated by hydroxyl radicals. Similar pathways were identified for photocatalytic and sonophotocatalytic tests, although the latter led to more oxidized compounds. Different reactor configurations (static and dynamic set ups) were studied. Sequential and simultaneous application of UV light and ultrasound led to similar performance. The role of water matrix was investigated using ultrapure and drinking water, showing marked detrimental effects of electrolytes on the DC degradation. Overall, the combined treatment proved more efficient than photocatalysis alone especially in demanding working conditions, like in drinking water matrices.
Calcium silicate hydrate (CSH) consisting of nanosheets has been successfully synthesized assisted by a tip ultrasonic irradiation (UI) method using calcium nitrate (Ca(NO3)·4H2O), sodium silicate (Na2SiO3·9H2O) and sodium dodecyl sulfate (SDS) in water. Systematic studies found that reaction time of ultrasonic irradiation and concentrations of surfactant (SDS) in the system were important factors to control the crystallite size and morphologies. The products were characterized by X-ray power diffraction (XRD), field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectrometry (FTIR). The size-strain plot (SSP) method was used to study the individual contributions of crystallite sizes and lattice strain on the peak broadening of the CSH. These characterization techniques revealed the successful formation of a crystalline phase with an average crystallite size of about 13 nm and nanosheet morphology at a reaction time of 10 min UI with 0.2 g SDS in solvent which were found to be optimum time and concentrations of SDS for the synthesis of CSH powders.
Biodiesel production via esterification/transesterification reactions can be catalyzed by homogenous or heterogeneous catalysts. Development of heterogeneous catalysts for biodiesel production is highly advantageous due to the ease of product purification and of catalyst recyclability. In this current work, a novel acidic [DABCODBS][CF3SO3]2 dicationic ionic liquid (DIL) was used as heterogeneous catalyst to produce biodiesel using oleic acid as model oil. The esterification was conducted under ultrasonic irradiation (20 kHz) using a 14 mm ultrasonic horn transducer operated at various duty cycles. It was observed that the duty cycle, amplitude, methanol to oil molar ratio, catalyst amount and reaction temperature were the major factors that greatly impact the necessary reaction time to lead to a high yield of biodiesel. The reaction conditions were optimized with the aid of Response Surface Methodology (RSM) designed according to the Quadratic model of the Box Behnken method. The optimum conditions were found to be at catalyst amount of 0.64 mol%, methanol to oil ratio of 14.3:1, temperature of 59 °C, reaction time of 83 min and amplitude of 60% in continuous mode. The results showed that the oleic acid was successfully converted into esters with conversion value of 93.20% together with significant reduction of reaction time from 7 h (using mechanical stirring) to 83 min (using ultrasonication). The results also showed that the acidic DIL catalyst we designed purposely was efficient to catalyze the ultrasonic-assisted esterification yielding high conversion of oleic acid to methyl oleate on short times. The DIL was also recycled and reused for at least five times without significant reduction in performance. Overall, the procedureoffersadvantages including short reaction time, good yield, operational simplicity and environmentally benign characteristics.
Palm oil mill effluent (POME) is a highly contaminating wastewater due to its high chemical oxygen demand (COD) and biochemical oxygen demand (BOD). Conventional treatment methods require longer residence time (10-15 days) and higher operating cost. Owing to this, finding a suitable and efficient method for the treatment of POME is crucial. In this investigation, ultrasound cavitation technology has been used as an alternative technique to treat POME. Cavitation is the phenomenon of formation, growth and collapse of bubbles in a liquid. The end process of collapse leads to intense conditions of temperature and pressure and shock waves which assist various physical and chemical transformations. Two different ultrasound systems i.e. ultrasonic bath (37 kHz) and a hexagonal triple frequency ultrasonic reactor (28, 40 and 70 kHz) of 15 L have been used. The results showed a fluctuating COD pattern (in between 45,000 and 60,000 mg/L) while using ultrasound bath alone, whereas a non-fluctuating COD pattern with a final COD of 27,000 mg/L was achieved when hydrogen peroxide was introduced. Similarly for the triple frequency ultrasound reactor, coupling all the three frequencies resulted into a final COD of 41,300 mg/L compared to any other individual or combination of two frequencies. With the possibility of larger and continuous ultrasonic cavitational reactors, it is believed that this could be a promising and a fruitful green process engineering technique for the treatment of POME.
