Multimode-ultrasound and microwave assisted natural ternary deep eutectic solvent sequential pretreatments for corn straw biomass deconstruction under mild conditions

Mild and effective pretreatments are essential to deconstruct lignocellulosic biomass so as to reuse cellulose content for value-added products. In this study, sequential multimode-ultrasound and microwave with natural ternary deep eutectic solvent (NATDES) pretreatments were used to deconstruct corn straw and optimized factors such as NATDES, ultrasonic, and microwave parameters. Results indicated that the ultrasound-NATDES or microwave-NATDES pretreatment could remove 37.86% and 52.36% lignin, respectively. When using sequential multimode-ultrasound and microwave assisted NATDES pretreatment, the delignification efficiency increased to 61.50%, and the cellulose content increased from 34.70% to 76.08%. In addition, the delignification of sequential multimode-ultrasound and microwave assisted NATDES pretreatment (under the mild conditions of microwave heating at 60 °C and 60 min) increased to 57.39%, and the cellulose content increased to 59.98%, too. This highlighted the effect of the combined ultrasound and microwave technology. Finally, the microstructural changes of mercury intrusion porosimeters, scanning electron microscopy, thermogravimetric, X-ray diffraction and Fourier transform mid-infrared spectroscopy were conducted to confirm the effectiveness of this method to deconstruct corn straw. A mechanism of the deconstruction of corn straw biomass in NATDES with the assistance of the sequential multimode-ultrasound and microwave heating was proposed. This research could open a window for future use of biomass energy by deconstructing lignocellulosic biomasses using environmentally friendly pretreatment methods.     

A novel sodium iodide and ammonium molybdate co-catalytic system for the efficient synthesis of 2-benzimidazoles using hydrogen peroxide under ultrasound irradiation

The reaction of aldehydes and o-phenylenediamine for the preparation of 2-benzimidazoles has been studied using hydrogen peroxide as an oxidant under ultrasound irradiation at room temperature in this paper. The combination of substoichiometric sodium iodide and ammonium molybdate as co-catalysts, together with using small amounts of hydrogen peroxide, makes this transformation very efficient and attractive under ultrasound. Thus, a mild, green and efficient method is established to carry out this reaction in high yield.     

Effect of ultrasound and high hydrostatic pressure (US/HHP) on the degradation of dextran catalyzed by dextranase

In our current research work, the effect of combination of ultrasonic irradiation and high hydrostatic pressure (US/HHP) on the enzymatic activity and enzymatic hydrolysis kinetic parameters of dextran catalytic by dextranase were investigated. Furthermore, the effects of US/HHP on the structure of dextranase were also discussed with the aid of fluorescence spectroscopy and circular dichroism (CD) spectroscopy. The maximum hydrolysis of dextran was observed under US (40 W at 25 kHz for 15 min) combined with HHP (400 MPa for 25 min), in which the hydrolysis of dextran increased by 163.79% compared with the routine thermal incubation at 50 °C. Results also showed that, V_max and K_M values, as well as, k_cat of dextranase under US/HHP treatment were higher than that under US, HHP and thermal incubation at 50 °C, indicated that, the substrate is converted into the product at an increased rate when compared with the incubation at 50 °C. Compared to the enzymatic reaction under US, HHP, and routine thermal incubation, dextranase enzymatic reaction under US/HHP treatment showed decreases in Ea, ΔG and ΔH, however small increase in ΔS value was observed. In addition, fluorescence and CD spectra reflected that US/HHP treatment had increased the number of tryptophan on dextranase surface with increased α-helix by 19.80% and reduced random coil by 6.94% upon US/HHP-treated dextranase protein compared to the control, which were helpful for the improvement of its activity. These results indicated that, the combination of US and HHP treatments could be an effective method for improving the hydrolysis of dextran in many industrial applications including sugar manufacturing processes.     

An efficient and green synthesis of novel benzoxazole under ultrasound irradiation

Ultrasound as green process and an alternative energy source was investigated for the environmentally benign synthesis of novel benzoxazoles from different azo-linked salicylic acid derivatives and 2-amino-4-chlorophenol in short reaction time and high yield. These benzoxazole compounds have been characterized by elemental analysis, FT-IR, ¹H NMR and ¹³C NMR spectroscopy.     

