Hydrolysis acceleration in an Al-Ga-Gr particle material utilizing ultrasound irradiation

The improvement of the hydrogen production rate and the hydrogen conversion ratio is crucial for hydrogen acquirement via Al-water reactions. Present work fabricated an Al-Ga-Gr hydrolyzing particle material, and presents the accelerated hydrolysis by ultrasound irradiation to achieve a high speed of hydrolysis and 100% yield within a short time, and provides a weak coupling model to address the acoustic pressure, velocity and thermal fields in the reactor. The obtained material is characterized with lamellar morphologies comprising AlGa solid solution and Gr. The hydrolysis is accelerated within the cavitation region by peeling off the reaction by-product layer to expose fresh aluminum, and deteriorates after the particle material traversing the cavitation/non-cavitation region boundary. Ultrasound promotes the hydrolysis progress from a diffusion governed mode to a dominated regime of interface reaction without a change to the activation energy.     

Enhancement of ultrasound-assisted extraction of sulforaphane from broccoli seeds via the application of microwave pretreatment

In this study, microwave pretreatment and grinding treatment were used to enhance sulforaphane formation, then ultrasonic-assisted extraction (UAE) was applied to extract sulforaphane using simultaneous hydrolysis and extraction method. The effects of various parameters, which were ultrasonic time, ultrasonic power, solid-water ratio and solid-ethyl acetate ratio on the extraction rate of sulforaphane were investigated. The results showed that microwave pretreatment enhanced sulforaphane formation. Excessive size reduction did not increase or even reduced extraction rate of sulforaphane. Simultaneous hydrolysis and extraction significantly increased extraction rate of sulforaphane compared to hydrolysis followed by extraction. UAE accelerated mass transfer and the solubilization of the targeted compounds due to the acoustic cavitation effect, thus enhanced enzymatic hydrolysis of glucoraphanin and the extraction rate of sulforaphane. The extraction rate of sulforaphane using UAE with simultaneous hydrolysis and extraction was 4.07-fold of the conventional extraction method. UAE was an effective method to extract sulforaphane from broccoli seeds since it led to higher yield of sulforaphane in a much shorter extraction time.     

Acoustic and hydrodynamic cavitation assisted hydrolysis and valorisation of waste human hair for the enrichment of amino acids

Hair waste in large amount is produced in India from temples and saloons, India alone exported approximately 1 million kg of hair in 2010. Incineration and degradation of waste human hair leads to environmental concerns. The hydrothermal process is a conventional method for the production of hair hydrolysate. The hydrothermal process is carried out at a very high temperature and pressure, which causes the degradation of heat-sensitive essential amino acids, thereby depleting the nutritional value. This work deals with alkaline hydrolysis of human hair using acoustic and hydrodynamic cavitation, and comparison with the conventional method. The optimal operating conditions for highest efficiency was observed, for the hydrolysis of 1 g of sample hairs in 100 mL of solution, at 4:1 (KOH: hair) ratio, soaking time of 24 h, the ultrasonic power density of 600 W dm⁻³ (20 KHz frequency and input power 200 W) or hydrodynamic cavitation inlet pressure of 4 or 7 bars. Cavitation results in rupture of disulfide linkages in proteins and mechanical effects lead to cleavage of several hydrogen bonds breaking the keratin sheet structure in hair. Breakdown of bonds leads to a decrease in viscosity of the solution. 10% and 6% reduction in viscosity is obtained at optimal conditions for ultrasonic and hydrodynamic cavitation treatment, respectively. FTIR analysis of produced hair hydrolysate confirmed that the disulfide bonds in hair proteins are broken down during cavitation. The amino acid of hair hydrolysate, prepared using cavitation, has a relatively higher digestibility and nutritional value due to the enhancement of amino-acid content, confirmed using amino acid analysis. Cavitation assisted hair hydrolysate has a potential application in agricultural engineering as a fertilizer for improvement of the quality of the soil and land. Cavitation based hair hydrolysate can also be used as an environmentally friendly and economical source of essential amino acids and digestibles for animal or poultry feed.     

