Ultrasound-assisted dextranase entrapment onto Ca-alginate gel beads

In this research work, dextranase has immobilized onto calcium alginate beads using a novel ultrasound method. The process of immobilization of the enzyme was carried out in a one-step ultrasound process. Effects of ultrasound conditions on loading efficiency and immobilization yield of the enzyme onto calcium alginate beads were investigated. Furthermore, the activity of the free and immobilized enzymes prepared with and without ultrasound treatment, as a function of pH, temperature, recyclability and enzyme kinetic parameters, was compared. The maximum loading efficiency and the immobilization yield were observed when the immobilized dextranase was prepared with an ultrasonic irradiation at 25 kHz, 40 W for 15 min, under which the loading efficiency and the immobilization yield increased by 27.21% and 18.77%, respectively, compared with the immobilized enzymes prepared without ultrasonic irradiation. On the other hand, immobilized enzyme prepared with ultrasonic irradiation showed V_max and K_M value higher than that for the immobilized enzyme prepared without ultrasonic irradiation, likewise, both the catalytic and specificity constants of immobilized enzyme prepared with ultrasonic irradiation were higher than that for immobilized enzyme prepared without ultrasound, indicating that, this new ultrasonic method improved the catalytic kinetics activity of immobilized dextranase at all the reaction conditions studied. Compared with immobilized enzyme prepared without ultrasound treatment, the immobilized enzymes prepared with ultrasound irradiation exhibited: a higher pH optimum, optimal reaction temperature, activation energy, and thermal stability, as well as, a higher recyclability, which, illustrating the effectiveness of the sonochemical method. To the best of our knowledge, this is the first report on the effect of ultrasound treatments on the immobilization of dextranase.     

Ultrasound-assisted lipase-catalyzed transesterification of soybean oil in organic solvent system

This work reports the transesterification of soybean oil with ethanol using two commercial immobilized lipases under the influence of ultrasound irradiation. The experiments were performed in an ultrasonic water bath, following a sequence of experimental designs to assess the effects of temperature, enzyme and water concentrations, oil to ethanol molar ratio and output irradiation power on the reaction yield. Results show that ultrasound-assisted lipase-catalyzed transesterification of soybean oil with ethanol might be a potential alternative route to conventional alkali-catalyzed method, as high reaction yields (∼90 wt.%) were obtained at mild irradiation power supply (∼100 W), and temperature (60 °C) in a relatively short reaction time, 4 h, using Lipozyme RM IM as catalyst. The repeated use of the catalyst under the optimum experimental condition resulted in a decay in both enzyme activity and product conversion after two cycles. The use of Novozym 435 led to lower conversions (about 57%) but the enzyme activity was stable after eight cycles of use, showing, however, a reduction in product conversion after the forth cycle.     

Ultrasound-assisted butyl acetate synthesis catalyzed by Novozym 435: Enhanced activity and operational stability

The influence of low-frequency ultrasound (40 kHz) in the esterification reaction between acetic acid and butanol for flavor ester synthesis catalyzed by the commercial immobilized lipase B from Candida antarctica (Novozym 435) was evaluated. A central composite design and the response surface methodology were used to analyze the effects of the reaction parameters (temperature, substrate molar ratio, enzyme content and added water) and their response (yields of conversion in 2.5 h of reaction). The reaction was carried out using n-hexane as solvent. The optimal conditions for ultrasound-assisted butyl acetate synthesis were found to be: temperature of 46 °C; substrate molar ratio of 3.6:1 butanol:acetic acid; enzyme content of 7%; added water of 0.25%, conditions that are slightly different from those found using mechanical mixing. Over 94% of conversion was obtained in 2.5 h under these conditions. The optimal acid concentration for the reaction was determined to be 2.0 M, compared to 0.3 M without ultrasound treatment. Enzyme productivity was significantly improved to around 7.5-fold for each batch when comparing ultrasound and standard mechanical agitation. The biocatalyst could be directly reused for 14 reactions cycles keeping around 70% of its original activity, while activity was virtually zeroed in the third cycle using the standard mixing system. Thus, compared to the traditional mechanical agitation, ultrasound technology not only improves the process productivity, but also enhances enzyme recycling and stability in the presence of acetic acid, being a powerful tool to improve biocatalyst performance in this type of reaction.     

