A simple new approach for mapping an ultrasonic tank for sonochemistry.

The most used piece of equipment for sonochemistry is the ultrasonic cleaning bath. However, what is sometimes forgotten by scientists new to sonochemistry is the vital importance of the shape and positioning of any reaction vessel in the bath to obtain the most efficient and reproducible results. In experiments using an ultrasonic bath, a glass vessel (reactor) is inserted into the water contained in the bath. The water acts as the coupling medium for the transfer of acoustic energy from the transducer to the vessel (termed indirect sonication). The position of the reaction vessel above the base of the US bath can change the energy transmitted into it over a wide range of values (in our system between 100-500 J). We have carried out a study of the vertical distribution of the ultrasound field in a common type of ultrasound bath, comparing conventional sonochemistry dosimeters with a new and very simple approach using the Ultrasonic Capillary Effect (UCE) which can be performed in any laboratory. The technique involves the use of a capillary tube, to locate the vertical positions of acoustic pressure maxima above a single transducer on the base of the bath. The results are compared with those obtained using calorimetry, iodimetry, a cavitometer and the perforation of aluminium foil. The results show that the optimum position for the reaction vessel can be located very simply using UCE.

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.

Fatty Acid Ethyl Esters (FAEE): A New, Green and Renewable Solvent for the Extraction of Carotenoids from Tomato Waste Products.

Currently there is a drive towards the minimisation and reclamation of valuable materials from the waste products of the food and beverage industry. This can be achieved through the extraction of residual nutraceuticals from such materials. Tomato pomace contains carotenoids and other chemicals which can be extracted directly into edible oils to improve the health-giving properties of such oils. We report here a novel green solvent, fatty acid ethyl esters (FAEE), which is significantly more effective than sunflower oil and hexane for the extraction of lycopene and beta-carotene from tomato skin waste. FAEE are a non-toxic renewable resource that is environmentally friendly and to our knowledge has never been used as a vegetal extraction fluid. The efficiency of FAEE extraction was significantly improved relative to both sunflower oil and hexane under ultrasound-assisted extraction (UAE) conditions. In addition, FAEE have the additional and significant advantage that once enriched with the extracted nutraceuticals can be used directly as a food additive.

Jean-Louis Luche and the Interpretation of Sonochemical Reaction Mechanisms.

Sonochemistry can be broadly defined as the science of chemical and physical transformations produced under the influence of sound. The use of sound energy is rather a young branch of chemistry and does not have the clear definitive rules of other, more established, divisions such as those in cycloaddition reactions or photochemistry. Nevertheless, there are a few guidelines which can help to predict what is going to happen when a reaction mixture is submitted to ultrasonic irradiation. Jean-Louis Luche, formulated some ideas of the mechanistic pathways involved in sonochemistry more than 30 years ago. He introduced the idea of "true" and "false" sonochemical reactions both of which are the result of acoustic cavitation. The difference was that the former involved a free radical component whereas only mechanical effects played a role the latter. The authors of this paper were scientific collaborators and friends of Jean-Louis Luche during those early years and had the chance to discuss and work with him on the mechanisms of sonochemistry. In this paper we will review the original rules (laws) as predicted by Jean-Louis Luche and how they have been further developed and extended in recent years.

30 Years of sonochemistry links with China.

Most scientists consider that sonochemistry became recognised as a discrete subject in the 1980's - some 40 years ago which coincidentally is when my own interests in the subject began. This review briefly outlines how I first became involved in sonochemistry and then in its development. However its main theme is the way in which my links with China through sonochemistry have developed from their beginnings in 1990. This was the subject of my presentation at AOSS4 and involves a range of topics which started with the extraction of natural products and surface treatment but later expanded to include therapeutic ultrasound and environmental protection.

Ultrasound assisted preparation of calcium alginate beads to improve absorption of Pb+2 from water.

Calcium alginate (CaAlg) beads were prepared using ultrasound for use in the removal of lead from natural and wastewaters by ion exchange. Ultrasound was applied in a batch mode with an ultrasonic bath or in a flow mode using an ultrasonic clamp-on device. For comparison purposes the synthesis was performed in batch mode in the absence of the ultrasound. The beads prepared using ultrasound showed a greater ion exchange capability which could be ascribed to a larger specific surface area as a result of surface roughening induced by cavitation. Scanning Electron Microscopy (SEM) images revealed that the roughening was in the form of corrugation for the product with the best ion exchange capability obtained in the flow process where preformed CaAlg droplets were subjected to ultrasound during the setting process. These beads performed 11% better for lead removal than those synthesized in the absence of ultrasound.

Ultrasonic stimulation of the brain to enhance the release of dopamine - A potential novel treatment for Parkinson's disease.