The impact of methanol mass transport on its conversion for the production of hydrogen and oxygenated reactive species in sono-irradiated aqueous solution

This study aims principally to assess numerically the impact of methanol mass transport (i.e., evaporation/condensation across the acoustic bubble wall) on the thermodynamics and chemical effects (methanol conversion, hydrogen and oxygenated reactive species production) of acoustic cavitation in sono-irradiated aqueous solution. This effect was revealed at various ultrasound frequencies (from 213 to 1000 kHz) and acoustic intensities (1 and 2 W/cm²) over a range of methanol concentrations (from 0 to 100%, v/v). It was found that the impact of methanol concentration on the expansion and compression ratios, bubble temperature, CH₃OH conversion and the molar productions inside the bubble is frequency dependent (either with or without consideration of methanol mass transport), where this effect is more pronounced when the ultrasound frequency is decreased. Alternatively, the decrease in acoustic intensity decreases clearly the effect of methanol mass transport on the bubble sono-activity. When methanol mass transfer is eliminated, the decrease of the bubble temperature, CH₃OH conversion and the molar yield of the bubble with the rise of methanol concentration was found to be more amortized as the wave frequency is reduced from 1 MHz to 213 kHz, compared to the case when the mass transport of methanol is taken into account. Our findings indicate clearly the importance of incorporating the evaporation and condensation mechanisms of methanol throughout the numerical simulations of a single bubble dynamics and chemical activity.     

Cavitation based cleaner technologies for biodiesel production and processing of hydrocarbon streams: A perspective on key fundamentals,missing process data and economic feasibility – A review

The present review emphasizes the role of hydrodynamic cavitation (HC) and acoustic cavitation in clean and green technologies for selected fuels (of hydrocarbon origins such as gasoline, naphtha, diesel, heavy oil, and crude oil) processing applications including biodiesel production. Herein, the role of cavitation reactors, their geometrical parameters, physicochemical properties of liquid media, liquid oxidants, catalyst loading, reactive oxygen species, and different types of emulsification and formation of radicals, formation as well as extraction of formed by-products are systematically reviewed. Among all types of HC reactors, vortex diode and single hole orifices revealed more than 95 % desulfurization yield and a 20 % viscosity reduction in heavy oil upgrading, while multi-hole orifice (100 holes) and slit Venturi allowed obtaining the best biodiesel production processes in terms of high (%) yield, low cost of treatment, and short processing time (5 min; 99 % biodiesel; 4.80 USD/m³). On the other hand, the acoustic cavitation devices are likely to be the most effective in biodiesel production based on ultrasonic bath (90 min; 95 %; 6.7 $/m³) and desulfurization treatment based on ultrasonic transducers (15 min; 98.3 % desulfurization; 10.8 $/m³). The implementation of HC-based processes reveals to be the most cost-effective method over acoustic cavitation-based devices. Finally, by reviewing the ongoing applications and development works, the limitations and challenges for further research are addressed emphasizing the cleaner production and guidelines for future scientists to assure obtaining comprehensive data useful for the research community.     

A high-temperature acoustic field measurement and analysis system for determining cavitation intensity in ultrasonically solidified metallic alloys

A high-temperature acoustic field measurement and analysis system (HTAFS) was self-designed and developed to achieve real-time acoustic field analysis and quantitative cavitation characterization within high-temperature liquids. The acoustic signal was acquired by a high-temperature resistant waveguide and calibrated by separate compensation of line and continuous spectra to eliminate frequency offsets. Moreover, a new method was proposed to derive from the continuous-spectrum sound intensity and line-spectrum sound intensity in the frequency band above 1.5 times the fundamental frequency to characterize the intensity of transient cavitation and stable cavitation. The acoustic field characteristics within solidifying liquid Al-7 %Si alloy were successfully determined by this system. With the increase of ultrasound amplitude, the acoustic pressure in the alloy melt increased to be stable, the transient cavitation intensity first rose and then declined, and the stable cavitation intensity remained unchanged. Combined with the structural evolution of the primary α(Al) phase, the transient cavitation intensity was determined to be the dominant factor for the ultrasound-induced grain refinement effect.     

