Ultrasonic Irradiation Conditions Research Articles

Acidic Ionic Liquids in Ultrasonic Irradiation Conditions Promote the Nucleophilic Addition to Chalcone Derivatives

Under solvent-free conditions and with the help of ultrasonic irradiation, the synthesis of pyrano[3,2-c]chromen and pyrano[3,2-c]quinolin derivatives was promoted by four different ionic liquids. All reaction was performed at 100 °C and had good to excellent yields. 1-butyl-1-methylpyrrolidin-1-ium acetate (A), 1-butyl-1-methylpiperidin-1-ium acetate (B), N,N,N-triethylbutan-1-aminium acetate (C), and tetrabutylammonium acetate (D) as perfect ionic liquids for this reaction show remarkable catalytic activity. The work was simply developed for the reaction of chalcones with 4-hydroxy-1-methylquinolin-2(1H)-one/4-hydroxycoumarin to perform pure products of pyran heterocycles.

Ultrasound-Promoted preparation and application of novel bifunctional core/shell Fe3O4@SiO2@PTS-APG as a robust catalyst in the expeditious synthesis of Hantzsch esters

In this work, D-(–)-α-phenylglycine (APG)-functionalized magnetic nanocatalyst (Fe3O4@SiO2@PTS-APG) was designed and successfully prepared in order to implement the principles of green chemistry for the synthesis of polyhydroquinoline (PHQ) and 1,4-dihydropyridine (1,4-DHP) derivatives under ultrasonic irradiation in EtOH. After preparing of the nanocatalyst, its structure was confirmed by different spectroscopic methods or techniques including Fourier transform infrared (FTIR) spectroscopy, energy-dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and thermal gravimetric analysis (TGA). The performance of Fe3O4@SiO2@PTS-APG nanomaterial, as a heterogeneous catalyst for the Hantzsch condensation, was examined under ultrasonic irradiation and various conditions. The yield of products was controlled under various conditions to reach more than 84% in just 10 min, which indicates the high performance of the nanocatalyst along with the synergistic effect of ultrasonic irradiation. The structure of the products was identified by melting point as well as FTIR and 1H NMR spectroscopic methods. The Fe3O4@SiO2@PTS-APG nanocatalyst is easily prepared from commercially available, lower toxic and thermally stable precursors through a cost-effective, highly efficient and environmentally friendly procedure. The advantages of this method include simplicity of the operation, reaction under mild conditions, the use of an environmentally benign irradiation source, obtaining pure products with high efficiency in short reaction times without using a tedious path, which all of them address important green chemistry principles. Finally, a reasonable mechanism is proposed for the preparation of polyhydroquinoline (PHQ) and 1,4-dihydropyridine (1,4-DHP) derivatives in the presence of Fe3O4@SiO2@PTS-APG bifunctional magnetic nanocatalyst.

A Sulfonic Acid Polyvinyl Pyridinium Ionic Liquid Catalyzes the Multi-Component Synthesis of Spiro-indoline-3,5'-pyrano[2,3-d]-pyrimidines and -Pyrazines.

A sulfonated poly-4-vinyl pyridinium (PVPy-IL-B-SO3H) containing an acidic pyridinium/HSO3- ionic liquid moiety was prepared and used as a catalyst for the three-component reaction of malononitrile with 1-alkylindoline-2,3-diones and 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione or methyl 5-hydroxy-1H-pyrazole-3-carboxylate, leading to methyl 6'-amino-5'-cyano-2-oxo-2'H-spiro[indoline-3,4'-pyrano[2,3-c]pyrazole]-3'-carboxylates or -3,4'-pyrano[2,3-d]pyrimidine]-6'-carbonitrile derivatives under ultrasonic irradiation conditions. The solid catalyst allows easy separation, is cheap, produces high yields under mild conditions, and does not require column chromatography for product isolation and purification.

