Ultrasound and microwave assisted synthesis of isoindolo-1,2-diazine: a comparative study

A comparative study, ultrasound (US) versus microwave (MW) versus conventional thermal heating (TH), for synthesis of isoindolo-1,2-diazine is described. The reaction pathway is fast, efficient and straight applicable, involving a Huisgen [3+2] dipolar cycloaddition of cycloimmonium ylides to 1,4-naphthoquinone. A feasible reaction mechanism for the obtaining of the fully aromatized tetra- and penta- cyclic isoindolo-1,2-diazine is presented. Under US irradiation the yields are much higher (sometimes substantially, by almost double), the reaction time decreases substantially, the reaction conditions are milder. The use of a generator with a higher nominal power induces higher yields and short reaction times. Overall the use of US it proved to be more efficient than MW or TH. A feasible explication for US efficiency is presented.     

Ultrasound assisted one pot synthesis of imidazole derivatives using diethyl bromophosphate as an oxidant

A one pot, three-component condensation of benzoin/benzyl, an aldehyde, and ammonium acetate using diethyl bromophosphate as a mild oxidant is achieved to form trisubstituted imidazole compounds. Under ultrasound irradiation, a smooth condensation occurs to get the 2, 4, 5-triaryl-1H-imidazole compounds in good to excellent yields. The study explores the scope and limitation of diethyl bromophosphate as an oxidant and suggests advantages, viz., simplicity of operation, reduction in time, and an increase in product yields.     

Ultrasound promoted synthesis of Nile Blue derivatives

Ultrasound irradiation was used for the first time towards the synthesis of new Nile Blue related benzo[a]phenoxazinium chlorides possessing isopentylamino, (2-cyclohexylethyl)amino and phenethylamino groups at 5-position of the heterocyclic system. The efficacy of sonochemistry was investigated with some of our earlier reported synthesis of benzo[a]phenoxazinium chlorides. This newer protocol proved competent in terms of reaction times and enhanced yields. Photophysical studies carried out in ethanol, water and simulated physiological conditions, revealed that emission maxima occurred in the range 644–656 nm, with high fluorescent quantum yields. Other attractive feature exhibited by these materials includes good thermal stability. These properties might be useful in the development of fluorescent probes for biotechnology.     

Ultrasound assisted lipase catalyzed synthesis of poly-6-hydroxyhexanoate

Ultrasonic irradiation greatly improved the Candida antarctica lipase B mediated ring opening polymerization of ε-caprolactone to poly-6-hydroxyhexanoate in the ionic liquid 1-ethyl-3-methylimidazolium tetraflouroborate. Compared to the conventional nonsonicated reaction, sonication improved the monomer conversion by 63% and afforded a polymer product of a narrower molecular weight distribution and a higher degree of crystallinity. Under sonication, the polydispersity index of the product was ∼1.44 compared to a value of ∼2.55 for the product of the conventional reaction. With sonication, nearly 75% of the monomer was converted to product, but the conversion was only ∼16% for the reaction carried out conventionally. Compared to conventional operation, sonication enhanced the rate of polymer propagation by >2-fold and the turnover number of the lipase by >3-fold.     

Ultrasound assisted synthesis of amide functionalized metal-organic framework for nitroaromatic sensing

Nano plates of zinc(II) based metal-organic framework (MOF) were prepared via ultrasonic method without any surfactants at room temperature and atmospheric pressure. Control of particle size and morphology was enhanced in this synthesis method. Nano plates of an interpenetrated amide-functionalized metal-organic framework, [Zn₂(oba)₂(bpfb)]·(DMF)₅, TMU-23, (H₂oba = 4,4′-oxybis(benzoic acid); bpfb = N,N′-bis-(4-pyridylformamide)-1,4-benzenediamine, DMF = N,N-dimethyl formamide), was synthesized under ultrasound irradiation in different concentrations of initial precursor. The nano structure and morphology of the synthesized MOF were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), powder X-ray diffraction, thermo gravimetric analysis (TGA), elemental analysis and FTIR spectroscopy. Moreover, Fluorescence emissions of nanoplates have been studied. Amide-functionalized MOF shows high selectivity for sensing of nitroaromatic compounds such as nitrophenol, nitroaniline, and nitrobenzene in acetonitrile solution. Fluorescence intensity decreased with increasing contents of nitroaromatics in acetonitrile solution due to fluorescence quenching effect.     