Single-transducer dual-frequency ultrasound generation to enhance acoustic cavitation

Dual- or multiple-frequency ultrasound stimulation is capable of effectively enhancing the acoustic cavitation effect over single-frequency ultrasound. Potential application of this sonoreactor design has been widely proposed such as on sonoluminescence, sonochemistry enhancement, and transdermal drug release enhancement. All currently available sonoreactor designs employed multiple piezoelectric transducers for generating single-frequency ultrasonic waves separately and then these waves were mixed and interfered in solutions. The purpose of this research is to propose a novel design of generating dual-frequency ultrasonic waves with single piezoelectric elements, thereby enhancing acoustic cavitation. Macroscopic bubbles were detected optically, and they were quantified at either a single-frequency or for different frequency combinations for determining their efficiency for enhancing acoustic cavitation. Visible bubbles were optically detected and hydrogen peroxide was measured to quantify acoustic cavitation. Test water samples with different gas concentrations and different power levels were used to determine the efficacy of enhancing acoustic cavitation of this design. The spectrum obtained from the backscattered signals was also recorded and examined to confirm the occurrence of stable cavitation. The results confirmed that single-element dual-frequency ultrasound stimulation can enhance acoustic cavitation. Under certain testing conditions, the generation of bubbles can be enhanced up to a level of five times higher than the generation of bubbles in single-frequency stimulation, and can increase the hydrogen peroxide production up to an increase of one fold. This design may serve as a useful alternative for future sonoreactor design owing to its simplicity to produce dual- or multiple-frequency ultrasound.     

Dependence of cavitation,chemical effect,and mechanical effect thresholds on ultrasonic frequency

Cavitation, chemical effect, and mechanical effect thresholds were investigated in wide frequency ranges from 22 to 4880 kHz. Each threshold was measured in terms of sound pressure at fundamental frequency. Broadband noise emitted from acoustic cavitation bubbles was detected by a hydrophone to determine the cavitation threshold. Potassium iodide oxidation caused by acoustic cavitation was used to quantify the chemical effect threshold. The ultrasonic erosion of aluminum foil was conducted to estimate the mechanical effect threshold. The cavitation, chemical effect, and mechanical effect thresholds increased with increasing frequency. The chemical effect threshold was close to the cavitation threshold for all frequencies. At low frequency below 98 kHz, the mechanical effect threshold was nearly equal to the cavitation threshold. However, the mechanical effect threshold was greatly higher than the cavitation threshold at high frequency. In addition, the thresholds of the second harmonic and the first ultraharmonic signals were measured to detect bubble occurrence. The threshold of the second harmonic approximated to the cavitation threshold below 1000 kHz. On the other hand, the threshold of the first ultraharmonic was higher than the cavitation threshold below 98 kHz and near to the cavitation threshold at high frequency.     

In situ studies on free-standing synthesis of nanocatalysts via acoustic levitation coupled with pulsed laser irradiation

Acoustic levitation is a distinctive and versatile tool for levitating and processing free-standing single droplets and particles. Liquid droplets suspended in an acoustic standing wave provide container-free environments for understanding chemical reactions by avoiding boundary effects and solid surfaces. We attempted to use this strategy for the production of well-dispersed uniform catalytic nanomaterials in an ultraclean confined area without the addition of external reducing agents or surfactants. In this study, we report on the synthesis of gold and silver nanoparticles (NPs) via acoustic levitation coupled with pulsed laser irradiation (PLI). In situ UV–Visible and Raman spectroscopic techniques were performed to monitor the formation and growth of gold and silver NPs. The PLI was used for the photoreduction of targeted metal ions present in the levitated droplets to generate metal NPs. Additionally, the cavitation effect and bubble movement accelerate the nucleation and decrease the size of NPs. The synthesized Au NPs with ∼ 5 nm size showed excellent catalytic behavior towards the conversion of 4-nitrophenol to 4-aminophenol. This study may open a new door for synthesizing various functional nanocatalysts and for achieving new chemical reactions in suspended droplets.     

Effect of gold nanoparticle size on acoustic cavitation using chemical dosimetry method

When a liquid is irradiated with high intensities of ultrasound irradiation, acoustic cavitation occurs. Acoustic cavitation generates free radicals from the breakdown of water and other molecules. Cavitation can be fatal to cells and is utilized to destroy cancer tumors. The existence of particles in liquid provides nucleation sites for cavitation bubbles and leads to decrease the ultrasonic intensity threshold needed for cavitation onset. In the present investigation, the effect of gold nanoparticles with appropriate amount and size on the acoustic cavitation activity has been shown by determining hydroxyl radicals in terephthalic acid solutions containing 15, 20, 28 and 35 nm gold nanoparticles sizes by using 1 MHz low level ultrasound. The effect of sonication intensity in hydroxyl radical production was considered.The recorded fluorescence signal in terephthalic acid solutions containing gold nanoparticles was considerably higher than the terephthalic acid solutions without gold nanoparticles at different intensities of ultrasound irradiation. Also, the results showed that the recorded fluorescence signal intensity in terephthalic acid solution containing finer size of gold nanoparticles was lower than the terephthalic acid solutions containing larger size of gold nanoparticles. Acoustic cavitation in the presence of gold nanoparticles can be used as a way for improving therapeutic effects on the tumors.     