Application of ultrasound as pretreatment for extraction of podophyllotoxin from rhizomes of Podophyllum peltatum

The effect of high-power ultrasound pretreatment on the extraction of podophyllotoxin from Podophyllum peltatum was investigated. Direct sonication by an ultrasound probe horn was applied at 24 kHz and a number of factors were investigated: particle size (0.18-0.6 mm), type of solvent (0-100% aqueous ethanol), ultrasonic treatment time (2-40 min), and power of ultrasound (0-100% power intensity, maximum power: 78 W). The optimal condition of ultrasound was achieved with 0.425-0.6 mm particle size, 10 min sonication time, 35 W ultrasound power, and water as the medium. There was no obvious degradation of podophyllotoxin with ultrasound under the applied conditions, and an improvement in extractability was observed. The SEM microscopic structure change of treated samples disclosed the effect of ultrasound on the tissue cells. The increased pore volume and surface area after ultrasonic treatment also confirmed the positive effect of ultrasound pretreatment on the extraction yield of podophyllotoxin from the plant cells.     

Convenient ultrasound mediated synthesis of substituted pyrazolones under solvent-free conditions

Smooth condensation of hydrazine derivatives with various ß-keto esters was performed under solvent-free conditions by using ultrasound irradiation to facilitate the formation of pyrazolone derivatives in good to excellent amounts within very short time periods.     

Alkaline and ultrasound assisted alkaline pretreatment for intensification of delignification process from sustainable raw-material

Alkaline and ultrasound-assisted alkaline pretreatment under mild operating conditions have been investigated for intensification of delignification. The effect of NaOH concentration, biomass loading, temperature, ultrasonic power and duty cycle on the delignification has been studied. Most favorable conditions for only alkaline pretreatment were alkali concentration of 1.75 N, solid loading of 0.8% (w/v), temperature of 353 K and pretreatment time of 6 h and under these conditions, 40.2% delignification was obtained. In case of ultrasound-assisted alkaline approach, most favorable conditions obtained were alkali concentration of 1 N, paper loading of 0.5% (w/v), sonication power of 100 W, duty cycle of 80% and pretreatment time of 70 min and the delignification obtained in ultrasound-assisted alkaline approach under these conditions was 80%. The material samples were characterized by FTIR, SEM, XRD and TGA technique. The lignin was recovered from solution by precipitation method and was characterized by FTIR, GPC and TGA technique.     

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.     

The effect of different parameters under ultrasound irradiation for synthesis of new nanostructured Fe3O4@bio-MOF as an efficient anti-leishmanial in vitro and in vivo conditions

In this work, a magnetic bio-metal–organic framework (MBMOF) nanocomposite with porous-layer open morphology is synthesized through a simple sonochemical approach and its effects on Leishmania major (MRHO/IR/75/ER) under both in vitro and in vivo conditions are investigated. The effects of sonication time, initial concentration of reagents and sonication power on size and morphology of MBMOF nanocomposites have been investigated and optimized. A comparison was then made between the structural information of the nanostructures and that of the bio-metal–organic framework crystals. Using the powder X-ray diffraction (PXRD), field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), energy dispersive analysis of X-ray (EDAX), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA), and Brunauer-Emmet-Teller (BET) techniques, the prepared MBMOF nanocomposites were characterized. The mean numbers of promastigotes (cell/ml) in different MBMOF concentrations (3.12, 6.25, 12.5, 25, 50, 100, 200 and 400 µg mL⁻¹) were determined by direct counting after 24, 48 and 72 h. Using MTT assays, the cytotoxic impacts of the MBMOF nanocomposites on promastigotes, intracellular amastigotes, and J774 macrophages were estimated. In order to investigate their therapeutic effects, the prepared MBMOF nanocomposites (25 and 12.5 µg mL⁻¹) were used as ointment three times a week to treat Leishmania major in BALB/c mice. The lesion size and weight of mice were assessed before and during the treatment. The parasitic loads were measured in spleen and liver through the culture. After 72 h, the INF-γ and IL-4 cytokines levels in the supernatant of the spleen culture were measured. To the best of the authors’ knowledge, this study is the first to attempt to synthesize the bio-MOFs through an in-situ sonosynthesis route under ultrasound irradiation and examine their cytotoxicity effects on Leishmania major under in vitro and in vivo conditions.     

Influence of ultrasound treatment on accessibility and regioselective oxidation reactivity of cellulose

Cellulose fibers were treated with ultrasound in order to improve the accessibility and the reactivity of cellulose. The influence of ultrasound treatment on changes of morphology structure, accessibility and oxidation reactivity of cellulose with sodium periodate were discussed. The results revealed an increase in cellulose’s accessibility in terms of water retention value (WRV) with increasing ultrasound treatment time, corresponding to 73.0%, 75.6%, 80.8%, 98.7% and 119.0% after treated for 0, 90, 180, 360 and 720 s, respectively. Furthermore, the regioselective oxidation reactivity of cellulose with sodium periodate was also successfully improved by the ultrasound treatment. However, no significant changes in crystallinity of cellulose were noted after ultrasound treatment. The oxidized products dialdehyde cellulose (DAC) was further characterized by means of FTIR, X-ray diffraction and SEM.     