Ultrasound assisted enzyme catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate

The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100 W), duty cycle 50% and temperature (60 °C) in a relatively short reaction time (4 h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4 h as compared to conventional stirring method (14 h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion.     

Ultrasound assisted enzyme catalyzed transesterification of waste cooking oil with dimethyl carbonate

This work reports the production of biodiesel with waste cooking oil and dimethyl carbonate in solvent free system through transesterification by immobilized enzyme (Novozym 435) under the influence of ultrasound irradiation. The experiments were conducted in an ultrasonic water bath under three different conditions i.e. ultrasonic irradiation (UI) without stirring, UI coupled with stirring and only stirring to compare their overall effects on fatty acid methyl esters (FAME) conversion. As compared with the conventional stirring method, where FAME conversion was 38.69% at 4 h, the UI without stirring significantly enhanced the conversion of enzymatic transesterification to 57.68% for the same reaction time. However the reaction rate was further increased under the condition of ultrasonication coupled with stirring and resulted into higher conversion of 86.61% for the same reaction time. Effects of reaction parameters, such as temperature, ratio of DMC/oil, speed of agitation and enzyme loading on the conversion were investigated. Furthermore, repeated use of Novozym 435 showed gradual decline in both conversion as well as enzyme activity.     

Ultrasound treatments improve germinability of soybean seeds: The key role of working frequency

In this paper, the effects of ultrasound with different frequency modes on the sprouting rate, sprouting vigor, metabolism-related enzyme activity and late nutrient accumulation in soybean were investigated, and the mechanism of dual-frequency ultrasound promoting bean sprout development was explored. The results showed that, compared with control, the sprouting time was shortened by 24 h after dual-frequency ultrasound treatment (20/60 kHz), and the longest shoot was 7.82 cm at 96 h. Meanwhile, ultrasonic treatment significantly enhanced the activities of protease, amylase, lipase and peroxidase (p < 0.05), particularly the phenylalanine ammonia-lyase increased by 20.50%, which not only accelerated the seed metabolism, but also led to the accumulation of phenolics (p < 0.05), as well as more potent antioxidant activity at later stages of sprouting. In addition, the seed coat exhibited remarkable cracks and holes after ultrasonication, resulting in accelerated water absorption. Moreover, the immobilized water in seeds increased significantly, which was beneficial to seed metabolism and later sprouting. These findings confirmed that dual-frequency ultrasound pretreatment has a great potential to be used for seed sprouting and promoting the accumulation of nutrients in bean sprouts by accelerating water absorption and increasing enzyme activity.     

The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

Synergism between ultrasonic pretreatment and white rot fungal enzymes on biodegradation of wheat chaff

Lignocellulosic biomass samples (wheat chaff) were pretreated by ultrasound (US) (40 kHz/0.5 W cm⁻²/10 min and 400 kHz/0.5 W cm⁻²/10 min applied sequentially) prior to digestion by enzyme extracts obtained from fermentation of the biomass with white rot fungi (Phanerochaete chrysosporium or Trametes sp.). The accessibility of the cellulosic components in wheat chaff was increased, as demonstrated by the increased concentration of sugars produced by exposure to the ultrasound treatment prior to enzyme addition. Pretreatment with ultrasound increased the concentration of lignin degradation products (guaiacol and syringol) obtained from wheat chaff after enzyme addition. In vitro digestibility of wheat chaff was also enhanced by the ultrasonics pretreatment in combination with treatment with enzyme extracts. Degradation was enhanced with the use of a mixture of the enzyme extracts compared to that for a single enzyme extract.     

Preparation of 1,3-bis(allyloxy)benzene under a new multi-site phase-transfer catalyst combined with ultrasonication – A kinetic study

In the present work, kinetics of synthesis of 1,3-bis(allyloxy)benzene was successfully carried out by O-allylation of resorcinol with allyl bromide using aqueous potassium hydroxide and catalyzed by a new multi-site phase-transfer catalyst viz., 1,3,5,7-tetrabenzylhexamethylenetetraammonium tetrachloride, MPTC under ultrasonic (40 kHz, 300 W) assisted organic solvent condition. The pseudo first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction rate can be greatly enhanced to seven fold faster with ultrasound irradiation than without ultrasound. The present study provides a method to synthesize ethers by ultrasound assisted liquid–liquid phase-transfer catalysis condition.     