Ultrasound enhanced production of mycelia and exopolysaccharide by Agaricus bitorquis (Quél.) Sacc. Chaidam

Agaricus bitorquis (Quél.) Sacc. Chaidam (ABSC), is a kind of rare edible macrofungi with a variety of biological ingredients, especially its polysaccharides. However, the low yield limits the popularity and promotion of rare edible macrofungi as well as its macrofungi polysaccharides. Hence, developing a positive and effective cultivation method is of great importance. Herein, an efficient ultrasonic (US) stimulation strategy was developed to improve mycelial growth and exopolysaccharides (EPS) biosynthesis from ABSC in submerged cultivation without light. A time design was employed to illustrate the effect of various process parameters including duration, starting point and times of US irradiation on ABSC productivity. 5 min US treatment for once upon ABSC after fermentation for 48 h could significantly improve EPS production and mycelia growth by above 26% and 15.03%, respectively. Furthermore, six times of 5 min US treatment could make the amount of EPS reach 218.78 ± 17.09 mg/g, which was 2.52-fold higher than that of the control. Moreover, the enhanced effect induced by US was further expounded by fermentation kinetics. Besides, the US treatment could increase mycelia permeability, change structure and reduce mycelial diameter to promote mass transfer, resulting in the improvement of EPS production and mycelia accumulation. The results demonstrated that the present proposed US intensification approach could be useful to boost up the fermentation of ABSC, which possibly applied to yield increase and fermentation product acquisition of macrofungi.     

Cavitation characteristics of flowing low and high boiling-point perfluorocarbon phase-shift nanodroplets during focused ultrasound exposures

This work investigated and compared the dynamic cavitation characteristics between low and high boiling-point phase-shift nanodroplets (NDs) under physiologically relevant flow conditions during focused ultrasound (FUS) exposures at different peak rarefactional pressures. A passive cavitation detection (PCD) system was used to monitor cavitation activity during FUS exposure at various acoustic pressure levels. Root mean square (RMS) amplitudes of broadband noise, spectrograms of the passive cavitation detection signals, and normalized inertial cavitation dose (ICD) values were calculated. Cavitation activity of low-boiling-point perfluoropentane (PFP) NDs and high boiling-point perfluorohexane (PFH) NDs flowing at in vitro mean velocities of 0–15 cm/s were compared in a 4-mm diameter wall-less vessel in a transparent tissue-mimicking phantom. In the static state, both types of phase-shift NDs exhibit a sharp rise in cavitation intensity during initial FUS exposure. Under flow conditions, cavitation activity of the PFH NDs reached the steady state less rapidly compared to PFP NDs under the lower acoustic pressure (1.35 MPa); at the higher acoustic pressure (1.65 MPa), the RMS amplitude increased more sharply during the initial FUS exposure period. In particular, the RMS-time curves of the PFP NDs shifted upward as the mean flow velocity increased from 0 to 15 cm/s; the RMS amplitude of the PFH ND solution increased from 0 to 10 cm/s and decreased at 15 cm/s. Moreover, amplitudes of the echo signal for the low boiling-point PFP NDs were higher compared to the high boiling-point PFH NDs in the lower frequency range, whereas the inverse occurred in the higher frequency range. Both PFP and PFH NDs showed increased cavitation activity in the higher frequency under the flow condition compared to the static state, especially PFH NDs. At 1.65 MPa, normalized ICD values for PFH increased from 0.93 ± 0.03 to 0.96 ± 0.04 and from 0 to 10 cm/s, then decreased to 0.86 ± 0.05 at 15 cm/s. This work contributes to our further understanding of cavitation characteristics of phase-shift NDs under physiologically relevant flow conditions during FUS exposure. In addition, the results provide a reference for selecting suitable phase-shift NDs to enhance the efficiency of cavitation-mediated ultrasonic applications.     