Alternate pulses of ultrasound and electricity enhanced electrochemical process for p-nitrophenol degradation

A novel alternated ultrasonic and electric pulse enhanced electrochemical process was developed and used for investigating its effectiveness on the degradation of p-nitrophenol (PNP) in an aqueous solution. The impacts of pulse mode, pH, cell voltage, supporting electrolyte concentration, ultrasonic power and the initial concentration of PNP on the performance of PNP degradation were evaluated. Possible pathway of PNP degradation in this system was proposed based on the intermediates identified by GC–MS. Experimental results showed that 94.1% of PNP could be removed at 2 h in the dual-pulse ultrasound enhanced electrochemical (dual-pulse US-EC) process at mild operating conditions (i.e., pulse mode of electrochemical pulse time (T_EC) = 50 ms and ultrasonic pulse time (T_US) = 100 ms, initial pH of 3.0, cell voltage of 10 V, Na₂SO₄ concentration of 0.05 M, ultrasonic powder of 48.8 W and initial concentration of PNP of 100 mg/L), compared with 89.0%, 58.9%, 2.4% in simultaneous ultrasound enhanced electrochemical (US-EC) process, pulsed electrochemical (EC) process and pulsed ultrasound (US), respectively. Moreover, energy used in the dual-pulse US-EC process was reduced by 50.4% as compared to the US-EC process. The degradation of PNP in the pulsed EC process, US-EC process and dual-pulse process followed pseudo-first-order kinetics. Therefore, the dual-pulse US-EC process was found to be a more effective technique for the degradation of PNP and would have a promising application in wastewater treatment.     

Silica sulfuric acid as mild and efficient catalyst for the preparation of poly-hydroxyl aromatic compounds under mild and heterogeneous conditions

A simple, clean and highly efficient method for the preparation of polyhydroxyl aromatic compounds is described from the reaction of 2,6-bis(methylol)phenols and different substituted phenols in the presence of silica sulfuric acid (SSA) as a heterogeneous catalyst. SSA afforded the clean synthesis of target compounds in much higher yields than traditional catalysts. The established method is also suitable for the synthesis of phloroglucinol derivatives (Phloroglucides) and other polyhydric phenols. Besides the easy work-up of the reaction mixture, the comfortable purification of the products is another advantage of this method.     

Effects of ultrasound and ultrasound assisted alkaline pretreatments on the enzymolysis and structural characteristics of rice protein

The objectives of this study were to investigate the effects of multi-frequency energy-gathered ultrasound (MFEGU) and MFEGU assisted alkaline pretreatments on the enzymolysis and the mechanism of two pretreatments accelerating the rice protein (RP) proteolysis process. The results showed that MFEGU and MFEGU assisted alkaline pretreatments improved significantly (P < 0.05) the degree of hydrolysis (DH) and the protein elution amount of RP. Furthermore under the same DH conditions, ultrasound and ultrasound assisted alkaline pretreatments were more save the enzymolysis time than the unpretreatment. The changes in UV–vis spectra, fluorescence emission spectra indicated unfolding and destruction of RP by MFEGU and MFEGU assisted alkaline pretreatments. The circular dichroism analysis showed that both pretreatments decreased α-helix but increased β-sheet and random coil of RP. Amino acid composition revealed that MFEGU and MFEGU assisted alkaline pretreatments could increase the protein elution amount and the ratio of hydrophobic amino acids. Atomic force microscopy (AFM) indicated that both pretreatments destroyed the microstructures and reduced the particle size of RP. Therefore, MFEGU and MFEGU assisted alkaline pretreatments are beneficial to improving the degree of hydrolysis due to its sonochemistry effect on the molecular conformation as well as on the microstructure of protein.     

A convenient and efficient protocol for the synthesis of 5-aryl-1,3-diphenylpyrazole catalyzed by hydrochloric acid under ultrasound irradiation

The synthesis of 5-aryl-1,3-diphenylpyrazole via the reactions of 3-aryl-2,3-epoxy-1-phenyl-1-propanone with phenylhydrazine was carried out in 69–99% yields at room temperature under ultrasound irradiation. This method provides several advantages such as operational simplicity, higher yield and environment friendly.     

An efficient and facile nitration of phenols with nitric acid/zinc chloride under ultrasonic conditions

An efficient and facile nitration of phenols using nitric acid/zinc chloride under ultrasonic condition has exhibited significant chemo as well as regioselectivity. This study has been extended to other aromatic compounds like naphthalene and anthracene.     