O/W nanoemulsions are isotropic colloidal systems constituted of oil droplets dispersed in continuous aqueous media and stabilised by surfactant molecules. Nanoemulsions hold applications in more widespread technological domains, more crucially in the pharmaceutical industry. Innovative nanoemulsion-based drug delivery system has been suggested as a powerful alternative strategy through the useful means of encapsulating, protecting, and delivering the poorly water-soluble bioactive components. Consequently, there is a need to generate an emulsion with small and consistent droplets. Diverse studies acknowledged that ultrasonic cavitation is a feasible and energy-efficient method in making pharmaceutical-grade nanoemulsions. This method offers more notable improvements in terms of stability with a lower Ostwald ripening rate. Meanwhile, a microstructured reactor, for instance, microchannel, has further been realised as an innovative technology that facilitates combinatorial approaches with the acceleration of reaction, analysis, and measurement. The recent breakthrough that has been achieved is the controlled generation of fine and monodispersed multiple emulsions through microstructured reactors. The small inner dimensions of microchannel display properties such as short diffusion paths and high specific interfacial areas, which increase the mass and heat transfer rates. Hence, the combination of ultrasonic cavitation with microstructures (microchannel) provides process intensification of creating a smaller monodispersed nanoemulsion system. This investigation is vital as it will then facilitate the creation of new nanoemulsion based drug delivery system continuously. Following this, the fabrication of microchannel and setup of its combination with ultrasound was conducted in the generation of O/W nanoemulsion, as well as optimisation to analyse the effect of varied operating parameters on the mean droplet diameter and dispersity of the nanoemulsion generated, besides monitoring the stability of the nanoemulsion. Scanning transmission electron microscopy (STEM) images were also carried out for the droplet size measurements. In short, the outcomes of this study are encouraging, which necessitates further investigations to be carried out to advance a better understanding of coupling microchannel with ultrasound to produce pharmaceutical-grade nanoemulsions.
The ability of sonication phenomena in facilitating separation of azeotropic mixtures presents a promising approach for the development of more intensified and efficient distillation systems than conventional ones. To expedite the much-needed development, a mathematical model of the system based on conservation principles, vapor-liquid equilibrium and sonochemistry was developed in this study. The model that was founded on a single stage vapor-liquid equilibrium system and enhanced with ultrasonic waves was coded using MATLAB simulator and validated with experimental data for ethanol-ethyl acetate mixture. The effects of both ultrasonic frequency and intensity on the relative volatility and azeotropic point were examined, and the optimal conditions were obtained using genetic algorithm. The experimental data validated the model with a reasonable accuracy. The results of this study revealed that the azeotropic point of the mixture can be totally eliminated with the right combination of sonication parameters and this can be utilized in facilitating design efforts towards establishing a workable ultrasonically intensified distillation system.
Improving dispersion stability of nanofluids through ultrasonication has been shown to be effective. Determining specific conditions of ultrasonication for a certain nanofluid is necessary. For this purpose, nanofluids of varying nanoparticle concentrations were prepared and studied to find out a suitable and rather mono-dispersed concentration (i.e., 0.5 vol.%, determined through transmission electron microscopy (TEM) analyses). This study aims to report applicable ultrasonication conditions for the dispersion of Al2O3 nanoparticles within H2O through the two-step production method. The prepared samples were ultrasonicated via an ultrasonic horn for 1-5h at two different amplitudes (25% and 50%). The microstructure, particle size distribution (PSD), and zeta potentials were analyzed to investigate the dispersion characteristics. Better particle dispersion, smaller aggregate sizes, and higher zeta potentials were observed at 3 and 5h of ultrasonication duration for the 50% and 25% of sonicator power amplitudes, respectively.
Nanofluids are promising in many fields, including engineering and medicine. Stability deterioration may be a critical constraint for potential applications of nanofluids. Proper ultrasonication can improve the stability, and possibility of the safe use of nanofluids in different applications. In this study, stability properties of TiO2-H2O nanofluid for varying ultrasonication durations were tested. The nanofluids were prepared through two-step method; and electron microscopies, with particle size distribution and zeta potential analyses were conducted for the evaluation of their stability. Results showed the positive impact of ultrasonication on nanofluid dispersion properties up to some extent. Ultrasonication longer than 150min resulted in re-agglomeration of nanoparticles. Therefore, ultrasonication for 150min was the optimum period yielding highest stability. A regression analysis was also done in order to relate the average cluster size and ultrasonication time to zeta potential. It can be concluded that performing analytical imaging and colloidal property evaluation during and after the sample preparation leads to reliable insights.
