Effects of ultrasound and temperature on copper electro reduction in Deep Eutectic Solvents (DES)

This paper concerns a preliminary study for a new copper recovery process from ionic solvent. The aim of this work is to study the reduction of copper in Deep Eutectic Solvent (choline chloride–ethylene glycol) and to compare the influence of temperature and the ultrasound effects on kinetic parameters. Solutions were prepared by dissolution of chloride copper salt CuCl₂ (to obtain Copper in oxidation degree II) or CuCl (to obtain Copper in oxidation degree I) and by leaching metallic copper directly in DES. The spectrophotometry UV–visible analysis of the leached solution showed that the copper soluble form obtained is at oxidation degree I (Copper I). Both cyclic voltammetry and linear voltammetry were performed in the three solutions at three temperatures (25, 50 and 80 °C) and under ultrasonic conditions (F = 20 kHz, PT = 5.8 W) to calculate the mass transfer diffusion coefficient kD and the standard rate coefficient k°. These parameters are used to determine that copper reduction is carried out via a mixed kinetic-diffusion control process. Temperature and ultrasound have the same effect on mass transfer for reduction of Cu^II/Cu^I. On the other hand, temperature is more beneficial than ultrasound for mass transfer of Cu^I/Cu. Standard rate constant improvement due to temperature increase is of the same order as that obtained with ultrasound. But, by combining higher temperature and ultrasound (F = 20 kHz, PT = 5.6 W at 50 °C), reduction limiting current is increased by a factor of 10 compared to initial conditions (T = 25 °C, silent), because ultrasonic stirring is more efficient in lower viscosity fluid. These values can be considered as key-parameters in the design of copper recovery in global processes using ultrasound.     

Propargylation of indene-1,3-dione under a new phase-transfer catalyst combined with ultrasonication – A kinetic study

In the present study, kinetics of synthesis of 2,2-di(prop-2-ynyl)-1H-indene-1,3(2H)-dione was successfully carried out by propargylation of indene-1,3-dione with propargyl bromide using aqueous potassium hydroxide and catalyzed by a newly synthesized phase-transfer catalyst viz., N-benzyl-N-ethyl-N-isopropylpropan-2-ammonium bromide, PTC 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 with ultrasound irradiation than without ultrasound.     

A convenient ultrasound-promoted regioselective synthesis of fused polycyclic 4-aryl-3-methyl-4,7-dihydro-1H-pyrazolo[3,4-b]pyridines

Fused polycyclic 4-aryl-3-methyl-4,7-dihydro-1H-pyrazolo[3,4-b]pyridines were obtained in a three-component regioselective reaction of 5-amino-3-methyl-1H-pyrazole, 2H-indene-1,3-dione and arylaldehydes in ethanol under ultrasound irradiation. This rapid method produced the products in short reaction times (4–5 min) and excellent yields (88–97%).     

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

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

Ultrasonic-assisted synthesis of 1,4-disubstituted 1,2,3-triazoles via various terminal acetylenes and azide and their quorum sensing inhibition

An efficient synthesis of 1,4-disubstituted 1,2,3-triazole derivatives was studied. 1,4-Disubstituted 1,2,3-triazoles containing isoxazole and thymidine structures were synthesized in 84–96% yields starting from various terminal isoxazole ether alkynes and β-thymidine azide derivatives via a 1,3-dispolar cycloaddition using copper acetate, sodium ascorbate as the catalyst under ultrasonic assisted condition. All the target compounds were characterized by HRMS, FT-IR, ¹H NMR and ¹³C NMR spectroscopy. Furthermore, the quorum sensing inhibitory activities of synthesized compounds were evaluated with Chromobacterium violaceum (C. Violaceum CV026) based on their inhibition of violacein production, with compound C₁₀-HSL as a positive control. The compounds 8a, 8c and 8f exhibited considerable levels of inhibitory activity against violacein production, and IC₅₀ values were 217 ± 19, 223 ± 20 and 42.8 ± 4.5 μM, respectively, which highlighted the potential of these compounds as lead structures for further research towards the development of novel QS inhibitors.     

