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1.
《Ultrasonics sonochemistry》2014,21(3):997-1001
The kinetics of pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated under ultrasonic irradiation with an application of 10% of the maximum power of the equipment and without sonication in acetonitrile–water binary mixtures with a content of acetonitrile ranging from 0.008 to 35 wt.%. Similar kinetic investigations were performed at intensities corresponding to 10%, 20%, 30%, 40%, and 50% of the input energy in solvent mixtures containing 10 wt.% and 25 wt.% acetonitrile. In parallel, the responses of KI and terephthalic acid dosimeters at applied irradiation levels were registered under the same experimental conditions. Significant kinetic sonication effects were found at sound intensities presumably not inducing cavitation in the solution. This result provides an experimental evidence of kinetic effects of ultrasound in the absence of cavitation. A disturbing impact of cavitation on the ultrasonic acceleration of the reaction was found. The implications of these findings were discussed.  相似文献   

2.
Molecular dynamics (MD) simulation of the structure of ethyl acetate solutions in two water–ethanol mixtures was performed at 280 and 330 K. The MD simulations revealed that ethyl acetate was preferentially solvated by ethanol, water being mainly located in the next solvation layer. With increasing temperature ethanol was gradually replaced by water in the first solvation shell. These findings explain the decrease in the rate of ester hydrolysis with increasing molar ratio of ethanol in the solution as the reaction rate was linearly dependent on the relative ethanol content in the first solvation shell of the ester. Predominance of ethanol results in decreased polarity and water activity in the shell and accordingly in a decreased reaction rate. Based on the results of the MD simulations, the principal conclusion of this work is that ultrasound enhances the kinetic energy (the effective temperature) of species in the solution and, in this way, evokes shifts in the solvation equilibria thus affecting the reaction rate. It appears that ultrasound does not completely break down the solvent shells or clusters in the solution as previously believed. Phenomena of thermo-solvatochromism and reaction rate levelling by ultrasound in binary solvents are described.  相似文献   

3.
A core–shell-type of meso-SiO2@Fe3O4 microsphere was synthesized via an ultrasonic-assisted surfactant-templating process using solvothermal synthesized Fe3O4 as core, tetraethoxysilane (TEOS) as silica source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by FT-IR, XRD, TEM, N2 adsorption–desorption technology, and vibrating sample magnetometer (VSM). The results show that as-prepared meso-SiO2@Fe3O4(E) and meso-SiO2@Fe3O4(C) microspheres, treated by acetone extraction and high temperature calcination, respectively, still maintain uniform core–shell structure with desirable mesoporous silica shell. Therein, the meso-SiO2@Fe3O4(E) microspheres possess a distinct pore size distribution in 1.8–3.0 nm with large specific surface area (468.6 m2/g) and pore volume (0.35 cm3/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is much shorter than that of the conventional method (12–24 h). The morphology of microspheres and the mesoporous structure of silica shell are significantly influenced by initial concentration of CTAB (CCTAB), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving the homogeneity of silica shell and the monodispersity of meso-SiO2@Fe3O4 microspheres.  相似文献   

4.
Source water eutrophication has caused serious problems in drinking water supplies, with enhanced coagulation widely used to remove the resulting algae. This paper investigates the use of sonication to improve the removal by coagulation of Microcystis aeruginosa, a common species of toxic algae. The results show that sonication significantly enhances the reduction of algae cells, solution UV254, and chlorophyll a without increasing the concentration of aqueous microcystins. The main mechanism involved the destruction during ultrasonic irradiation of gas vacuoles inside algae cells that acted as ‘nuclei’ for acoustic cavitation and collapse during the “bubble crush” period, resulting in the settlement of cyanobacteria. Coagulation efficiency depended strongly on the coagulant dose and sonication conditions. When the coagulant dose was 0.5 mg/l, 5 s of ultrasonic irradiation increased algae removal efficiency from 35% to 67%. As further sonication enhanced the coagulation efficiency only slightly due to better mixing, optimal sonication time was 5 s. The most effective sonication intensity was 47.2 W/cm2, and the highest removal ratio of M. aeruginosa was 93.5% by the sonication–coagulation method. Experiments with reservoir water showed that this method could be successfully applied to natural water containing multiple species of algae.  相似文献   

5.
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, Vmax and KM values, as well as, kcat 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.  相似文献   