Comparison of ultrasound and microwave assisted extraction of diosgenin from Trigonella foenum graceum seed

From the recent market trend, there is a huge demand for the bioactive compounds from various food matrices that could be capable enough to combat the emerging health effects in day-to-day life. Fenugreek is a well-known spice from ancient times for its medicinal and health benefits. In the present study, two methods of green extraction microwave (MAE) and ultrasound (UAE) assisted were studied in regard of extraction of fenugreek diosgenin. In this study, solvent type (acetone, ethanol, hexane and petroleum ether), solvent concentration (40, 60, 80 and 100%) and treatment time (1.5, 3.0, 4.5 and 6.0 min and 30, 40, 50 and 60 min for MAE and UAE method respectively) was varied to observe the effect of these parameters over extract yield and diosgenin content. The results of this study revealed that treatment time, type of solvent and its concentration and method adopted for extraction of diosgenin has significant effect. In relation with better yield extract and diosgenin content, the yield of fenugreek seed extract was 7.83% with MAE and 21.48% with UAE of fenugreek seed powder at 80% ethanol concentration at 6 and 60 min respectively. The content of diosgenin was observed in fenugreek seed powder extract was 35.50 mg/100 g in MAE and 40.37 mg/100 g in UAE with 80% ethanol concentration at 6 and 60 min respectively. The overall range of yield of fenugreek extract was varied from 1.04% to 32.48% and diosgenin content was 15.82 mg/100 g to 40.37 mg/100 g of fenugreek seed powder including both extraction methods. This study revealed that UAE would impose better ways for preparing fenugreek extract and observing diosgenin content from fenugreek seeds.     

Ultrasound with low intensity assisted the synthesis of nanocrystalline TiO2 without calcination

A novel method has been developed for the preparation of nano-sized TiO₂ with anatase phase. Nanoparticles with diameter about 6 nm were prepared at a relatively low temperature (75 °C) and short time. The synthesis was carried out by the hydrolysis of titanium tetra-isopropoxide (TTIP) in the presence of water, ethanol, and dispersant under ultrasonic irradiation (500 kHz) at low intensity. The results show that variables such as water/ethanol ratio, irradiation time, and temperature have a great influence on the particle size and crystalline phases of TiO₂ nanoparticles. Characterization of the product was carried out by different techniques such as powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and UV–vis spectroscopy.     

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 synthesis of performic acid in a continuous flow microstructured reactor

The present work establishes in depth study of ultrasound assisted preparation of performic acid (PFA) in a continuous flow microstructured reactor. The influence of various parameters viz. formic acid: hydrogen peroxide molar ratio, flow rate, temperature and catalyst loading on the PFA formation were studied in a continuous flow microstructured reactor. In a continuous microstructured reactor in the presence of ultrasonic irradiation, the formation of PFA was found to be dependent on the molar ratio of formic acid: hydrogen peroxide, flow rate of reactants, temperature and catalyst loading (Amberlite IR-120H). The optimized parameter values are 1:1 M ratio, 50 mL/h, 40 °C and 471 mg/cm³ respectively. Further, the performance of Amberlite IR-120H catalyst was evaluated for three successive cycles in continuous microstructured reactor. The performance of catalyst was found to be decreased with the usage of the catalyst and is attributed to neutralization of the sulfonic acid groups, catalyst shrinkage, or loss in pore sites. The experimental results revealed that, for an ultrasound assisted synthesis of PFA in continuous microstructured reactor the observed reaction time was even less than 10 min. The observed intensification in the PFA synthesis process can be attributed to the intense collapse of the cavities formed at low temperature during ultrasonic irradiations, which further improved the heat and mass transfer rates with the formation of H₂O₂ during the reaction. The combined use of ultrasound and a continuous flow microstructured reactor has proved beneficial process of performic acid synthesis.     