Ultrasound-ionic liquid enhanced enzymatic and acid hydrolysis of biomass cellulose

The purpose of this paper was to investigate the effect of ultrasound-ionic liquid (IL) pretreatment on the enzymatic and acid hydrolysis of the sugarcane bagasse and wheat straw. The lignocellulosic biomass was dissociated in ILs ([Bmim]Cl and [Bmim]AOC) aided by ultrasound waves. Sonication was performed at different frequencies (20, 28, 35, 40, and 50 kHz), a power of 100 W, a time of 30 min and a temperature of 80 °C. The changes in the structure and crystallinity of the cellulose were studied by Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and thermal gravimetric analysis (TGA). The amounts of the total reducing sugars, glucose, cellobiose, xylose and arabinose in the hydrolysates were determined. The results of FT-IR, XRD and TGA revealed that the structure of cellulose of both biomass samples remained intact after the pretreatment, but the crystallinity decreased. The enzymatic and acid hydrolysis of the biomass samples pretreated with the ultrasound-IL result in higher yields of the reducing sugars compared with the IL-pretreated sample. Enzymatic hydrolysis of bagasse and wheat straw pretreated with [Bmim]Cl-ultrasound resulted in maximal yields of glucose at 20 kHz (40.32% and 53.17%) and acid hydrolysis resulted in maximal yields of glucose at 40 kHz (33.32% and 48.07%). Enzymatic hydrolysis of bagasse and wheat straw pretreated with [Bmim]OAc-ultrasound show maximal yields of glucose at 28 kHz and acid hydrolysis at 50 kHz. Combination of ultrasound with [Bmim]OAc is more effective than [Bmim]Cl in terms of the yields of reducing sugar.     

Ultrasound assisted dispersal of a copper nanopowder for electroless copper activation

This paper describes the ultrasound assisted dispersal of a low wt./vol.% copper nanopowder mixture and determines the optimum conditions for de-agglomeration. A commercially available powder was added to propan-2-ol and dispersed using a magnetic stirrer, a high frequency 850 kHz ultrasonic cell, a standard 40 kHz bath and a 20 kHz ultrasonic probe. The particle size of the powder was characterized using dynamic light scattering (DLS). Z-Average diameters (mean cluster size based on the intensity of scattered light) and intensity, volume and number size distributions were monitored as a function of time and energy input. Low frequency ultrasound was found to be more effective than high frequency ultrasound at de-agglomerating the powder and dispersion with a 20 kHz ultrasonic probe was found to be very effective at breaking apart large agglomerates containing weakly bound clusters of nanoparticles. In general, the breakage of nanoclusters was found to be a factor of ultrasonic intensity, the higher the intensity the greater the de-agglomeration and typically micron sized clusters were reduced to sub 100 nm particles in less than 30 min using optimum conditions. However, there came a point at which the forces generated by ultrasonic cavitation were either insufficient to overcome the cohesive bonds between smaller aggregates or at very high intensities decoupling between the tip and solution occurred. Absorption spectroscopy indicated a copper core structure with a thin oxide shell and the catalytic performance of this dispersion was demonstrated by drop coating onto substrates and subsequent electroless copper metallization. This relatively inexpensive catalytic suspension has the potential to replace precious metal based colloids used in electronics manufacturing.     

Indium-mediated regioselective synthesis of ketones from arylstannanes under solvent-free ultrasound irradiation

The solvent-free indium-promoted reaction of alkanoyl chlorides with sterically and electronically diverse arylstannanes is a simple and direct method for the regioselective synthesis of primary, secondary and tertiary alkyl aryl ketones in good to excellent isolated yields (42–84%) under mild and neutral conditions. The protocol is also adequate for the synthesis of aryl vinyl ketones. Reaction times are drastically reduced (from 3–32 h to 10–70 min) under ultrasonic irradiation. Evidences for the involvement of a homolytic aromatic ipso-substitution mechanism, in which indium metal acts as radical initiator, are presented. It is possible the transference of two aryl groups from tin, thus improving effective mass yield, working with diarylstannanes as starting substrates.     

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.     

The disinfection effect of a novel continuous-flow water sterilizing system coupling dual-frequency ultrasound with sodium hypochlorite in pilot scale

In this paper, a self-designed novel continuous-flow water disinfection system coupling dual-frequency ultrasound (US) with chemical disinfectant sodium hypochlorite (NaClO) was tested in a pilot scale using a simulated effluent containing Bacillus subtilis (B. subtilis), one of the indicators of water treatment efficiency. A suspension having a B. subtilis concentration of approximately 10⁴ CFU/mL was introduced into the system to (1) investigate disinfection efficiency of US pretreatment with NaClO (US + NaClO) and simultaneous US and NaClO (US/NaClO) disinfection under different single frequencies; (2) further examine the disinfection efficiency of these two processes with dual-frequency US; and (3) identify dosage reduction of chlorine in this disinfection system. The results demonstrated that lower dual-frequency (17 kHz + 33 kHz) US pretreatment with NaClO disinfection and simultaneous higher dual-frequency (70 kHz + 100 kHz) US and NaClO were beneficial to bacterial inactivation in terms of sterilizing efficiency. It has also been observed that US pretreatment with lower combination of 17 + 33 kHz frequencies showed better enhancement in which log reduction reached to 3.82 after 10 min chlorine reaction (chlorine alone was 0.22 log reduction), nearly 1 log reduction higher than single frequencies at the same constant power. Consequently, at equivalent power dissipation levels, US of lower frequencies combination pretreatment with NaClO disinfection performed such a promising process that one-thirds (from 12 mg/L NaClO reduced to 8 mg/L NaClO) of the required NaClO dosage was reduced for the ideal disinfection efficiency of 4 log reduction, namely 100% disinfection. And the utilization efficiency of NaClO was increased from 37.67% to 85.25% in 30 min of treatment time using an optimized combination of pretreatment and chlorination.     