The aim of this study was to evaluate the effect of ultrasound on the intestinal adherence ability, cell growth, and cholesterol removal ability of parent cells and subsequent passages of Lactobacillus fermentum FTDC 1311. Ultrasound significantly decreased the intestinal adherence ability of treated parent cells compared to that of the control by 11.32% (P<0.05), which may be due to the protein denaturation upon local heating. Growth of treated parent cells also decreased by 4.45% (P<0.05) immediately upon ultrasound (0-4h) and showed an increase (P<0.05) in the viability by 2.18-2.34% during the later stage of fermentation (12-20 h) compared to that of the control. In addition, an increase (P<0.05) in assimilation of cholesterol (>9.74%) was also observed for treated parent cells compared to that of the control, accompanied by increased (P<0.05) incorporation of cholesterol into the cellular membrane. This was supported by the increased ratio of membrane cholesterol:phospholipids (C:P), saturation of cholesterol in the apolar regions, upper phospholipids regions, and polar regions of membrane phospholipids of parent cells compared to that of the control (P<0.05). However, such traits were not inherited by the subsequent passages of treated cells (first, second, and third passages). Our data suggested that ultrasound treatment could be used to improve cholesterol removal ability of parent cells without inducing permanent damage/defects on treated cells of subsequent passages.
This study aimed to evaluate the effect of ultrasound treatment on the cholesterol removing ability of lactobacilli. Viability of lactobacilli cells was significantly increased (P < 0.05) immediately after treatment, but higher intensity of 100 W and longer duration of 3 min was detrimental on cellular viability (P < 0.05). This was attributed to the disruption of membrane lipid bilayer, cell lysis and membrane lipid peroxidation upon ultrasound treatment at higher intensity and duration. Nevertheless, the effect of ultrasound on membrane properties was reversible, as the viability of ultrasound-treated lactobacilli was increased (P < 0.05) after fermentation at 37 °C for 20 h. The removal of cholesterol by ultrasound-treated lactobacilli via assimilation and incorporation of cholesterol into the cellular membrane also increased significantly (P < 0.05) upon treatment, as observed from the increased ratio of membrane C:P. Results from fluorescence anisotropies showed that most of the incorporated cholesterol was saturated in the regions of phospholipids tails, upper phospholipids, and polar heads of the membrane bilayer.
Ultrasound (US) demonstrates remarkable potential in synthesising nanomaterials, particularly nanobiomaterials targeted towards biomedical applications. This review briefly introduces existing top-down and bottom-up approaches for nanomaterials synthesis and their corresponding synthesis mechanisms, followed by the expounding of US-driven nanomaterials synthesis. Subsequently, the pros and cons of sono-nanotechnology and its advances in the synthesis of nanobiomaterials are drawn based on recent works. US-synthesised nanobiomaterials have improved properties and performance over conventional synthesis methods and most essentially eliminate the need for harsh and expensive chemicals. The sonoproduction of different classes and types of nanobiomaterials such as metal and superparamagnetic nanoparticles (NPs), lipid- and carbohydrate-based NPs, protein microspheres, microgels and other nanocomposites are broadly categorised based on the physical and/or chemical effects induced by US. This review ends on a good note and recognises US-driven synthesis as a pragmatic solution to satisfy the growing demand for nanobiomaterials, nonetheless some technical challenges are highlighted.
Ultrasound was applied simultaneously with adsorption process in most of the previous studies. However, this method is not practical to treat huge amounts of coloured wastewater effluent. In this study, the efficiency of ultrasound pre-treated peanut husk powder at different power levels (1.5-3.5 W) in dye adsorption with several conditions of initial dye concentration (20-100 mg/L), contact time (0.5-5 h), solution pH (2-8), and dosage (0.1-0.3 g) was studied and compared with ultrasound simultaneous adsorption process and the control. Adsorption efficiency of indirect ultrasound pre-treated peanut husk powder has increased 25.78%, 13.64% and 1.5% compared with the control, ultrasound simultaneous adsorption and direct ultrasound pre-treated sample respectively at 60 mg/L of initial dye concentration. Indirect ultrasound pre-treated sample at 3.5 W has achieved the highest adsorption efficiency of 89.96% at solution pH 8 and 94.83% at 0.3 g dose for 3 h. The surface feature and textural properties of samples were characterized by using scanning electron microscopy and surface characterization analyser. The result indicated that more porous structure was created on the ultrasound pre-treated sample at increasing power levels.
The current work proposed an alternative ultrasound (US) technology, namely the high-intensity ultrasonic tubular reactor (HUTR) for preparing Pickering emulsions. Using the non-toxic and environmentally friendly cellulose nanocrystal (CNC) as a solid stabilizer, Pickering emulsions were produced using the HUTR and the results showed that Pickering emulsions as small as 1.5 µm can be produced using HUTR at the US power and sonication time of 300 W and 15 min respectively. Additionally, the sizes of Pickering emulsion obtained are found to remain the same upon 30 days of storage. The performance of HUTR in emulsion preparation is compared to conventional US horn system at the same US power. It was observed that the use of HUTR allowed generation of Pickering emulsion that is significantly smaller (around 7.40 μm) and with better droplet size distribution (Coefficient of variation, CV = 31%) as compared to those prepared with US horn method (12.75 µm, CV = 36%). This is owing to the better distribution of cavitation activity in the treatment chamber of HUTR as compared to those in the horn, according to the sonochemiluminescence (SCL) study. From the 30-days storage stability analysis, the CNC-PE prepared using HUTR was found to more stable against droplet coalescence in comparison to those prepared using US horn. Our findings suggested that the HUTR possessed superior Pickering emulsification capacity when compared to conventional US horn. Further work will be necessary to evaluate the feasibility of such intensifying tubular reactor technology for larger scale emulsification and other process intensification applications.
