超声波和紫外光协同降解酸性橙Ⅱ水溶液的机理研究

以含有多个苯环的典型偶氮染料-酸性橙Ⅱ为研究对象,研究了超声波和紫外光分别辐照及共同辐照下的降解现象。酸性橙Ⅱ水溶液在超声波及紫外光分别辐照下均发生显著降解,反应过程符合准一级反应动力学规律。在超声波和紫外光共同辐照下,反应过程也符合准一级反应动力学规律,同时酸性橙Ⅱ水溶液降解呈现显著的声光协同效应,即同一辐照时间内超声波和紫外光共同辐照下酸性橙Ⅱ的降解率大于超声波和紫外光单独辐照下各自降解率之和。动力学分析结果表明,该协同效应可归因于紫外光对超声空化过程中产生的过氧化氢的裂解作用。      

Dehydration reaction of hydroxenin monoacetate in carbon tetrachloride and an aliphatic alcohol under ultrasound irradiation

A new method for the preparation of an E/Z mixture of vitamin A acetate from hydroxenin monoacetate is described. This two-step reaction was studied by changing the reaction parameters (reaction temperature, ultrasound power, and reaction time) and the alcohol used. This approach consists of the dehydration reaction of hydroxenin monoacetate under ultrasound irradiation in CCl4 and an aliphatic alcohol under an inert atmosphere. The formation of small amounts of HCl from CCl4 and an aliphatic alcohol under ultrasound irradiation is followed by the dehydration reaction of hydroxenin monoacetate. An E/Z mixture of vitamin A acetate was obtained resulting in the desired pentaenes. Some ethers derivatives were also formed as by-products, isolated and characterized. Study of the reaction mechanism is also reported here.     

Dynamical properties of iodine release in potassium iodide solution under combination of ultrasound and light irradiations

Dynamical process of iodine release in potassium iodide solution has been investigated under the irradiations of ultrasound and visible light respectively and simultaneously. Under ultrasonic irradiation, the efficiency of iodine release increases almost linearly with the irradiation time, indicating the zero-order reaction. On the other hand, the efficiency of iodine release increases exponentially with the irradiation time under visible light irradiation and combined irradiation of ultrasound and visible light, suggesting the pseudo first-order kinetics. We further find a significant synergistic effect induced by combined irradiation of ultrasound and visible light, which may be due to the well-mixed condition in the photochemical reactor with the applying simultaneous ultrasound. We further investigate influence of the initial concentration of potassium iodide on the synergistic effect.     

Synthesis and characterization of Ag nanoparticles@Polyethylene fibers under ultrasound irradiation

The polyethylene fibers containing Ag nanoparticles were prepared through the chemical reduction under ultrasound irradiation. The effect of reducing reagent, power of ultrasound irradiation, reaction time and temperature in growth of the nanometric Ag were studied. Particle sizes and morphology of nanoparticle are depending on power of ultrasound irradiation. Results show a decrease in the particles size as increasing power of ultrasound irradiation. Also, an increase in temperature led to increase of particle size. The polyethylene fibers containing Ag nanoparticles were characterized with powder X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Improved synthesis of diethyl 2,6-dimethyl-4-aryl-4H-pyran-3,5-dicarboxylate under ultrasound irradiation

Diethyl 2,6-dimethyl-4-aryl-4H-pyran-3,5-dicarboxylates (1) have been synthesized by the reaction of aryl aldehyde and 1,3-diketone catalyzed by ZnCl₂ under ultrasound irradiation. The effects of changes in the ultrasonic power, temperature, and reaction time are discussed. With the optimized reaction conditions, various aryl aldehydes were used to synthesize 4H-pyrans (1) under the influence of ultrasound irradiation. Compared with the conventional thermal methods, the remarkable advantages of this method are the simple experimental procedure, shorter reaction time and high yield of product.     

Ultrasonic-assisted synthesis of flavones by oxidative cyclization of 2′-hydroxychalcones using iodine monochloride

This paper presents an efficient methodology for the synthesis of flavones via the oxidative cyclization of 2′-hydroxychalcones in the presence of iodine monochloride with DMSO under ultrasound irradiation. Ultrasonic irradiation enhances the cyclization reaction and leads to reduced reaction time at lower reaction temperatures while generating flavones with high yields.     

Ultrasound irradiation promoted efficient solvent-free lipase-catalyzed production of mono- and diacylglycerols from olive oil

This work reports the enzymatic production of mono- and diacylglycerols under the influence of ultrasound irradiation, in a solvent-free system, with and without the presence of surfactants at a constant temperature of 65°C, glycerol to oil molar ratio of 2:1 and a commercial immobilized lipase (Novozym 435) as catalyst. For this purpose, two operation modes were adopted: the use of a sonotrode (ultrasonic probe), without agitation, varying reaction time, irradiation amplitude (25-45% of the total power) and type of surfactant, and a mechanically stirred reactor (600 rpm) under ultrasound irradiation in a water bath, testing different surfactants. Results show that very satisfactory MAG and DAG yields, above 50 wt.%, can be obtained without the use of surfactant, at mild irradiation power supply (～130 W), with no important enzyme activity losses verified, in a relatively short reaction time (2h), and low enzyme content (7.5 wt.%). Also, reaction kinetic results show that contents of MAG+DAG as high as ～65 wt.% can be achieved at longer times (6h), indicating a promising route for producing MAG and DAG using ultrasound irradiation.     