Investigation of acoustic cavitation energy in a large-scale sonoreactor

Acoustic cavitation energy distributions were investigated for various frequencies such as 35, 72, 110 and 170 kHz in a large-scale sonoreactor. The energy analyses were conducted in three-dimensions and the highest and most stable cavitation energy distribution was obtained not in 35 kHz but in 72 kHz. However, the half-cavitation-energy distance was larger in the case of 35 kHz ultrasound than in the case of 72 kHz, demonstrating that cavitation energy for one cycle was higher for a lower frequency. This discrepancy was due to the large surface area of the cavitation-energy-meter probe. In addition, 110 and 170 kHz ultrasound showed a very low and poor cavitation energy distribution. Therefore larger input power was required to optimize the use of higher frequency ultrasound in the sonoreactor with long-irradiation distance. The relationship between cavitation energy and sonochemical efficiency using potassium iodide (KI) dosimetry was best fitted quadratically. From 7.77 × 10^?10 to 4.42 × 10^?9 mol/J of sonochemical efficiency was evaluated for the cavitation energy from 31.76 to 103. 67 W. In addition, the cavitation energy attenuation was estimated under the assumption that cavitation energy measured in this study would be equivalent to sound intensity, resulting in 0.10, 0.18 and 2.44 m^?1 of the attenuation coefficient (α) for 35, 72 and 110 kHz, respectively. Furthermore, α/(frequency)² was not constant, as some previous studies have suggested.     

Purification of serratiopeptidase from Serratia marcescens NRRL B 23112 using ultrasound assisted three phase partitioning

The ultrasound assisted three phase partitioning (UATPP) is a novel bioseparation method for separation and purification of biomolecules. In the present work, UATPP was investigated for the first time for purification of serratiopeptidase from Serratia marcescens NRRL B 23112. Effect of various process parameters such as ammonium sulphate saturation, t-butanol to crude extract ratio, pH, ultrasonic frequency, ultrasonic intensity, duty cycle and irradiation time were evaluated and optimized. The optimized conditions were found to be as follows: ammonium sulphate saturation 30% (w/v), pH 7.0, t-butanol to crude ratio 1:1 (v/v), ultrasound frequency 25 kHz, ultrasound intensity 0.05 W/cm², duty cycle 20% and irradiation time 5 min. The maximum purity and recovery obtained from UATPP was 9.4-fold and 96% respectively as compared to the three phase partitioning (TPP) (4.2-fold and 83%). Also the process time for UATPP was significantly reduced to 5 min from 1 h as compared to TPP. The results indicate that, UATPP is an efficient technique for the purification of serratiopeptidase with maximum purity, recovery and reduced processing time.     

Sonochemical degradation of ethyl paraben in environmental samples: Statistically important parameters determining kinetics,by-products and pathways

The sonochemical degradation of ethyl paraben (EP), a representative of the parabens family, was investigated. Experiments were conducted at constant ultrasound frequency of 20 kHz and liquid bulk temperature of 30 °C in the following range of experimental conditions: EP concentration 250–1250 μg/L, ultrasound (US) density 20–60 W/L, reaction time up to 120 min, initial pH 3–8 and sodium persulfate 0–100 mg/L, either in ultrapure water or secondary treated wastewater.A factorial design methodology was adopted to elucidate the statistically important effects and their interactions and a full empirical model comprising seventeen terms was originally developed. Omitting several terms of lower significance, a reduced model that can reliably simulate the process was finally proposed; this includes EP concentration, reaction time, power density and initial pH, as well as the interactions (EP concentration) × (US density), (EP concentration) × (pH_o) and (EP concentration) × (time).Experiments at an increased EP concentration of 3.5 mg/L were also performed to identify degradation by-products. LC–TOF–MS analysis revealed that EP sonochemical degradation occurs through dealkylation of the ethyl chain to form methyl paraben, while successive hydroxylation of the aromatic ring yields 4-hydroxybenzoic, 2,4-dihydroxybenzoic and 3,4-dihydroxybenzoic acids. By-products are less toxic to bacterium V. fischeri than the parent compound.     