Comparison of two different ultrasound reactors for the treatment of cellulose fibers

The pulp and paper industry is in continuous need for energy-efficient production processes. In the refining process of mechanical pulp, fibrillation is one of the essential unit operations that count for up to 80% of the total energy use. This initial study explores the potential and development of new type of scalable ultrasound reactor for energy efficient mechanical pulping. The developed reactor is of continuous flow type and based on both hydrodynamic and acoustic cavitation in order to modify the mechanical properties of cellulose fibers. A comparison of the prototype tube reactor is made with a batch reactor type where the ultrasonic horn is inserted in the fluid. The pulp samples were sonicated by high-intensity ultrasound, using tuned sonotrodes enhancing the sound pressure and cavitation intensity by a controlled resonance in the contained fluid. The resonant frequency of the batch reactor is 20.8 kHz and for the tube reactor it is 22.8 kHz. The power conversion efficiency for the beaker setup is 25% and 36% in case of the tube reactor in stationary mode. The objective is to verify the benefit of resonance enhanced cavitation intensity when avoiding the effect of Bjerkenes forces. The setup used enables to keep the fibers in the pressure antinodes of the contained fluid. In case of the continuous flow reactor the effect of hydrodynamic cavitation is also induced. The intensity of the ultrasound in both reactors was found to be high enough to produce cavitation in the fluid suspension to enhance the fiber wall treatment. Results show that the mechanical properties of the fibers were changed by the sonification in all tests. The continuous flow type was approximately 50% more efficient than the beaker. The effect of keeping fibers in the antinode of the resonant mode shape of the irradiation frequency was also significant. The effect on fiber properties for the tested mass fraction was determined by a low-intensity ultrasound pulse-echo based measurement method, and by a standard pulp analyzer.     

改进前处理方法测量土壤中痕量汞的重复性和重现性

为验证新的汞前处理方法,在本次实验中进行4次重现性验证,同一样品汞含量的平行值重复性较好,除第1次外,其他3次重现性均较好;4次实验中的校准曲线线性重现性非常好,斜率和截距变化不大,均在合理变化范围之内;初次实验中标准样品的汞含量测定值与理论值大部分不相符,经分析标准样品中汞元素不高,使得消解液中的汞的含量在检出限以下,导致仪器误差的增大,通过在验证实验中加大标准样品的取样量顺利地解决问题。     

Effects of ultrasonic conditions on the interfacial property and emulsifying property of cellulose nanoparticles from ginkgo seed shells

Cellulose microparticles from ginkgo seed shells were treated by ultrasonic treatments within the selected output powders (150–600 W) and durations (10–60 min) to produce cellulose nanoparticles. The main aim of this study was to investigate effects of ultrasonic conditions on the interfacial property and emulsifying property of those cellulose nanoparticles. Compared to ultrasonic output powers, ultrasonic durations showed the greater influence on morphology and physical properties of cellulose nanoparticles. Atomic force microscopy revealed that noodle-like cellulose particles with 1100 nm in length gradually became the short rod-like nanoparticles with 300 nm in length with increasing of ultrasonic duration from 10 min to 60 min. Moreover, results of contact angles indicated that ultrasound could significantly improve hydrophobicity of cellulose nanoparticles. The interfacial shear rheology showed that although all cellulose nanoparticles exhibited the similar interface adsorption behavior which showed the initial lag-phase of adsorption, followed by the interface saturation, the time of this initial lag-phase was affected by ultrasonic conditions. The increase of ultrasonic duration and ultrasonic power could shorten the time of this initial lag-phase, suggesting the resulting cellulose nanoparticles easier adsorption at the O/W interface. It was probably attributed to its small size and high hydrophobicity induced by intense ultrasonic treatments. Meanwhile, the cellulose nanoparticles with small size and higher hydrophobicity exhibited the better emulsifying ability to stabilize oil-in-water emulsions due to the formation of the viscoelastic interfacial film. This study improved understanding about changes in interfacial and emulsifying properties of cellulose nanoparticles caused by ultrasonic treatments.     

A mild and efficient ultrasound-assisted synthesis of diaryl ethers without any catalyst

Diaryl ethers have been prepared by a mild and efficient S_NAr reaction by coupling of various phenols including that having a electron-withdrawing group with activated fluoroarenes using sonication in good to excellent yields at very low temperature (58 °C) under catalyst-free.     

An efficient deprotection of oximes to carbonyls catalyzed by silica sulfuric acid in water under ultrasound irradiation

Deprotection of oximes to the corresponding carbonyl compounds in silica sulfuric acid/surfactant/paraformaldehyde system can be carried out in excellent yields at 50 °C in water under ultrasound irradiation.