Ultrasound assisted reactions of steroid analogous of anticipated biological activities

A new, fast, efficient and general method for preparation of steroid analogous of anticipated biological activity under ultrasound irradiation and classical heating is reported. The reaction pathway involves two steps: quaternization of phthalazine heterocycle followed by a 3+2 dipolar cycloaddition of cycloimmonium ylides to dienophiles. Under ultrasound the reaction time decreases substantially, the yields are higher, the reaction conditions are milder. A comparative study ultrasound verses classical heating has been done.     

Ultrasonic-assisted synthesis of chrysin derivatives linked with 1,2,3-triazoles by 1,3-dipolar cycloaddition reaction

The 1,3-dipolar cycloaddition reaction between 7-(3-azidopropoxy)-5-hydroxyflavone and phenylacetylene was carried out to investigate the synthesis of 7-(3-(4-phenyl-1,2,3-triazol-1-yl)propoxy)- 5-hydroxyflavone in presence of ultrasound (sono-synthesis) and absence of ultrasound (conventional method) under relatively optimized solvent and catalyst conditions. The reaction rate was notably accelerated with the help of ultrasound irradiation. An experiment was especially carried out for investigating the acceleration mechanism of ultrasound on the cycloaddition. A novel series of chrysin derivatives linked with 1,2,3-triazoles were obtained by the copper(I)-catalyzed 1,3-dipolar Huisgen cycloaddition reaction using t-BuOH/H(2)O (1:1 v/v) as reaction solvents and CuSO(4)·5H(2)O/sodium ascorbate as the catalyst at room temperature in the presence of ultrasound irradiation. Their structures are elucidated by NMR, ESI MS, IR and Elemental analysis.     

Removal of organic matter and ammonia nitrogen from landfill leachate by ultrasound

Experiments on the removal of organic matters and ammonia nitrogen from landfill leachate by ultrasound irradiation were carried out. The effects of COD reduction and ammonia removal of power input, initial concentration, initial pH and aeration were studied. It was found that the sonolysis of organic matters proceeds via reaction with ()OH radicals; a thermal reaction also occurs with a small contribution. The rise of COD at some intervals could be explained by the complexity of organic pollutant sonolysis in landfill leachate. Ultrasonic irradiation was shown to be an effective method for the removal of ammonia nitrogen from landfill leachate. After 180 min ultrasound irradiation, up to 96% ammonia nitrogen removal efficiency can be obtained. It was found that the mechanism of ammonia nitrogen removal by ultrasound irradiation is largely that the free ammonia molecules in leachate enter into the cavitation bubbles and transform into nitrogen molecules and hydrogen molecules via pyrolysis under instant high temperature and high pressure in the cavitation bubbles.     

Ethoxylation of p-chloronitrobenzene using phase-transfer catalysts by ultrasound irradiation: a kinetic study

Ethoxy-4-nitrobenzene was synthesized by the reaction of 4-chloronitrobenzene with potassium ethoxide in a homogeneous system using benzyltriethylammonium chloride (QCl) as a phase-transfer catalyst at 50 degrees C under ultrasound irradiation conditions. The use of phase-transfer catalysts and ultrasound has been compared and demonstrated in this nucleophilic substitution reactions. The kinetics of the reaction depends on the effect of amount of catalyst, quaternary ammonium salts, agitation speed, amount of potassium hydroxide, amount of ethanol, temperature and the frequency of the ultrasound waves on the conversion of the reaction.     

Ultrasound assisted the chemoselective 1,1-diacetate protection and deprotection of aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate salt as a eco-benign,efficient and reusable solid acid catalyst

Poly(4-vinylpyridinium) hydrogen sulfate solid acid was found to be efficient catalyst for preparation of 1,1-diacetate using ultrasound irradiation at ambient temperature and neat condition. Deprotection of the resulting 1,1-diacetates were achieved using the same catalyst in methanol solvent under ultrasound irradiation at room temperature. This new method consistently has the advantage of excellent yields and short reaction times. Utilization of solvent free, simple reaction conditions, isolation, and purification makes this manipulation very interesting from an economic and environmental perspective. Further, the catalyst can be reused and recovered for several times.     