Synchrotron quantification of ultrasound cavitation and bubble dynamics in Al–10Cu melts

Knowledge of the kinetics of gas bubble formation and evolution under cavitation conditions in molten alloys is important for the control casting defects such as porosity and dissolved hydrogen. Using in situ synchrotron X-ray radiography, we studied the dynamic behaviour of ultrasonic cavitation gas bubbles in a molten Al–10 wt% Cu alloy. The size distribution, average radius and growth rate of cavitation gas bubbles were quantified under an acoustic intensity of 800 W/cm² and a maximum acoustic pressure of 4.5 MPa (45 atm). Bubbles exhibited a log-normal size distribution with an average radius of 15.3 ± 0.5 μm. Under applied sonication conditions the growth rate of bubble radius, R(t), followed a power law with a form of R(t) = αt^β, and α = 0.0021 & β = 0.89. The observed tendencies were discussed in relation to bubble growth mechanisms of Al alloy melts.     

Sonothrombolysis with an acoustic net-assisted boiling histotripsy: A proof-of-concept study

Whilst sonothrombolysis is a promising and noninvasive ultrasound technique for treating blood clots, bleeding caused by thrombolytic agents used for dissolving clots and potential obstruction of blood flow by detached clots (i.e., embolus) are the major limitations of the current approach. In the present study, a new sonothrombolysis method is proposed for treating embolus without the use of thrombolytic drugs. Our proposed method involves (a) generating a spatially localised acoustic radiation force in a blood vessel against the blood flow to trap moving blood clots (i.e., generation of an acoustic net), (b) producing acoustic cavitation to mechanically destroy the trapped embolus, and (c) acoustically monitoring the trapping and mechanical fractionation processes. Three different ultrasound transducers with different purposes were employed in the proposed method: (1) 1-MHz dual focused ultrasound (dFUS) transducers for capturing moving blood clots, (2) a 2-MHz High Intensity Focused Ultrasound (HIFU) source for fractionating blood clots and (3) a passive acoustic emission detector with broad bandwidth (10 kHz to 20 MHz) for receiving and analysing acoustic waves scattered from a trapped embolus and acoustic cavitation. To demonstrate the feasibility of the proposed method, in vitro experiments with an optically transparent blood vessel-mimicking phantom filled with a blood mimicking fluid and a blood clot (1.2 to 5 mm in diameter) were performed with varying the dFUS and HIFU exposure conditions under various flow conditions (from 1.77 to 6.19 cm/s). A high-speed camera was used to observe the production of acoustic fields, acoustic cavitation formation and blood clot fragmentation within a blood vessel by the proposed method. Numerical simulations of acoustic and temperature fields generated under a given exposure condition were also conducted to further interpret experimental results on the proposed sonothrombolysis. Our results clearly showed that fringe pattern-like acoustic pressure fields (fringe width of 1 mm) produced in a blood vessel by the dFUS captured an embolus (1.2 to 5 mm in diameter) at the flow velocity up to 6.19 cm/s. This was likely to be due to the greater magnitude of the dFUS-induced acoustic radiation force exerted on an embolus in the opposite direction to the flow in a blood vessel than that of the drag force produced by the flow. The acoustically trapped embolus was then mechanically destructed into small pieces of debris (18 to 60 μm sized residual fragments) by the HIFU-induced strong cavitation without damaging the blood vessel walls. We also observed that acoustic emissions emitted from a blood clot captured by the dFUS and cavitation produced by the HIFU were clearly distinguished in the frequency domain. Taken together, these results can suggest that our proposed sonothrombolysis method could be used as a promising tool for treating thrombosis and embolism through capturing and destroying blood clots effectively.     

Effects of ultrasonic reactor design on sewage sludge disintegration

The impact of ultrasound (US) reactor design on cavitation intensity distribution and disintegration efficiency was studied for sewage sludge pre-treatment, using a US flatbed reactor of variable reaction chamber height (RCH, 20–100 mm). Mapping of cavitation intensity and treatment effects was conducted using (i) hydrophone measurements, (ii) aluminum foil tests, and (iii) soluble chemical oxygen demand (COD) analyses. The overall disintegration efficiency was evaluated based on average COD solubilization. The impact of flow on treatment (in)homogeneity was additionally examined using computational fluid dynamics (CFD). Results of all measurement techniques suggest that small RCHs (20 mm, for instance) enable uniform and intense treatments, while large RCHs, which are subjected to strong sound wave attenuation, entail inhomogeneous treatments where large fractions of substrate are no longer exposed to notable cavitation activity. For instance, COD solubilization (relative to alkaline hydrolysis) measured in the channel center dropped from 6.4% to zero as RCH widened from 20 mm to 100 mm. Flow-through sonication further aggravates treatment inhomogeneity due to the high flow rates in the low-cavitation channel centers. Overall disintegration efficiency declined with increasing RCH, showing a drop in average COD solubilization by 73% from RCH = 20 mm to RCH = 100 mm. The drop correlated with average cavitation noise levels (R² = 0.82), indicating that hydrophone measurements may be a suitable tool for US reactor design optimization. Overall, results suggest that reactor geometry has a critical impact on both treatment (in)homogeneity and treatment efficiency and that equal specific energy inputs do not imply equal US treatments.     