6.
The ultrasonic horn and bath reactors were compared based on production of angiotensin-converting-enzyme (ACE) inhibitory peptides from defatted wheat germ proteins (DWGP). The DWGP was sonicated before hydrolysis by Alcalase. Degree of hydrolysis, ACE-inhibitory activity, surface hydrophobicity, fluorescence intensity, free sulfhydryl (SH), and disulfide bond (SS) were determined. The highest ACE-inhibitory activity of DWGP hydrolysate was obtained at power intensity of 191.1 W/cm2 for 10 min in the ultrasonic horn reactor. The fixed frequency of 33 kHz and the sweep frequency of 40 ± 2 kHz resulted in the maximum ACE-inhibitory activity. The combined irradiation of dual fixed frequency (24/68 kHz) produced significant increase in ACE-inhibitory activity compared with single frequency (33 kHz). The ultrasonic probe resulted in significant higher ACE-inhibitory activity compared with ultrasonic bath operating at single or dual fixed and sweep frequencies. The changes in conformation of the DWGP due to sonication were confirmed by the changes in fluorescence intensity, surface hydrophobicity, SHf and SS contents and they were found in conformity with the ACE-inhibitory activity in case of the ultrasonic horn reactor but not in bath reactor.  相似文献   

7.
Density (ρ), ultrasonic velocity (u), adiabatic compressibility (β), apparent molar volume (Ø), acoustic impedance (Z), intermolecular free length (Lf), relative association (RA) of binary mixtures of 2′-chloro-4-methoxy-3-nitro benzil (abbreviated as 2CBe) in ethanol, acetonitrile, chloroform, dioxane and benzene were measured at different concentrations at 298 K. Several useful parameters such as excess density, excess ultrasonic velocity, excess adiabatic compressibility, excess apparent molar volume, excess acoustic impedance and excess intermolecular free length have been calculated. These parameters are used to explain the nature of intermolecular interactions taking place in the binary mixture. The above study is useful in understanding the solute – solvent interactions occurring in different concentrations at room temperature.  相似文献   

8.
Density (ρ), ultrasonic velocity (U), for the binary mixtures of 4-methoxy benzoin (4MB) with ethanol, chloroform, acetonitrile, benzene, and di-oxane were measured at 298 K. The solute–solvent interactions and the effect of the polarity of the solvent on the type of intermolecular interactions are discussed here. From the above data, adiabatic compressibility (β), intermolecular free length (Lf), acoustic impedance (Z), apparent molar volume (Ø), relative association (RA) have been calculated. Other useful parameters such as excess density, excess velocity and excess adiabatic compressibility have also been calculated. These parameters were used to study the nature and extent of intermolecular interactions between component molecules in the binary mixtures.  相似文献   

9.
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.  相似文献   

10.
In our current research work, the effect of ultrasound irradiation on the enzymatic activity and enzymatic hydrolysis kinetic parameters of dextran catalysis by dextranase were investigated. Furthermore, the effects of ultrasound irradiation on the structure of dextranase were investigated with the aid of fluorescence spectroscopy and circular dichroism (CD) spectroscopy. The maximum activity of dextranase was observed when the sample was treated with ultrasound at 25 kHz, 40 W for 15 min, under which the enzyme activity increased by 13.43% compared the routine thermal incubation at 50 °C. Experimental Kinetics results, demonstrated that, both the Vmax and KM values of dextranase increased with ultrasound-treated compared with the incubation at 50 °C. Likewise, both the catalytic and specificity constants were higher under the effects of an ultrasonic field, indicating that, the substrate is converted into the product at an increased rate when compared with the incubation at 50 °C.On the other hand, fluorescence and CD spectra reflected that the ultrasound irradiation had increased the number of tryptophan on dextranase surface with increased α-helix by 15.74% and reduced random coil by 5.41% upon ultrasound-treated dextranase protein compared to the control, which were helpful for the improvement of its activity.  相似文献   

11.
Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al2O3) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm?2, Waq = 0.67 W mL?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al2O3 dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al2O3. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)3. Silent hydrolysis of m-Al2O3 yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment.  相似文献   

12.
The inertial cavitation activity depends on the sonication parameters. The purpose of this work is development of dual frequency inertial cavitation meter for therapeutic applications of ultrasound waves. In this study, the chemical effects of sonication parameters in dual frequency sonication (40 kHz and 1 MHz) were investigated in the progressive wave mode using iodide dosimetry. For this purpose, efficacy of different exposure parameters such as intensity, sonication duration, sonication mode, duty factor and net ultrasound energy on the inertial cavitation activity have been studied. To quantify cavitational effects, the KI dosimeter solution was sonicated and its absorbance at a wavelength of 350 nm was measured. The absorbance values in continuous sonication mode was significantly higher than the absorbance corresponding to the pulsed mode having duty factors of 20–80% (p < 0.05). Among different combination modes (1 MHz100% + 40 kHz100%, 1 MHz100% + 40 kHz80%, 1 MHz80% + 40 kHz100%, 1 MHz80% + 40 kHz80%), the continuous mode for dual frequency sonication is more effective than other combinations (p < 0.05). The absorbance for this combined dual frequency mode was about 1.8 times higher than that obtained from the algebraic summation of single frequency sonications. It is believed that the optimization of dual frequency sonication parameters at low-level intensity (<3 W/cm2) by optically assisted cavitation event sensor can be useful for ultrasonic treatments.  相似文献   