Ultrasound assisted enzyme catalyzed hydrolysis of waste cooking oil under solvent free condition

The present work demonstrates the hydrolysis of waste cooking oil (WCO) under solvent free condition using commercial available immobilized lipase (Novozyme 435) under the influence of ultrasound irradiation. The process parameters were optimized using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound intensity. It has been observed that ultrasound-assisted lipase-catalyzed hydrolysis of WCO would be a promising alternative for conventional methods. A maximum conversion of 75.19% was obtained at mild operating parameters: molar ratio of oil to water (buffer pH 7) 3:1, catalyst loading of 1.25% (w/w), lower ultrasound power 100 W (ultrasound intensity – 7356.68 W m⁻²), duty cycle 50% and temperature (50 °C) in a relatively short reaction time (2 h). The activation energy and thermodynamic study shows that the hydrolysis reaction is more feasible when ultrasound is combined with mechanical agitation as compared with the ultrasound alone and simple conventional stirring technique. Application of ultrasound considerably reduced the reaction time as compared to conventional reaction. The successive use of the catalyst for repetitive cycles under the optimum experimental conditions resulted in a loss of enzymatic activity and also minimized the product conversion.     

Ultrasound assisted acid catalyzed lactose hydrolysis: Understanding into effect of operating parameters and scale up studies

The current work deals with the value addition of lactose by transforming into hydrolyzed lactose syrup containing glucose and galactose in major proportion using the novel approach of ultrasound assisted acid catalyzed lactose hydrolysis. The hydrolysis of lactose was performed in ultrasonic bath (33 kHz) at 50% duty cycle at different temperatures as 65 °C and 70 °C and two different hydrochloric acid (HCl) concentrations as 2.5 N and 3 N. It was observed that acid concentration, temperature and ultrasonic treatment were the major factors in deciding the time required to achieve ∼90% hydrolysis. The ultrasonic assisted approach resulted in reduction in the reaction time and the extent of intensification was established to be dependent on the temperature, acid concentration and time of ultrasonic exposure. It was observed that the maximum process intensification obtained by introduction of ultrasound in the lactose hydrolysis process performed at 70 °C and 3 N HCl was reduction in the required time for ∼90% hydrolysis from 4 h (without the presence of ultrasound) to 3 h. The scale-up study was also performed using an ultrasonic bath with longitudinal horn (36 kHz as operating frequency) at 50% duty cycle, optimized temperature of 70 °C and acid concentration of 3 N. It was observed that the reaction was faster in the presence of ultrasound and stirring by axial impeller at rpm of 225 ± 25. The time required to complete ∼90% of hydrolysis remained almost the same as observed for small scale study on ultrasonic bath (33 kHz) at 50% duty cycle. The use of recovered lactose from whey samples instead of pure lactose did not result in any significant changes in the progress of hydrolysis, confirming the efficacy of the selected approach. Overall, the work has presented a novel ultrasound assisted approach for intensified lactose hydrolysis.     

Ultrasound assisted intensification of biodiesel production using enzymatic interesterification

Ultrasound assisted intensification of synthesis of biodiesel from waste cooking oil using methyl acetate and immobilized lipase obtained from Thermomyces lanuginosus (Lipozyme TLIM) as a catalyst has been investigated in the present work. The reaction has also been investigated using the conventional approach based on stirring so as to establish the beneficial effects obtained due to the use of ultrasound. Effect of operating conditions such as reactant molar ratio (oil and methyl acetate), temperature and enzyme loading on the yield of biodiesel has been investigated. Optimum conditions for the conventional approach (without ultrasound) were established as reactant molar ratio of 1:12 (oil:methyl acetate), enzyme loading of 6% (w/v), temperature of 40 °C and reaction time of 24 h and under these conditions, 90.1% biodiesel yield was obtained. The optimum conditions for the ultrasound assisted approach were oil to methyl acetate molar ratio of 1:9, enzyme loading of 3% (w/v), and reaction time of 3 h and the biodiesel yield obtained under these conditions was 96.1%. Use of ultrasound resulted in significant reduction in the reaction time with higher yields and lower requirement of the enzyme loading. The obtained results have clearly established that ultrasound assisted interesterification was a fast and efficient approach for biodiesel production giving significant benefits, which can help in reducing the costs of production. Reusability studies for the enzyme were also performed but it was observed that reuse of the catalyst under the optimum experimental condition resulted in reduced enzyme activity and biodiesel yield.     