The effects of liquid height/volume,initial concentration of reactant and acoustic power on sonochemical oxidation

Even though much knowledge on acoustic cavitation and its application has been accumulated over the past decades, further research is still required to develop industrial uses of acoustic cavitation. It is because the available information is mainly based on small-scale sonoreactors and the design and optimization of sonoreactors for large-scale applications have not been widely studied. In this study, the effects of liquid height/volume, initial concentration of the reactant and input acoustic power on sonochemical oxidation reactions including iodide ion oxidation, As(III) oxidation, and hydrogen peroxide generation were investigated using a 291 kHz sonoreactor with various liquid height/volumes (50, 100, 200, 300, 500, and 1000 mL) and input powers (23, 40, and 82 W). As the liquid height/volume and the input power changed, the power density varied from 23 to 1640 W/L and the maximum cavitation yields of triiodide ion for 23, 40, and 82 W were observed at 0.05, 0.1, and 0.2/0.3 L, respectively. It was found that low power was more effective for the small volume and the large volume required high power level and the moderate power density, approximately 400 W/L, was suggested for the sonochemical oxidation of iodide ion in the 291 kHz sonoreactor in this study. Similar results were observed in the generation of hydrogen peroxide and the sonochemical oxidation of As(III) to As(V). It was also revealed that KI dosimetry could be applicable for the estimation of the sonochemical reactions of non-volatile compounds such as As(III).     

Hydrodynamic cavitation-assisted continuous pre-treatment of sugarcane bagasse for ethanol production: Effects of geometric parameters of the cavitation device

For biotechnological conversion of lignocellulosic biomass, a pre-treatment step is required before enzymatic hydrolysis of carbohydrate fractions of the material, which is required to produce fermentable sugars for generation of ethanol or other products in a biorefinery. The most of the reported pre-treatment technologies are in batch operation mode, presenting some disadvantages as dead times in the process. In this context, hydrodynamic cavitation (HC)-assisted alkaline hydrogen peroxide (AHP) pre-treatment in continuous process was proposed for pre-treatment of sugarcane bagasse (SCB). The system was designed with a main reactor containing two devices to generate cavitation by passing liquid medium through orifice plates. For SCB pretreated in continuous process, 52.79, 34.31, 22.13 and 15.81 g of total reducing sugars (TRS) per 100 g of SCB were released in samples pretreated using orifice plates with a number of holes of 24 (d = 0.45 mm), 16 (d = 0.65 mm), 12 (d = 0.8 mm) and 8 (d = 1 mm), respectively. Computational Fluid Dynamics (CFD) tools showed that 0.94 of vapor phase volume fraction and 0.19 of cavitation number were achieved at 31 m/s of throat velocity and upstream pressure of 350,000 Pa. By using pretreated SCB, 28.44 g of ethanol/L (84.31% of yield respect to theoretical value) was produced by immobilized Scheffersomyces stipitis NRRL-Y7124 in a simultaneous hydrolysis and fermentation process at high solid loading (16% S/L). Thus, HC-assisted process was proved as a promising technology for valorization of lignocellulosic biomass.     