Ultrasound assisted modulation of yeast growth and inactivation kinetics

The yeast Saccharomyces cerevisiae is well known for its application in the food industry for the purpose of developing fermented food. The ultrasound (US) technology offer a wide range of applications for the food industry, including the enhancement of fermentation rates and inactivation of microbial cells. However, a better understanding and standardization of this technology is still required to ensure the scaling-up process. This study investigated the effect of the US technology on the growth of S. cerevisiae using frequencies of 20, 25, 45 and 130 kHz, treatment periods from 2 to 30 min. Furthermore, yeast kinetics subjected to US treatments were evaluated using modelling tools and scanning electron microscopy (SEM) analysis to explore the impact of sonication on yeast cells. Yeast growth was monitored after different US treatments plotting optical density (OD) at 660 nm for 24 h at 30 ⁰C. Growth curves were fitted using models of modified Gompertz and Scale-Free which showed good parameters of the fit. In particular, US frequencies of 45 and 130 kHz did not have a disruptive effect in lag phase and growth rate of the yeast populations, unlike the frequency of 20 kHz. Moreover, inactivation curves of yeast cells obtained after exposure to 20 and 25 kHz also observed the best fit using the Weibull model. US frequency of 20 kHz achieved significant reductions of 1.3 log cfu/mL in yeast concentration and also induced important cell damage on the external structures of S. cerevisiae. In conclusion, the present study demonstrated the significant effect of applying different US frequencies on the yeast growth for potential application in the food industry.     

A new reactor for process intensification involving the simultaneous application of adjustable ultrasound and microwave radiation

Ultrasound (US) and Microwaves (MW) are effective methods for processes intensification. Their combined use in the same reactor can lead to remarkable results. Recently there has been a resurgence of interest in this field for new synthetic applications using reactors based upon existing technologies. We describe here a new type of apparatus in which the thermal energy is continuously removed from the system making possible the use of high power and adjustable ultrasonic and microwave densities throughout the process. The installation consists of a glass reactor located in a monomode applicator which is immersed at the same time in an ultrasonic device which can be operated at different frequencies and powers. A liquid, transparent to microwaves, was used to couple ultrasonic energy to the reactor and to remove the heat generated. Comsol software was used to get information about the distribution of ultrasonic and microwave energy between the reactor liquid and the coupling fluid. The performance was assessed using the conversion of p-nitrophenol into 4-nitrocatechol as a chemical dosimeter and a transesterification.     

Effects of ultrasound synergized with microwave on structure and functional properties of transglutaminase-crosslinked whey protein isolate

In the present study, ultrasound (400 W, U), microwave heating (75 ℃ for 15 min, M) and ultrasound synergized with microwave heating (UM) pretreatments of whey protein isolate (WPI) were applied to investigate and compare their influence on structure, physicochemical and functional characteristic of transglutaminase (TGase)-induced WPI. From the results of size exclusion chromatography, it could be seen that all three physical pretreatments could promote the formation of polymers in TGase cross-linked WPI, whose polymer amounts were increased by the order of U, UM and M pretreatment. Among three physical methods, M pretreatment had the strongest effect on structure and functional characteristics of TGase-induced WPI. Furthermore, compared with TGase-induced WPI, α-helix and β-turn of M−treated TGase-induced WPI (M−WPI−TGase) were reduced by 7.86% and 2.93%, whereas its β-sheet and irregular curl were increased by 15.37% and 7.23%. Zeta potential, emulsion stability and foaming stability of M−WPI−TGase were increased by 7.8%, 59.27% and 28.95%, respectively. This experiment exhibited that M was a more effective pretreatment method than U, UM for WPI, which could promote its reaction with TGase and improve its functional properties.     