Synergistic effects on iodine release in potassium iodide solution by combination of ultrasound and visible light irradiations

Iodine release in potassium iodide solution has been investigated under the irradiations of ultrasound and visible light respectively and simultaneously. We have observed that the amount of iodine liberated under the combined irradiation of ultrasound and visible light is larger than the sum of that under the respective irradiations of ultrasound and visible light, indicating a synergistic effect of ultrasound and visible light irradiations. Based on the investigation of the reaction kinetics of iodine liberated, we have ascribed the synergistic effect to the perfect stirring of the photochemical reactor induced by the applying simultaneous ultrasound. The ideal stirring can result in the homogenization of the primary light effect in the whole reaction medium, which induces the acceleration of the photochemical reaction. On behavior of our knowledge, there are few reports on the investigations of utilizing the combination of ultrasonic energy and light energy to accelerate the reaction yield and rate as well as the kinetics of the reaction.     

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.     

Quantification of ultrasonic intensity based on the decomposition reaction of porphyrin

A simple method is proposed for quantification of the effective ultrasonic intensity in the reaction vessel based on the decomposition reaction of 5,10,15,20-tetrakis(4-sulfotophenyl) porphyrin (H₂TPPS⁴⁻). The change of concentration of porphyrin in solution irradiated by the ultrasound wave depends on the irradiation time and the output power of ultrasound generator. The decomposition ratio of porphyrin is defined as the ratio of the concentration of porphyrin after ultrasonic irradiation to that before ultrasonic irradiation. A linear relationship between the decomposition ratio of porphyrin and the concentration Fe³⁺ in the Fricke solution under sonication was obtained. The decomposition ratio was related to the absorption dose in radiation chemistry.     

An investigation of lipase catalysed sonochemical synthesis: A review

Ultrasonic irradiation has recently gained attention of researchers for its process intensification in numerous reactions. Earlier ultrasound was known for its application either to deactivate enzyme activity or to disrupt the cell. However, in recent years, practice of ultrasonic irradiation began to emerge as a tool for the activation of the enzymes under mild frequency conditions. The incorporation of ultrasound in any of enzymatic reactions not only increases yield but also accelerates the rate of reaction in the presence of mild conditions with better yield and less side-products. To attain maximum yield, it is crucial to understand the mechanism and effect of sonication on reaction especially for the lipase enzyme. Thus, the influence of ultrasound irradiation on reaction yield for different parameters including temperature, enzyme concentration, mole ratio of substrates, solvents ultrasonic frequency and power was reviewed and discussed. The physical effect of cavitation determined by bubble dynamics and rate of reaction through kinetic modelling also needs to be assessed for complete investigation and scale up of synthesis. Thus, prudish utilisation of ultrasound for enzymatic synthesis can serve better future for sustainable and green chemistry.     

Lipase-catalyzed diacylglycerol production under sonochemical irradiation

The present paper describes a protocol for production of diacylglycerol by the partial hydrolysis of soybean oil catalyzed by lipase under ultrasound irradiation. Better yields and shorter reaction times were obtained under sonication as compared to the thermal process.     

Synthesis of alpha-oximinoketones under ultrasound irradiation

The reaction of 6-acylmethylphenanthridines with isoamyl nitrite results alpha-oximino-6-acylmethylphenanthridines in 73-95% yields in DMF under ultrasound irradiation. Compared with conventional methods, the main advantages of the present procedure are milder conditions, shorter reaction time and higher yields.     

Kinetics of ultrasound-assisted lipase-catalyzed glycerolysis of olive oil in solvent-free system

This work reports experimental kinetic data of solvent-free glycerolysis of olive oil using a commercial immobilized lipase (Novozym 435) under the influence of ultrasound irradiation. The experiments were performed in a mechanically stirred reactor under ultrasound irradiation, evaluating the effects of temperature (50-70 °C), enzyme concentration (2.5-10 wt%) and glycerol to oil molar ratio (0.8:1-3:1). Results show that ultrasound-assisted lipase-catalyzed glycerolysis might be a potential alternative route to conventional methods, as high contents of reaction products, especially monoglycerides, were achieved at mild irradiation power supply (∼130 W) and temperature, in a relatively short reaction time (2 h) and low enzyme content (7.5 wt%). To completeness, two simplified kinetic modeling approaches, based on the ordered-sequential bi bi mechanism and reaction stoichiometry, were employed to represent the experimental data, thus allowing a better understanding of the reaction kinetics.     

Sonochemically synthesis of pyrazolones using reusable catalyst CuI nanoparticles that was prepared by sonication

A simple and green process to prepare copper iodide in nano scale via sonication was carried out. Subsequently, this nanoparticles was used as an efficient catalyst for the synthesis of 2-aryl-5-methyl-2,3-dihydro-1H-3-pyrazolones via four-component reaction of hydrazine, ethyl acetoacetate, aldehyde and β-naphthol in water under ultrasound irradiation. The combinatorial synthesis was attained for this procedure with applying ultrasound irradiation while making use of water as green ambient. Simple work-up, excellent yield of products and short reaction times are some of the important features of this protocol. Notably, this catalyst could be recycled and reused for five times without noticeably decreasing the catalytic activity.