Chemical Viscosity Reduction of Heavy Oil by Multi-Frequency Ultrasonic Waves with the Main Harmonics of 20–60 kHz

Ultrasound technologies are well-known for their ability to intensify the heat and mass transfer processes. Hence, ultrasonic treatment processes are widely applied for the separation of oil–water emulsions, optimization of oil pumping processes, cleaning the bottomhole zone, etc. However, the main phenomenon under the positive influence of ultrasonic waves on such processes is the cavitation bubbles implosion on the water–oil boundary. It is well-known that ultrasound energy contributes to the reversible viscosity reduction in heavy oil systems. However, it is possible to exhibit chemical destruction of the weakest carbon–heteroatom bonds in the structure of the asphaltenes. This study investigates the influences of controllable ultrasound waves with frequency ranges of 20–60 kHz under the exposure time of 60 s on the rheology of a heavy crude oil sample produced from the Ashalcha reservoir (Tatarstan Republic, Russia). The specific feature of this study is the application of multi-frequency ultrasonic exposure with a wide spectrum of side harmonics with the frequency up to 400 kHz. The results of the Saturates, Aromatics, Resins and Asphaltenes (SARA) analysis method support the chemical consequences of ultrasonication of crude oil. The content of resins under the irradiation of ultrasound waves altered from 32.5 wt.% to 29.4 wt.%, while the number of aromatics hydrocarbons raised from 24.3 wt.% to 34.1 wt.%. The Gas Chromatography—Mass Spectroscopy (GC-MS) analytical analysis method was applied to qualitatively compare the composition of saturated and aromatics fractions between the initial and upgraded heavy crude oil in order to show the chemical destruction of asphaltene bonds after the ultrasonic treatment. It was demonstrated that ultrasound waves allowed chemical conversion of asphaltene fragments that led to irreversible viscosity reduction. The viscosity of the heavy oil sample under the favorable ultrasonic irradiation conditions reduced from 661.2 mPa·s to 178.8 mPa·s. This advantage can be used to develop enhanced oil recovery methods and partial upgrading processes in downstream conditions.

Control of amyloidogenic protein aggregation by ultrasonic irradiation

Protein aggregation causes intractable diseases such as Alzheimer’s disease. In these diseases, crystal-like protein aggregates, so-called amyloid fibrils, form in vivo and induce severe malfunction of biological tissues. Amyloid fibril formation comprises primary nucleation from a supersaturated solution of protein monomers and subsequent fibril growth. Within them, primary nucleation possesses an extremely high energy barrier, resulting in a long induction time for nucleation, typically over a decade in vivo and several days even in a test tube. Our previous study (1) revealed that ultrasonic irradiation to supersaturated protein solution drastically accelerates amyloid formation because of the effects of ultrasonic cavitation, which is applicable to clinical diagnosis (2). However, the degree of acceleration has not been controlled yet. Furthermore, the reproducibility of the induction time for nucleation highly depends on ultrasonic-irradiation conditions and the degree of supersaturation of initial protein solutions. Herein, we systematically investigate the optimized condition to accurately control amyloid formation using an originally developed sonoreactor (3) and discuss the underlying mechanism governing ultrasonic induction of amyloid formation. (1) K. Nakajima et al., Ultrason. Sonochem. 36, 206-211 (2017). (2) K. Nakajima et al., Nat. Commun. 13, 5689 (2022). (3) K. Nakajima et al., Ultrason. Sonochem. 73 105508 (2022).

In vivo evaluation of Sono-chemo therapy via hollow gold nanoshells conjugated to mitoxantrone on breast cancer.