Ultrasound assisted one-pot, three-components synthesis of pyrimido[1,2-a]benzimidazoles and pyrazolo[3,4-b]pyridines: A new access via phenylsulfone synthon

A simple, facile, efficient and three-components procedure for the synthesis of pyrimido[1,2-a]benzimidazoles and pyrazolo[3,4-b]pyridines utilizing phenylsulfone synthon, under ultrasonic irradiation was developed.     

Ultrasound assisted enzymatic depolymerization of aqueous guar gum solution

The present work investigates the effectiveness of application of low intensity ultrasonic irradiation for the intensification of enzymatic depolymerization of aqueous guar gum solution. The extent of depolymerization of guar gum has been analyzed in terms of intrinsic viscosity reduction. The effect of ultrasonic irradiation on the kinetic and thermodynamic parameters related to the enzyme activity as well as the intrinsic viscosity reduction of guar gum using enzymatic approach has been evaluated. The kinetic rate constant has been found to increase with an increase in the temperature and cellulase loading. It has been observed that application of ultrasound not only enhances the extent of depolymerization but also reduces the time of depolymerization as compared to conventional enzymatic degradation technique. In the presence of cellulase enzyme, the maximum extent of depolymerization of guar gum has been observed at 60 W of ultrasonic rated power and ultrasonic treatment time of 30 min. The effect of ultrasound on the kinetic and thermodynamic parameters as well as the molecular structure of cellulase enzyme was evaluated with the help of the chemical reaction kinetics model and fluorescence spectroscopy. Application of ultrasound resulted in a reduction in the thermodynamic parameters of activation energy (E_a), enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) by 47%, 50%, 65% and 1.97%, respectively. The changes in the chemical structure of guar gum treated using ultrasound assisted enzymatic approach in comparison to the native guar gum were also characterized by FTIR. The results revealed that enzymatic depolymerization of guar gum resulted in a polysaccharide with low degree of polymerization, viscosity and consistency index without any change in the core chemical structure which could make it useful for incorporation in food products.     

Optimization and comparison of ultrasound/microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomatoes

The extracting technology including ultrasonic and microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomato paste were optimized and compared. The results showed that the optimal conditions for UMAE were 98 W microwave power together with 40 KHz ultrasonic processing, the ratio of solvents to tomato paste was 10.6:1 (V/W) and the extracting time should be 367 s; as for UAE, the extracting temperature was 86.4 °C, the ratio of the solvents to tomato paste was 8.0:1 (V/W) and the extracting time should be 29.1 min, while the percentage of lycopene yield was 97.4% and 89.4% for UMAE and UAE, respectively. These results implied that UMAE was far more efficient extracting method than UAE.     

A simplified green chemistry approaches to synthesis of 2-substituted 1,2,3-triazoles and 4-amino-5-cyanopyrazole derivatives conventional heating versus microwave and ultrasound as ecofriendly energy sources

Cyanoacetamides 3 were prepared via reacting ethyl cyanoacetate with benzylamine. Yields and reaction times needed for reaction completion at room temperature, by microwaves (μω) heating and under ultrasound (US) irradiations are compared. The formed cyanoacetamides were coupled with aromatic diazonium salts and the formed arylhydrazones were used as precursors to title triazoles and pyrazoles via reacting the former with hydroxylamine and chloroacetonitrile. Yields of products formed via conventional heating are compared with those of μω and US irradiation.     

Poly(sodium-p-styrenesulfonate) assisted microwave synthesis of ordered mesoporous carbon supported Pd nanoparticles for formic acid electro-oxidation

Pd nanoparticles highly dispersed onto the surface of ordered mesoporous carbons (OMCs) were synthesized successfully by poly(sodium-p-styrenesulfonate) (PSS) assisted microwave synthesis. Here, PSS served as a bifunctional molecule both for solubilizing and dispersing OMCs into aqueous solution and for jointing Pd²⁺ to facilitate the subsequent uniform formation of Pd nanoparticles on their surfaces. The effects of PSS on structural and electrochemical properties of Pd/OMCs were investigated. It was found that the addition of PSS facilitated Pd nanoparticles to disperse on the carbon surface. Electrochemical properties showed that Pd catalysts prepared with addition of PSS displayed better electrochemical activity and stability for formic acid electro-oxidation than those without PSS.     