Green and novel ultrasonic extraction with UHPLC-MSMS analysis of natural sweetener (Glycyrrhizic acid) from Glycyrrhiza glabra; a multifactorial mechanistic evaluation based on statistical analysis

A novel, green and eco-friendly, cost-effective, fast, and reliable high energy ultrasonication (US) extraction with UHPLC-MSMS (Ultrahigh performance liquid chromatography with mass spectrometry) quantification of Glycyrrhizic acid (GZA) is reported herein for the first time. The study provides useful insights regarding the effect of US-factors with statistical analysis and mechanisms, involved in GZA-extraction and analysis. An US-extraction method (US-MD) was developed using three levels of US factors: solvents (AC (acetone), EtOH (ethanol), H₂O (water)), time (1, 2, 3 min), amplitudes (30, 40, 50%), pulse (10/0.5, 20/0.5, 30/0.5 sec), particle sizes (0.5, 1, 1.4 mm), and temperatures (20, 30, 40 °C). The US-MD was further validated with high accuracy 98.96 ± 6.82 and r² = 0.995 whereas, an in-house analytical method (UHPLC-MSMS) was developed and validated to quantify the GZAamount. UHPLCMSMS-MD resulted in a retention time of 0.31 min with MSMS (821.400 > 351.200) in a 1 min run time whereas, UHPLCMSMS-MV showed high accuracy and precision with r² = 0.998 for GZA. Statistical analysis of K-mean clustering finalized US-set-of-factors showing optimum extract yield (mg/1mg) of 0.48 with sum (2.41 ± 014) and mean (0.27) along with a high GZA-amount (μg/mg) of 8.23 with sum (43.31 ± 2.07) and mean (4.81) for H₂O in 3 min at 40 °C using particle size (1.4 mm), amplitude (50%), and pulse (30/0.5). Large scale application of US-UHPLCMSMS confirmed the evaluation power of the method showing the order for GZA amount; Egypt > Pakistan > Syria > India > Palestine > America > Georgia > Morocco. A significant effect for US factors Vs extract yield and GZA amount was observed however, solvent*GZA-amount and extract yield*particle size were more significantly correlated compared to time*temperature*amplitude*pulse analyzed via PCA, GLM-UniANOVA, K-mean, and Pearson’s correlation (P ≤ 0.05). A combined mechanism of shear stress, macroturbulence due to acoustic cavitation and implosions, sonochemical, and sonocapillary effect were noted for the US technique producing higher extract yield and GZA amount from licorice.     

Piezo/sono-catalytic activity of ZnO micro/nanoparticles for ROS generation as function of ultrasound frequencies and dissolved gases

We report an accurate study on sonocatalytic properties of different ZnO micro and nanoparticles to enhance OH radical production activated by cavitation. In order to investigate some of the still unsolved aspects related to the piezocatalytic effect, the degradation of Methylene Blue and quantification of radicals production have been evaluated as function of different ultrasonic frequencies (20 kHz and 858 kHz) and dissolved gases (Ar, N₂ and air). The results shown that at low frequency the catalytic effect of ZnO particles is well evident and influenced by particle dimension while at high frequency a reduction of the degradation efficiency have been observed using larger particles. An increase of radical production have been observed for all ZnO particles tested while the different saturating gases have poor influence. In both ultrasonic set-up the ZnO nanoparticles resulted the most efficient on MB degradation revealing that the enhanced radical production may arise more from bubbles collapse on particles surface than the discharge mechanism activate by mechanical stress on piezoelectric particles. An interpretation of these effects and a possible mechanism which rules the sonocatalytic activity of ZnO will be proposed and discussed.     

Treatment of cyanide containing wastewater using cavitation based approach

Industrial wastewater streams containing high concentrations of biorefractory materials like cyanides should ideally be treated at source. In the present work, degradation of potassium ferrocyanide (K₄F_e(CN)₆) as a model pollutant has been investigated using cavitational reactors with possible intensification studies using different approaches. Effect of different operating parameters such as initial concentration, temperature and pH on the extent of degradation using acoustic cavitation has been investigated. For the case of hydrodynamic cavitation, flow characteristics of cavitating device (venturi) have been established initially followed by the effect of inlet pressure and pH on the extent of degradation. Under the optimized set of operating parameters, the addition of hydrogen peroxide (ratio of K₄F_e(CN)₆:H₂O₂ varied from 1:1 to 1:30 mol basis) as process intensifying approach has been investigated. The present work has conclusively established that under the set of optimized operating parameters, cavitation can be effectively used for degradation of potassium ferrocyanide. The comparative study of hydrodynamic cavitation and acoustic cavitation suggested that hydrodynamic cavitation is more energy efficient and gives higher degradation as compared to acoustic cavitation for equivalent power/energy dissipation. The present work is the first one to report comparison of cavitation based treatment schemes for degradation of cyanide containing wastewaters.