Conventional methods of cancer treatment include surgery, chemotherapy, radiation therapy, and immunotherapy. Chemotherapy, as one of the main methods of cancer treatment, due to the lack of targeted distribution of the drug in tumor tissues, is not able to destroy cancer cells and also affects healthy tissues and causes serious side effects in patients. Sonodynamic therapy (SDT) is a promising strategy for non-invasive treatment of deep solid cancer tumors. In this study, for the first time, the sono-sensitive activity of mitoxantrone was investigated and then mitoxantrone (MTX) was conjugated to hollow gold nanostructure (HGN) to improve the efficiency of in vivo SDT. Firstly, after the synthesis of hollow gold nanoshells and the PEGylation process, conjugation of MTX was performed. Then, after evaluating the toxicity of the treatment groups in vitro, in order to perform an in vivo study, 56 male Balb/c mice that had been tumorized by subcutaneous injection of 4T1 cells were divided into eight groups of breast tumor model. Ultrasonic irradiation (US) conditions including intensity of 1.5 W/cm2 (with a frequency of 800 kHz, 5 min), MTX concentration of 2 μM, and HGN dose of 2.5 mg/kg (unit of animal weight) were used. The results show that administration of PEG-HGN-MTX caused a slight reduction in tumor size and growth compared with free MTX. Ultrasound also improved the therapeutic effect of the gold nanoshell in treated groups, and the HGN-PEG-MTX-US treated groups were able to significantly reduce and control tumor size and growth. The findings also show that MTX and HGN can be used as sonosensitizers in SDT. Also, HGN-PEG-MTX can act as a sono-chemotherapy agent for the combination of sonodynamic therapy and chemotherapy for in vivo breast tumors.

Ultrasound Assisted Facile Synthesis of 2-Benzylidenebenzofuran-3(2H)-ones

2-Benzylidenebenzofuran-3(2H)-ones commonly known as aurones, are an important class of oxygen heterocyclic compounds of flavonoid family. They exhibit some biological activities such as antioxidant, antifungal, anticancer, enzyme inhibitory, antiparasitic and antileishmanial activities. They are also responsible for imparting yellow color to the flowers and fruits. Owing to their varied importance, a simple and efficient method for the synthesis of 2-benzylidenebenzofuran-3(2H)-ones involving the reaction of 1-(2'-hydroxy-phenyl)-3-phenyl-propenones with copper acetate in ethanol under ultrasonic irradiation conditions has been described. The present method offers a faster reaction and a higher yield than conventional methods.

Room-temperature and ambient-pressure conversion of renewable carbohydrates to value-added aromatic N-heterocycles under ultrasonic irradiation conditions

We report a new approach that allows highly efficient one-step conversion of biomass-derived carbohydrates to high-value 2-methylquinoxalines in the presence of aryl-1,2-diamines in water at room temperature and under ambient pressure.

One-pot Synthesis of Substituted Benzimidazole Derivatives under Ultrasonic Irradiation Using ZnFe2O4 Reusable Catalyst

Herein, an efficient one-pot synthesis is described, of substituted benzimidazole derivatives (3a-j) from a condensation of various o-phenylenediamine (1a-j) aromatic aldehyde (2a-j) using ZnFe2O4 as a nano-catalyst under ultrasonic irradiation conditions. All forms of aldehydes with an electron releasing or electron –withdrawing substituent have a significant yield. The catalyst can easily be recovered after completion of the reaction and reused without affecting its activity. Prepared benzimidazole derivatives showed moderate to good anti-tuberculosis results.

The Preparation of a Library of Fused Nitrogen Heterocyclic Compounds Catalyzed by Zn2SnO4 Nanoparticles

A green and facile precipitation method was developed for the preparation of Zn2SnO4 nano-particles in an orange peel (from north Iran) waste extract medium. The as-prepared and calcined samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), and UV–vis, photoluminescence (PL) and diffuse reflectance spectroscopy (DRS). The catalytic potential of the fresh sample of Zn2SnO4 nano-particles was examined on the four-component reaction of 2-hydroxynaphthalene-1,4-dione, 2-aminoaniline, 2-aminopyridine/pyrazin-2-amine, and N-methyl-4-piperidone/aromatic aldehydes under ultrasonic irradiation (US) condition leads to the preparation of some phenazine derivatives.