Ultrasound-assisted conversion of tannic acid to gallic acid as a strategy to obtain value-added products

In this work, ultrasound was applied for the conversion of tannic acid into gallic acid using only diluted H₂O₂ as reagent. Experiments were carried out using several types of ultrasonic horns operating at 20 kHz (VC750W processor). The following experimental conditions were evaluated: H₂O₂ concentration (0.2 to 8.5 mol L⁻¹), horn type (10 to 25 mm of diameter), ultrasound amplitude (20 to 70%), sonication time (10 to 45 min), tannic acid concentration (170 to 1360 mg L⁻¹), and reaction temperature (50 to 90 °C). Gallic acid production was monitored with ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS). The isolated gallic acid was confirmed with nuclear magnetic resonance (¹H and ¹³C NMR). It is important to emphasize that this study was developed as a proof of concept to demonstrate the potential of ultrasound for tannic acid conversion into gallic acid using just diluted H₂O₂. Under selected conditions gallic acid production yield was 128 ± 4 mg g⁻¹ of initial tannic acid (using 170 mg L⁻¹ of tannic acid as starting material). Reaction time was set as 30 min, which was carried out using 1 mol L⁻¹ H₂O₂ and ultrasound amplitude of 50% at 90 °C. At silent conditions (mechanical stirring, from 100 to 1000 rpm), gallic acid production was halved (less than 78 ± 4 mg g⁻¹ of initial tannic acid).     

Influence of sodium alginate pretreated by ultrasound on papain properties: Activity,structure, conformation and molecular weight and distribution

The aim of the study was to investigate the impact of sodium alginate (ALG) pretreated by ultrasound on the enzyme activity, structure, conformation and molecular weight and distribution of papain. ALG solutions were pretreated with ultrasound at varying power (0.05, 0.15, 0.25, 0.35, 0.45 W/cm²), 135 kHz, 50 °C for 20 min. The maximum relative activity of papain increased by 10.53% when mixed with ALG pretreated by ultrasound at 0.25 W/cm², compared with the untreated ALG. The influence of ultrasound pretreated ALG on the conformation and secondary structure of papain were assessed by fluorescence spectroscopy and circular dichroism spectroscopy. The fluorescence spectra revealed that ultrasound pretreated ALG increased the number of tryptophan on papain surface, especially at 0.25 W/cm². It indicated that ultrasound pretreatment induced molecular unfolding, causing the exposure of more hydrophobic groups and regions from inside to the outside of the papain molecules. Furthermore, ultrasound pretreated ALG resulted in minor changes in the secondary structure of the papain. The content of α-helix was slightly increased after ultrasound pretreatment and no significant change was observed at different ultrasound powers. ALG pretreated by ultrasound enhanced the stability of the secondary structure of papain, especially at 0.25 W/cm². The free sulfhydryl (SH) content of papain was slightly increased and then decreased with the increase of ultrasonic power. The maximum content of free SH was observed at 0.25 W/cm², under which the content of the free SH increased by 6.36% compared with the untreated ALG. Dynamic light scattering showed that the effect of ultrasound treatment was mainly the homogenization of the ALG particles in the mixed dispersion. The gel permeation chromatography coupled with the multi-angle laser light scattering photometer analysis showed that the molecular weight (M_w) of papain/ALG was decreased and then increased with the ultrasonic pretreatment. Results demonstrated that the activity of immobilized papain improved by ultrasonic pretreatment was mainly caused by the variation of the conformation of papain and the effect of interactions between papain and ALG. This study is important to explain the intermolecular interactions of biopolymers and the mechanism of enzyme immobilization treated by ultrasound in improving the enzymatic activity. As expected, ALG pretreated by appropriate ultrasound is promising as a bioactive compound carrier in the field of immobilized enzyme.     