Sonodynamic therapy (SDT) emerges as a promising non-invasive alternative for eradicating malignant tumours. However, its therapeutic efficacy remains limited due to the lack of sonosensitisers with high potency and biosafety. Previously, gold nanorods (AuNRs) have been extensively studied for their applications in photodynamic or photothermal cancer therapy, but their sonosensitising properties are largely unexplored. Here, we reported the applicability of alginate-coated AuNRs (AuNRsALG) with improved biocompatibility profiles as promising nanosonosensitisers for SDT for the first time. AuNRsALG were found stable under ultrasound irradiation (1.0 W/cm2, 5 min) and maintained structural integrity for 3 cycles of irradiation. The exposure of the AuNRsALG to ultrasound irradiation (1.0 W/cm2, 5 min) was shown to enhance the cavitation effect significantly and generate a 3 to 8-fold higher amount of singlet oxygen (1O2) than other reported commercial titanium dioxide nanosonosensitisers. AuNRsALG exerted dose-dependent sonotoxicity on human MDA-MB-231 breast cancer cells in vitro, with ∼ 81% cancer cell killing efficacy at a sub-nanomolar level (IC50 was 0.68 nM) predominantly through apoptosis. The protein expression analysis showed significant DNA damage and downregulation of anti-apoptotic Bcl-2, suggesting AuNRsALG induced cell death through the mitochondrial pathway. The addition of mannitol, a reactive oxygen species (ROS) scavenger, inhibited cancer-killing effect of AuNRsALG-mediated SDT, further verifying that the sonotoxicity of AuNRsALG is driven by the production of ROS. Overall, these results highlight the potential application of AuNRsALG as an effective nanosonosensitising agent in clinical settings.
Sequentially precipitated Mg-promoted nickel-silica catalysts with ageing performed under various ultrasonic intensities were employed to study the catalyst performance in the partial hydrogenation of sunflower oil. Results from various characterisation studies showed that increasing ultrasonic intensity caused a higher degree of hydroxycarbonate erosion and suppressed the formation of Ni silicates and silica support, which improved Ni dispersion, BET surface area and catalyst reducibility. Growth of silica clusters on the catalyst aggregates were observed in the absence of ultrasonication, which explained the higher silica and nickel silicate content on the outer surface of the catalyst particle. Application of ultrasound also altered the electron density of the Ni species, which led to higher activity and enhanced product selectivity for sonicated catalysts. The catalyst synthesised with ultrasonic intensity of 20.78 Wcm-2 achieved 22.6% increase in hydrogenation activity, along with 28.5% decrease in trans-C18:1 yield at IV = 70, thus supporting the feasibility of such technique.
Glassy carbon particles (millimetric or micrometric sizes) dispersions in water were treated by ultrasound at 20kHz, either in a cylindrical reactor, or in a "Rosette" type reactor, for various time lengths ranging from 3h to 10h. Further separations sedimentation allowed obtaining few nanoparticles of glassy carbon in the supernatant (diameter <200nm). Thought the yield of nanoparticle increased together with the sonication time at high power, it tended to be nil after sonication in the cylindrical reactor. The sonication of glassy carbon micrometric particles in water using "Rosette" instead of cylindrical reactor, allowed preparing at highest yield (1-2wt%), stable suspensions of carbon nanoparticles, easily separated from the sedimented particles. Both sediment and supernatant separated by decantation of the sonicated dispersions were characterized by laser granulometry, scanning electron microscopy, X-ray microanalysis, and Raman and infrared spectroscopies. Their multiscale organization was investigated by transmission electron microscopy as a function of the sonication time. For sonication longer than 10h, these nanoparticles from supernatant (diameter <50nm) are aggregated. Their structures are more disordered than the sediment particles showing typical nanometer-sized aromatic layer arrangement of glassy carbon, with closed mesopores (diameter ∼3nm). Sonication time longer than 5h has induced not only a strong amorphization (subnanometric and disoriented aromatic layer) but also a loss of the mesoporous network nanostructure. These multi-scale organizational changes took place because of both cavitation and shocks between particles, mainly at the particle surface. The sonication in water has induced also chemical effects, leading to an increase in the oxygen content of the irradiated material together with the sonication time.