Derivation of Ultrasonic Irradiation Condition to Inhibit the Growth of Microcystis aeruginosa

Objectives : The optimal ultrasonic irradiation conditions were derived through laboratory-scale experiments to evaluate growth inhibition effect of Microcystis aeruginosa (M. aeruginosa), which is the main specie of Cyanobacterial Harmful Algal Blooms (CyanoHABs) in Republic of Korea.Methods : The experiment was conducted by changing ultrasonic frequency, intensity, and initial cell concentration to observe the growth inhibition effect of M. aerginosa. The experiment was performed using shielded acrylic reactor [20 cm (W) × 20 cm (L) × 30 cm (H)]. Experiments were conducted using large volume (7.2 L) of water samples with high concentrations of M. aeruginosa, and the ultrasonic irradiation time was fixed at 3 hours.Results and Discussion : In all experiments, pictorial view of M. aeruginosa samples, chlorophyll-a (Chl-a) and cell number of M. aerginosa were observed. As a result of ultrasonic irradiation on M. aeruginosa, the decrease in both Chl-a concentration and cell number of M. aeruginosa was monitored after sonication compared to the decrease during sonication. In addition, the rebound growth was confirmed after certain period of growth inhibition of M. aeruginosa. The optimal ultrasonic irradiation conditions for the growth inhibition of M. aeruginosa were obtained at the lower frequency and the higher intensity. Whereas algal growth inhibition was observed with high concentration (4.5 × 106 cells mL-1) of M. aeruginosa, algal growth inhibition was not monitored with low concentration (1.1 × 106 cells mL-1) of M. aeruginosa.Conclusion : Through this study, the algal growth inhibition by ultrasonic was effective. Although the growth inhibition effect persisted for a certain period of time, subsequent regrowth was observed. Therefore, periodic ultrasonic irradiation is necessary for long-term growth inhibition of algal in field applications.

Sono-hollow fiber membrane contactors: A new approach for CO2 separation by physical/chemical absorbents

Herein, the nano adsorbents of Fe3O4 and Fe3O4@SiO2–NH2 were first synthesized and then dispersed in distilled water as a base fluid for Carbon dioxide (CO2) separation from a gas stream using a polypropylene hollow fiber membrane contactor (PP HFMC) and the separation experiment was performed under non-ultrasonic/ultrasonic irradiation for the first time. The impacts of varying liquid and gas flow rates, nanoparticles (NPs) loading, absorbents viscosity, NPs stability, and ultrasonic irradiation intensity were evaluated on the performance of Fe3O4 and Fe3O4@SiO2–NH2 nanofluids in CO2 separation. According to the obtained results, Fe3O4@SiO2–NH2 nanofluid was considerably powerful compared to Fe3O4 nanofluid due to the advantage of chemical reaction with CO2. Furthermore, ultrasound irradiation effectively raised the CO2 absorption capacity of Fe3O4 and Fe3O4@SiO2–NH2 nanofluids up to 13.37 and 16.41%, respectively. Ultimately, at the best operational condition, the CO2 separation enhancement factors of 58.44 and 84.45% were achieved by Fe3O4@SiO2–NH2 nanofluid under non-ultrasonic irradiation and ultrasonic irradiation conditions.

Silica nanospheres KCC-1 as a good catalyst for the preparation of 2-amino-4H-chromenes by ultrasonic irradiation

Fibrous nano-silica sphere (KCC-1) has appeared as a good and efficient catalyst for ultrasonic irradiation conditions in chemical reactions. This catalyst has the unique properties such as a fibrous surface morphology, high surface area and high mechanical stability. The results indicated that the KCC-1 nanocatalyst could be used as high-performance catalysts under high temperature and pressure condition in organic reaction under ultrasonic irradiation. Morphology, structure, and composition of the fibrous nano-silica sphere were described by N2 adsorption–desorption analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and Fourier-transform infrared spectroscopy (FT-IR). In this work, we used KCC-1@NH2 nanosilica as a basic catalyst for the preparation of chromenes under ultrasonic irradiation conditions for the first time. The recyclability, nontoxicity and high stability of the catalyst, combined with low reaction times and excellent yields, make the present protocol very useful for the synthesis of the title products under ultrasonic conditions. The produced products were confirmed via 1H NMR, 13C NMR, FT-IR analysis.