Synergetic decolorization of azo dyes using ultrasounds,photocatalysis and photo-fenton reaction

In the present work, ultrasound irradiation, photocatalysis with TiO₂, Fenton/Photo-Fenton reaction, and the combination of those techniques were investigated for the decolorization of industrial dyes in order to study their synergy. Three azo dyes were selected from the weaving industry. Their degradation was examined via UV illumination, Fenton and Photo-Fenton reaction as well as ultrasound irradiation at low (20 kHz) and high frequencies (860 kHz). In these experiments, we investigated the simultaneous action of the ultrasound and UV irradiation by varying parameters like the duration of photocatalysis and ultrasound irradiation frequency. At the same time, US power, temperature, amount of TiO₂ photocatalyst and amount of Fenton reagent remained constant. Due to their diverse structure, each azo dye showed different degradation levels using different combinations of the above-mentioned Advanced Oxidation Processes (AOPs). The Photo-Fenton reagent is more effective with US 20 kHz and US 860 kHz for the azo dyes originated from the weaving industry at pH = 3 as compared to pH = 6.8. The combination of the Photo-Fenton reaction with 860 kHz ultrasound irradiation for the same dye gave an 80% conversion at the same time. Experiments have shown a high activity during the first two hours. After that threshold, the reaction rate is decreased. FT-IR and TOC measurements prove the decolorization due to the destruction of the chromophore groups but not complete mineralization of the dyes.     

Effects of ultrasound on the enzymatic degradation of pectin

Ultrasound-assisted enzymatic maceration (UAEM) has gained considerable interest in the fruit juice industry, owing to its potential to increase juice yield and content of polyphenols while simultaneously saving time and energy. In this study, the effects of UAEM (ultrasonic probe, 20 kHz, 21 W*cm⁻² and 33 W*cm⁻²) on pectin degradation in a continuous circulation system were investigated over 60 and 90 min. Main pectinolytic enzymes activities of (polygalacturonase, pectin lyase and pectin methylesterase) of a commercial enzyme preparation were examined for individual synergistic effects with US. Pectin hydrolysis by UAEM differed significantly compared to treatment with ultrasound or enzymes alone regarding the profile of degradation products compared to treatment with ultrasound or enzymes alone. Ultrasound fragmented pectin to less branched oligomers of medium molecular weight (Mp approx. 150 kDa), which were further degraded by pectinolytic activities. The low molecular weight fraction (<30 kDa), which is known to be beneficial for juice-quality by adding nutritional value and stabilizing polyphenols, was enriched in small oligomers of homogalacturonan-derived, rhamnogalacturonan I-derived, and rhamnogalacturonan II-derived residues. Synergistic effects of ultrasound application enhanced the effective activities of polygalacturonase and pectin lyase and even prolonged their performance over 90 min, whereas the effective activity of pectin methylesterase was not affected. Final marker concentrations determined by each enzyme assay revealed a considerable higher total process output after UAEM treatment at reduced temperature (30 °C) comparable to the output after conventional batch maceration at 50 °C. The obtained results demonstrate the high potential of UAEM to produce high-quality juice by controlling pectin degradation while reducing process temperature and equally highlight the matrix and enzyme specific effects of a simultaneous US treatment.     

Insights into the novel application of Fe-MOFs in ultrasound-assisted heterogeneous Fenton system: Efficiency,kinetics and mechanism

In this work, as a new strategy, ultrasound/H₂O₂/MOF system was firstly applied by environmental-benign Fe-MOFs (MIL-53, MIL-88B and MIL-101) for tetracycline hydrochloride removal. The synthetic Fe-MOFs were characterized by XRD, FTIR, SEM, XPS, N₂ sorption-desorption isotherms and CO-FTIR. MIL-88B demonstrated the best catalytic performance because of its highest amount of Lewis acid sites. Influencing factors, contrast experiment, and corresponding dynamics were carried out to obtain the best experimental conditions and reaction system. Under optimal conditions ([Tetracycline hydrochloride] = 10 mg/L, [MIL-88B] = 0.3 g/L, [H₂O₂] = 44 mM, [ultrasound power] = 60 W, and pH = 5.0), the-first-order kinetic rate constant k was calculated to be 0.226 min⁻¹, higher than the simple combination of the ultrasound system (0.004) and MIL-88B/H₂O₂ system (0.163), indicating the importance of synergistic effect between ultrasound and Fenton reaction. EPR test and quenching experiment proved that ·OH is mainly responsible for tetracycline hydrochloride removal. The major reaction path is the adsorption and decomposition of H₂O₂ by coordinative unsaturated iron sites on Fe-MOF, but it is not the only path. The direct decomposition of H₂O₂ and the cavitation effect caused by ultrasound also contribute to the generation of OH.     