13.
The degradation of Acid Blue 92 (AB92) solution was investigated using a sonocatalytic process with pure and neodymium (Nd)-doped ZnO nanoparticles. The nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The 1% Nd-doped ZnO nanoparticles demonstrated the highest sonocatalytic activity for the treatment of AB92 (10 mg/L) with a degradation efficiency (DE%) of 86.20% compared to pure ZnO (62.92%) and sonication (45.73%) after 150 min. The results reveal that the sonocatalytic degradation followed pseudo-first order kinetics. An empirical kinetic model was developed using nonlinear regression analysis to estimate the pseudo-first-order rate constant (kapp) as a function of the operational parameters, including the initial dye concentration (5–25 mg/L), doped-catalyst dosage (0.25–1 g/L), ultrasonic power (150–400 W), and dopant content (1–6% mol). The results from the kinetic model were consistent with the experimental results (R2 = 0.990). Moreover, DE% increases with addition of potassium periodate, peroxydisulfate, and hydrogen peroxide as radical enhancers by generating more free radicals. However, the addition of chloride, carbonate, sulfate, and t-butanol as radical scavengers declines DE%. Suitable reusability of the doped sonocatalyst was proven for several consecutive runs. Some of the produced intermediates were also detected by GC–MS analysis. The phytotoxicity test using Lemna minor (L. minor) plant confirmed the considerable toxicity removal of the AB92 solution after treatment process.  相似文献   

14.
In this research work, dextranase has immobilized onto calcium alginate beads using a novel ultrasound method. The process of immobilization of the enzyme was carried out in a one-step ultrasound process. Effects of ultrasound conditions on loading efficiency and immobilization yield of the enzyme onto calcium alginate beads were investigated. Furthermore, the activity of the free and immobilized enzymes prepared with and without ultrasound treatment, as a function of pH, temperature, recyclability and enzyme kinetic parameters, was compared. The maximum loading efficiency and the immobilization yield were observed when the immobilized dextranase was prepared with an ultrasonic irradiation at 25 kHz, 40 W for 15 min, under which the loading efficiency and the immobilization yield increased by 27.21% and 18.77%, respectively, compared with the immobilized enzymes prepared without ultrasonic irradiation. On the other hand, immobilized enzyme prepared with ultrasonic irradiation showed Vmax and KM value higher than that for the immobilized enzyme prepared without ultrasonic irradiation, likewise, both the catalytic and specificity constants of immobilized enzyme prepared with ultrasonic irradiation were higher than that for immobilized enzyme prepared without ultrasound, indicating that, this new ultrasonic method improved the catalytic kinetics activity of immobilized dextranase at all the reaction conditions studied. Compared with immobilized enzyme prepared without ultrasound treatment, the immobilized enzymes prepared with ultrasound irradiation exhibited: a higher pH optimum, optimal reaction temperature, activation energy, and thermal stability, as well as, a higher recyclability, which, illustrating the effectiveness of the sonochemical method. To the best of our knowledge, this is the first report on the effect of ultrasound treatments on the immobilization of dextranase.  相似文献   

15.
Present study is devoted on the efficient application of Sn (O, S)-NPs -AC for simultaneous sonicated accelerated adsorption of some dyes from single and multi-components systems. Sn (O, S) nanoparticles characterization by FESEM, EDX, EDX mapping and XRD revel its nano size structure with high purity of good crystallinity. Present adsorbent due to its nano spherical shape particles with approximate diameter of 40–60 nm seems to be highly effective in this regard. The effects of five variables viz. pH (3.5–9.5), 0.010–0.028 g of adsorbent and 0.5–6.5 min mixing by sonication is good and practical conditions for well and expected adsorption of MB and CV over concentration range of 3–15 mg L−1. Combination of response surface methodology (RSM) based on central composite design (CCD) and subsequent of analysis of variance (ANOVA) and t-test statistics were used to test the significance of the independent variables and their interactions. Regression analysis reveal that experimental data with high repeatability and efficiency well represented by second-order polynomial model with coefficient of determination value of 0.9988 and 0.9976 for MB and CV, respectively following conditions like pH 8.0, 0.016 g adsorbent, 15 mg L−1 of both dyes 4 min sonication time is proportional with achievement of experimental removal percentage of 99.80% of MB and 99.87% of CV in batch experiment. Evaluation and estimation of adsorption data with Langmuir and Freundlich isotherm well justify the results based on their correlation coefficient and error analysis confirm that Langmuir model is good model with adsorption capacity of 109.17 and 115.34 mg g−1 in single system and 95.69 and 102.99 mg g−1 in binary system for MB and CV, respectively. MB and CV kinetic and rate of adsorption well fitted by pseudo-second order equation both in single and binary systems and experimental results denote more and favorable adsorption of CV than respective value in single system. The pseudo-second-order rate constant k2 in binary system larger than single system.  相似文献   