Sono and nano: A perfect synergy for eco-compatible Biginelli reaction

Abstract In this study, we evaluated the performance of nano-γ-Fe2O3–SO3H catalyst in the Biginelli reaction and synthesized 3,4-dihydropyrimidine-2-(1H)-ones. This reaction was carried out under solvent-free and ultrasonic irradiation conditions and belonged to one-pot multicomponent reactions (MCRs) with an adopted aromatic aldehyde, ethyl acetoacetate, and urea as starting materials for the beginning of the reaction. The synthesized materials were efficient in synthesizing 3,4-dihydropyrimidine-2-(1H)-ones via the Biginelli reaction under reaction conditions. Thus, the advantages of using nano-γ-Fe2O3–SO3H in the Biginelli reaction are short reaction time, high efficiency, green method, solvent free, and cost-effective. Furthermore, nano-γ-Fe2O3–SO3H as a heterogeneous catalyst can be recycled five times without significantly reducing catalytic activity.

Synthesis and Characterization of a Novel and Reusable Adenine Based Acidic Nanomagnetic Catalyst and Its Application in the Preparation of 2-Substituted-2,3-dihydro -1H-perimidines under Ultrasonic Irradiation and Solvent-Free Condition

In this study, a novel and reusable adenine-based nano magnetic catalyst namely Fe3O4@SiO2@(CH2)3NHCO-adenine sulfonic acid was designed and synthesized. The structure of the titled catalyst was fully characterized using several skills including FT‐IR spectroscopy, X‐ray (EDX) analysis, X‐ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM), Thermal Gravimetric Analysis (TGA), and Vibrating-Sample Magnetometer (VSM). Then, the catalytic performance of Fe3O4@SiO2@(CH2)3NHCO-adenine sulfonic acid was subjected toward the synthesis of 2,3-dihydro-2-aryl-1H-perimidines using 1,8-diamino naphthalene and aryl aldehydes under ultrasonic irradiation and solvent-free condition. Also, some new compounds of perimidines were synthesized in the presence of this catalyst, and the catalyst has been shown high potent of recovering and reusing capability.

Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (poly(NIPAM-co-HEMA)) is a temperature-responsive copolymer that is expected to be applicable as an advanced functional polymeric material in various fields. In this study, a novel method was developed to control the responsive temperature of poly(NIPAM-co-HEMA) using an ultrasonic polymerization technique. Initially, the behavior of the reaction was investigated using NIPAM and HEMA monomers under ultrasonic irradiation. A high ultrasonic power was found to produce a high reaction rate and low number average molecular weight of the copolymer. The polydispersity of the synthesized copolymer was approximately 1.5 for all ultrasonic powers examined. In the early stage of the reaction, the molar fraction of NIPAM in the copolymer was lower than the initial molar fraction of the monomers. It was concluded that ultrasonic irradiation affected the initiation reaction and polymer degradation, but did not affect the propagation reaction. Furthermore, the effect of the ultrasonic irradiation conditions on the temperature responsiveness of the copolymer was investigated. The lower critical solution temperature (LCST) of the copolymer was found to increase with increasing ultrasonic irradiation time. In addition, in the early stages of the reaction, the measured values of the LCST were higher than the estimated values using copolymer composition. This can be attributed to some parts of the copolymer chain possessing a higher NIPAM fraction than the overall fraction due to different reactivities of the monomers and terminated radicals. This hypothesis was indirectly verified by the synthesis of a block copolymer from the PNIPAM homopolymer and HEMA monomer.

Development of New Thiazole Complexes as Powerful Catalysts for Synthesis of Pyrazole-4-Carbonitrile Derivatives under Ultrasonic Irradiation Condition Supported by DFT Studies.