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 three phase partitioning of a fibrinolytic enzyme

The present investigation is aimed at ultrasound assisted three phase partitioning (UATPP) of a fibrinolytic enzyme from Bacillus sphaericus MTCC 3672. Three phase partitioning integrates the concentration and partial purification step of downstream processing of a biomolecule. Three phase system is formed with simultaneous addition of ammonium sulfate to crude broth and followed by t-butanol. UATPP of a fibrinolytic enzyme was studied by varying different process parameters such as ammonium sulfate saturation concentration, pH, broth to t-butanol ratio, temperature, ultrasound frequency, ultrasonication power, and duty cycle. The optimized parameters yielding maximum purity of 16.15-fold of fibrinolytic enzyme with 65% recovery comprised of 80% ammonium sulfate saturation, pH 9, temperature 30 °C, broth to t-butanol ratio 0.5 (v/v), at 25 kHz frequency and 150 W ultrasonication power with 40% duty cycle for 5 min irradiation time. SDS PAGE analysis of partitioned enzyme shows partial purification with a molecular weight in the range of 55–70 kDa. Enhanced mass transfer of UATPP resulted in higher fold purity of fibrinolytic enzyme with reduced time of operation from 1 h to 5 min as compared to conventional TPP. Outcome of our findings highlighted the use of UATPP as an efficient biosepartion technique.     

Ultrasound-assisted copper deposition on a polymer membrane and application for methanol steam reforming

Copper particles were electrolessly deposited on a palladium aerosol activated polymer membrane in the presence of ultrasound. An application of ultrasound introduced a faster deposition (220 μg min^?1 in deposition rate) and finer copper particles (9 nm in crystallite size) than those (11 and 41 μg min^?1; 27 and 32 nm) in the absence of ultrasound (i.e. respectively 20 and 45 °C in bath temperature with mechanical agitation). A better performance of methanol steam reforming (0.59 in mean conversion during 5 h operation; 1.3 and 1.6 times respectively higher than those from 20 to 45 °C cases) at a 300 °C reaction temperature was materialized for the ultrasound application, probably due to a finer (i.e. a more textured) copper particle deposition on a polymer membrane.     

Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter

Ultrasonic frequencies of 20 kHz, 382 kHz, 584 kHz, 862 kHz (and 998 kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862 kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862 kHz is around 10% more efficient at generating hydroxyl radicals than the 382 kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42 °C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382 kHz and 862 kHz, though 582 kHz is substantially lower, when the power levels are set at approximately 9 W for all systems. An equivalent power level of 9 W could not be obtained for the 998 kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound.     

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.     

Ultrasound assisted the preparation of 1-butoxy-4-nitrobenzene under a new multi-site phase-transfer catalyst – Kinetic study

In the present research work deals with the preparation of 1-butoxy-4-nitrobenzene was successfully carried out by 4-nitrophenol with n-butyl bromide using aqueous potassium carbonate and catalyzed by a new multi-site phase-transfer catalyst (MPTC) viz., N¹,N⁴-diethyl-N¹,N¹,N⁴,N⁴-tetraisopropylbutane-1,4-diammonium dibromide, 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 greatly enhanced with ultrasound irradiation than without ultrasound. The present study provides a method to synthesize nitro aromatic ethers by ultrasound assisted liquid–liquid multi-site phase-transfer catalysis condition.     

Reaction of tert-butyl isocyanate and tert-butyl isothiocyanate at the Ge(100) − 2 × 1 Surface

The adsorption of tert-butyl isothiocyanate and tert-butyl isocyanate at the Ge(100) ? 2 × 1 surface was probed using multiple internal reflection Fourier transform infrared (FTIR) spectroscopy X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) modeling. Results indicate that there are multiple surface products for each molecule. FTIR studies of tert-butyl isothiocyanate reveal adsorption through an S-dative bonded state, while XPS studies further suggest a reactive desorption product which leaves excess sulfur atoms at the surface. Studies of tert-butyl isocyanate indicate that the molecule dissociatively adsorbs at the surface, resulting in tert-butyl and germyl isocyanate groups, as the major pathway, in addition to forming several minor products, including a [2 + 2] cycloaddition product across the C=N bond. DFT was used to simulate vibrational spectra and map the reaction pathways, and confirms that the assigned products are energetically favorable.