Ultrasound assisted synthesis of some new 1,3,4-thiadiazole and bi(1,3,4-thiadiazole) derivatives incorporating pyrazolone moiety

Novel substituted 1,3,4-thiadiazole and bi(1,3,4-thiadiazole) were synthesized from reaction of 1-methyl-5-oxo-3-phenyl-2-pyrazolin-4-thiocarbox-anilide with a series of different hydrazonyl halides or N,N'-diphenyl-oxalodihydrazonoyl dichloride. The reactions were carried out under both conventional and ultrasonic irradiation conditions. In general, improvement in rates and yields were observed when reactions were carried out under sonication compared with classical condition. Structures of the products were established on analytical and spectral data.     

Investigation on the influence of ultrasonic pretreatment on color,quality and antioxidant attributes of microwave dried Inula viscosa (L.)

Impact of various ultrasound pretreatment and microwave drying parameters on the qualitative and antioxidant characteristics of Inula viscosa (L.) was investigated in this study. The leaves of Inula viscosa (L.) were sonicated for 10, 20, and 30 min in an ultrasonic bath (37 kHz, 150 Watts). Microwave drying was done at three distinct times (1, 3, and 5 min) and with three different microwave power levels (100, 180, and 300 Watts). Microwave dried samples were tested for color characteristics (L*, a*, b*), chlorophyll, carotenoid, total phenol, and antioxidant content. All dried samples were prepared by infusing them in hot water as tea, and the sensorial properties of teas including odor, color, aroma, and overall acceptability were evaluated by panelists. For 10, 20, and 30 min of ultrasound pretreatment, the L* values of leaves varied from 37.70 to 49.76, 34.97 to 46.25, and 27.88 to 43.34, respectively. The total carotenoid concentration ranged from 0.12 to 0.32 mg/g DW, while the total chlorophyll content was from 0.44 to 0.94 mg/g DW. The antioxidant activity of Inula viscosa (L.) leaves that were dried at 300 Watts for 5 min did not change significantly as a result of ultrasound pretreatment. There was a significant positive correlation between aroma and TPC, as well as between color and overall acceptability. The darkest-colored teas were deemed preferable by the panelists.     

Hybrid high-intensity ultrasound and microwave treatment: A review on its effect on quality and bioactivity of foods

With the growing of consumer’s demand for products ready to eat that can be elaborated with greener technologies without affecting to their organoleptic characteristics, the application of ultrasound combined with microwaves has been widely studied on food preservation treatments (drying, frying), extraction of high-value added compounds and enzymatic hydrolysis of proteins. This review presents a complete picture of current knowledge on the ultrasound combined with microwaves including the mechanisms, influencing factors, advantages and drawbacks, emphasising in several synergistic effects observed in different processes of strong importance in the food industry. Recent research has shown that this hybrid technology could not only minimise the disadvantages of power US for drying and frying but also improve the product quality and the efficiency of both cooking processes by lowering the energy consumption. Regarding extraction, current studies have corroborated that the combined method presents higher yields in less time, in comparison with those in the respective ultrasound and microwave separately. Additionally, recent results have indicated that the bioactive compounds extracted by this combined technology exhibit promising antitumor activities as well as antioxidant and hepatoprotective effects. Remarkably, this hybrid technology has been shown as a good pre-treatment since the structural changes that are produced in the molecules facilitate the subsequent action of enzymes. However, the combination of these techniques still requires a proper design to develop and optimized conditions are required to make a scale process, and it may lead to a major step concerning a sustainable development and utilization of bioactive compounds from natural products in real life.