In this study, we are interested in preparing Fe(III), Pd(II), and Cu(II) complexes from new thiazole derivatives. All syntheses were elaborately elucidated to estimate their molecular and structural formulae, which agreed with those of mononuclear complexes. The square-planer geometry of Pd(II) complex (MATYPd) was the starting point for its use as a heterocatalyst in preparing pyrazole-4-carbonitrile derivatives 4a–o using ultrasonic irradiation through a facile one-pot reaction. The simple operation, short-time reaction (20 min), and high efficiency (97%) were the special advantages of this protocol. Furthermore, this green synthesis strategy was advanced by examination of the reusability of the catalyst in four consecutive cycles without significant loss of catalytic activity. The new synthesis strategy presented remarkable advantages in terms of safety, simplicity, stability, mild conditions, short reaction time, excellent yields, and use of a H2O solvent. This catalytic protocol was confirmed by the density functional theory (DFT) study, which reflected the specific characteristics of such a complex. Logical mechanisms have been suggested for the successfully exerted essential physical parameters that confirmed the superiority of the Pd(II) complex in the catalytic role. Optical band gap, electrophilicity, and electronegativity features, which are essential parameters for the catalytic behavior of the Pd(II) complex, are based mainly on the unsaturated valence shell of Pd(II).

Preparation of thiazolidin-4-one derivatives using ZnO–NiO–NiFe2O4 nano-composite system

The hydrothermal synthesis of ZnO–NiO–NiFe2O4 nano-composite is reported. The sample was utilized to characterize via XRD, FE-SEM, EDS, FT-IR, UV–Vis, and BET techniques. The sample consisted of three different phases as ZnO (hexagonal), NiO (cubic), and NiFe2O4 (cubic) with the average particle size as 34 nm and specific surface area, average pore diameter, and pore volume as 64.35 m2 g−1, 13.02 nm, and 0.201 cm3 g−1, respectively. Catalytic behavior of the nano-composite was investigated on the synthesis of thiazolidin-4-one derivatives under thermal and ultrasonic irradiation condition. Our results show that the catalytic activity of ZnO–NiO–NiFe2O4 nano-composite is much higher than ZnO, NiO, and NiFe2O4 metal oxides. All products were prepared in high yields with short reaction times. In addition, the catalyst was recovered for at least five times.

Ultrasonic‐Assisted Hypervalent Iodine‐Catalyzed Cyclization of (E)‐2‐Hydroxystilbenes to Benzofurans Using Iodobenzene as Pre‐catalyst

AbstractA rapid, and metal‐free approach for the synthesis of functionalized benzofurans 10 is illustrated by PhI 9 catalyzed cyclization of 2‐hydroxystilbenes 8. The 2‐hydroxystilbenes 8 were cyclized using 10 mol % PhI as a precatalyst, 2.0 equiv. of m‐CPBA as an oxidant and 2.4 equiv. of TFA as an additive at room temperature under ultrasonic irradiation condition. The functionalized benzofurans 10 were gained in good to excellent yields with shorter reaction times.

Fabrication of a new heterogeneous tungstate-based on the amino-functionalized metal-organic framework as an efficient catalyst towards sonochemical oxidation of alcohols under green condition

Ultrasonic-assisted reactions, as a green technique, are often more efficient compared to those traditional protocols. To this end, the selective and solvent-free oxidation of aromatic alcohols to the corresponding aldehydes and ketones were investigated in the presence of Co-ABDC/W at room temperature under ultrasonic irradiation conditions for the first time in this paper. The structure, particle size, thermal stability, and morphology of the fabricated heterogeneous catalyst and the products were characterized by FT-IR, EDS, FE-SEM, XRD, TGA, and GC analyses. In this regard, immobilization of tungstate had a significant effect on thermal stability (around 450 °C for 40% weight loss) and catalytic performance. Moreover, the efficiency of two different oxidation methods, including ultrasound irradiations and reflux, were comparatively investigated by GC spectrometry. Obtained sonoxidation results presented higher conversions ranging (84 to 100%) than reflux condition via shorter reaction times. The influences of the reaction parameters, such as hydrogen peroxide concentration, and catalyst loading, were also investigated. The proposed method offers several advantages, such as excellent conversions, selective oxidations, environmentally-benign procedure, short reaction times, and easy workup. Notably, this is the first report that focuses on using amino-functionalized MOFs with ultrasonic irradiation for selective oxidation reactions.