Esterification of sodium 4-hydroxybenzoate by ultrasound-assisted solid–liquid phase-transfer catalysis using dual-site phase-transfer catalyst

The catalytic esterification of sodium 4-hydroxybenzoate with benzyl bromide by ultrasound-assisted solid–liquid phase-transfer catalysis (U-SLPTC) was investigated using the novel dual-site phase-transfer catalyst 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl dichloride (BTBAMBC), which was synthesized from the reaction of 4,4′-bis(chloromethyl)-1,1′-biphenyl and tributylamine. Without catalyst and in the absence of water, the product yield at 60 °C was only 0.36% in 30 min of reaction even under ultrasound irradiation (28 kHz/300 W) and 250 rpm of stirring speed. When 1 cm³ of water and 0.5 mmol of BTBAMBC were added, the yield increased to 84.3%. The catalytic intermediate 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl di-4-hydroxybenzoate was also synthesized to verify the intrinsic reaction which was mainly conducted in the quasi-aqueous phase locating between solid and organic phases. Pseudo-first-order kinetic equation was used to correlate the overall reaction, and the apparent rate coefficient with ultrasound (28 kHz/300 W) was 0.1057 min⁻¹, with 88% higher than that (0.0563 min⁻¹) without ultrasound. The esterification under ultrasonic irradiation using BTBAMBC by solid–liquid phase-transfer catalysis was developed.     

Synergistic effects of combining ultrasound with the Fenton process in the degradation of Reactive Blue 19

The decoloration of reactive dye C.I. Reactive Blue 19 (RB 19) using combined ultrasound with the Fenton process has been investigated. The effect of varying the concentrations of hydrogen peroxide and iron sulfate, initial pH, ultrasonic power, initial dye concentration and dissolved gas on the decoloration and degradation efficiencies was measured. Calibration of the ultrasound systems was performed using calorimetric measurements and oxidative species monitoring using the Fricke dosimeter and degradations were carried out with a 20 kHz probe type transducer at 2, 4, 6 and 8 W cm⁻² of acoustic intensity at 15, 25, 50 and 75 mg L⁻¹ initial dye concentrations. First order rate kinetics was observed. It was found that while the degradation rate due to ultrasound alone was slow, sonication significantly accelerated the Fenton reaction. While the results were similar to those reported for other dyes, the effects occurred at lower concentrations. The rate and extent of decoloration of RB 19 increased with rising hydrogen peroxide concentration, ultrasonic powers and iron sulfate concentration but decreased with increasing dye concentration. An optimum pH value of pH = 3.5 was found. The rate of decoloration was higher when dissolved oxygen was present as compared with nitrogen and argon confirming the solution phase mechanism of the degradation.     

Frequency and power dependence of ultrasonic degassing

We investigated the time variation of ultrasonic degassing for air-saturated water and degassed water with a sample volume of 100 mL at frequencies of 22, 43, 129, 209, 305, 400, 514, 1018, and 1960 kHz and ultrasonic power of 15 W. Ultrasonic degassing was evaluated by dissolved oxygen concentration. Ultrasonic degassing was also investigated at a frequency of 1018 kHz and ultrasonic powers of 5, 10, 15, and 20 W. The dissolved oxygen concentration varied with the ultrasonic irradiation time and became constant after prolonged ultrasonic irradiation. The constant dissolved oxygen concentration value depended on the frequency and ultrasonic power but not the initial dissolved oxygen concentration. The degassing rate at 101.3 kPa was higher in the frequency range of 200 kHz to 1 MHz. The frequency dependence of the degassing rate was almost the same as that of the sonochemical efficiency obtained by the potassium iodide (KI) method. Ultrasonic degassing in the frequency range of 22–1960 kHz was also investigated under reduced pressure of 5 kPa. Degassing was accelerated when ultrasonic irradiation was applied under reduced pressure. However, under a reduced pressure of 5 kPa, the lower the frequencies, the higher is the degassing rate. The sonochemical reaction rate was examined by the KI method for varying dissolved air concentrations before ultrasonic irradiation. Cavitation did not occur when the initial dissolved oxygen concentration was less than 2 mg·L⁻¹. Therefore, the lower limit of ultrasonic degassing under 101.3 kPa equals 2 mg·L⁻¹ dissolved oxygen concentration. A model equation for the time variation of dissolved oxygen concentration due to ultrasonic irradiation was developed, and the degassing mechanism was discussed.