16.
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.  相似文献   

17.
《Ultrasonics sonochemistry》2014,21(3):1140-1149
Modified chitosans with 3,4-dihydroxy benzoyl groups (CS-DHBA) and 3,4,5-trihydroxy benzoyl groups (CS-THBA) were synthesized and their chemical structures were determined by Fourier transform infrared (FT-IR) and 1H nuclear magnetic resonance (1H NMR) spectroscopy. Then, ultrasonic degradation of CS, CS-DHBA and CS-THBA in 1% acetic acid solution was investigated. The kinetics studies of degradation were followed by gel permeation chromatography (GPC). The results indicated that the weight-average molecular weight of chitosan decreased obviously after ultrasound treatment, but molecular weights of CS-DHBA and CS-THBA decreased slowly with increasing sonication time. Degradation kinetics model based on 1/Mt−1/M0 = kt was used to estimate the degradation rate constant. It was found that the rates of degradation of CS-DHBA and CS-THBA are lower than CS, and follow the order: CS4 > CS8 > CS12 > CS-THBA4 > CS-THBA8  CS-DHBA4 > CS-THBA12 > CS-DHBA8 > CS-DHBA12. The antioxidant activity of the CS, CS-DHBA and CS-THBA before and after sonication was investigated by the radical scavenging activity method using 1,1-diphenyl-2-picrylhydrazyl (DPPH). The DPPH scavenging free radical capacity of CS-THBA and CS-DHBA increased up to 89% and 74% respectively, when the concentration reached 6 μg/ml. The ultrasonic treatment of CS-DHBA and CS-THBA after 30 min decreased the DPPH free radical scavenging activity but ultrasonic treatment of CS increased the DPPH free radical scavenging activity.  相似文献   

18.
《Ultrasonics sonochemistry》2014,21(4):1358-1365
Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe2O3 and CuO were prepared, characterized and tested in degradation of NB (10 mg L−1) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H2O2 after 10 min of sonication in presence of α-Fe2O3 (1.0 g L−1), (k = 0.58 min−1) and after 25 min in case of CuO (k = 0.126 min−1). α-Fe2O3 showed also effective degradation under the conditions of 0.1 g L−1 oxide and 5.0 mM of H2O2, even though with a lower rate constant (0.346 min−1). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.  相似文献   

19.
The present work investigated the enzymolysis kinetics, thermodynamics and model of porcine cerebral protein (PCP) which was pretreated by single-frequency countercurrent and pulsed ultrasound. The kinetic constants for ultrasonic pretreated and traditional enzymolysis have been determined. Results showed that the value of KM in ultrasonic PCP (UPCP) enzymolysis decreased by 9% over that in the traditional enzymolysis. The values of reaction rate constant (k) for UPCP enzymolysis increased by 207%, 121%, 62%, and 45% at 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased activation energy (Ea), change in enthalpy (ΔH) and entropy (ΔS) by 76%, 82% and 31% in PCP, respectively. However, ultrasound had little change in Gibbs free energy (ΔG) value in the temperature range of 293–323 K. Therefore, a general kinetic equation for the enzymolysis model of UPCP by a simple empirical equation was suggested. The experimental values fits with the enzymolysis kinetic model with a low average relative error (4%) confirmed that the kinetic model was accurate to reflect the enzymolysis process. The positive effect of single-frequency countercurrent and pulsed ultrasound in this study and application of the kinetic model may be useful for the release of bioactive peptides from meat processing by-products.  相似文献   

20.
In this study, a high-molecular-weight polysaccharide PL-N isolated from the alkaline extract of Phellinus linteus mycelia was degraded by ultrasound. Results showed that ultrasound treatment at different ultrasonic intensities decreased the intrinsic viscosity and molecular weight of PL-N, as well as narrowed the molecular weight distribution. A larger reduction in intrinsic viscosity and molecular weight was caused by a higher ultrasonic intensity. The degradation kinetics model was fitted to (1/Mt  1/M0) = k·t, and the reaction rate constant (k) increased with increasing ultrasonic intensity. Ultrasound degradation did not change the primary structure of PL-N, and scanning electron microscopy analysis indicated that the morphology of the original PL-N was different from that of degraded PL-N fractions. Antioxidant activity assays in vitro indicated that the degraded PL-N fraction with low molecular weight had stronger hydroxyl radical scavenging capacity and higher TEAC and FRAP values.  相似文献   

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