Parkinson's disease (PD) is characterized by the decrease of dopamine (DA) production and release in the substantia nigra and striatum regions of the brain. Transcranial ultrasound has been exploited recently for neuromodulation of the brain in a number of fields. We have stimulated DA release in PC12 cells using low-intensity continuous ultrasound (0.1 W/cm2 - 0.3 W/cm2, 1 MHz), 12 h after exposure at 0.2 W/cm2, 40 s, the amount of DA content eventually increased 78.5% (p = 0.004). After 10-day ultrasonic treatment (0.3 W/cm2, 5 min/d), the DA content in the striatum of PD mice model restored to 81.07% of the control (vs 43.42% in the untreated PD mice model). In addition to this the locomotion activity was restored to the normal level after treatment. We suggest that the low intensity ultrasound-induced DA release can be attributed to a combination of neuron regeneration and improved membrane permeability produced by the mechanical force of ultrasound. Our study indicates that the application of transcranial ultrasound applied below FDA limits, could provide a candidate for relatively safe and noninvasive PD therapy through an amplification of DA levels and the stimulation of dopaminergic neuron regeneration without contrast agents.

Can sonochemistry take place in the absence of cavitation? - A complementary view of how ultrasound can interact with materials.

A hypothesis is advanced for a mechanism by which ultrasound could help to activate chemical reactions, even in the absence of cavitation. It is suggested that the compression phase of an acoustic wave could produce transient solid-like structures within the solution. These structures would result in an "ordering effect" of the molecules in which electrical charges could develop. Such electrical charges could facilitate electron movement from one molecule to another triggering therefore chemical reactions. Such reactions could occur even in the absence of cavitation especially if the solvent or reagents employed show piezoelectric/electrostriction properties. Similar transient ordering effects could be induced by the shockwave accompanying bubble collapse and these would help to explain some of the anomalous effects observed in sonochemistry under cavitation.

Cytotoxicity Study of Textile Fabrics Impregnated With CuO Nanoparticles in Mammalian Cells.

Copper and copper compounds have multifunctional properties (antibacterial, antiviral, and antifungal) with promising applications. Copper in its nanoparticle (Cu NPs) forms has been widely used in various industrial and commercial applications. In the current research, the cytotoxic effects of textile fabrics impregnated with copper oxide nanoparticles (CuO NPs) were studied in mammalian cell lines. CuO NPs were impregnated onto textile substrates using 2 different techniques: the sonochemical generation and impregnation of NPs from metal complexes ( insitu) and a "throwing the stones" technology using commercially prepared CuO NPs. The cytotoxicity of these 2 textile fabric types was assayed on human dermal fibroblast (HDF) cells and human hepatocellular carcinoma cells (HepG2) and was evaluated by indirect contact using an MTT assay. The impregnated fabrics were not exposed to the cells, rather their leachates were used to test cytotoxicity. The fabrics were soaked into the growth media for up to 7 days, and the leachates from day 1 and day 7 were incubated with the cell lines for 24 hours prior to the testing. The discharge or leaching from antimicrobial nanomaterials into the surroundings and surface waters is posing a serious environmental threat, which needs to be addressed. Hence, with regard to product safety, it is a good approach to study the fabric leachates rather than the intact material. The results showed that CuO NPs are not toxic to HDF cells. However, cytotoxicity was seen in HepG2 cells with cell viability decreasing by 20% to 25% for all the fabrics after 24 hours.

Ultrasound technology for food fermentation applications.

Fermentation processes involve the participation of enzymes and organic catalysts, generated by range of microorganisms to produce chemical transformations. Ultrasound can be used in such processes to either monitor the progress of fermentation or to influence its progress. High frequency ultrasound (>2MHz) has been extensively reported as a tool for the measurement of the changes in chemical composition during fermentation providing real time information on reaction progress. Low frequency ultrasound (20-50kHz) can influence the course of fermentation by improving mass transfer and cell permeability leading to improved process efficiency and production rates. It can also be used to eliminate micro-organisms which might otherwise hinder the process. This review summarises key applications of high and low frequency ultrasound in food fermentation applications.

Effect of sonication frequency on the disruption of algae.

In this study, the efficiency of ultrasonic disruption of Chaetoceros gracilis, Chaetoceros calcitrans, and Nannochloropsis sp. was investigated by applying ultrasonic waves of 0.02, 0.4, 1.0, 2.2, 3.3, and 4.3 MHz to algal suspensions. The results showed that reduction in the number of algae was frequency dependent and that the highest efficiency was achieved at 2.2, 3.3, and 4.3MHz for C. gracilis, C. calcitrans, and Nannochloropsis sp., respectively. A review of the literature suggested that cavitation, rather than direct effects of ultrasonication, are required for ultrasonic algae disruption, and that chemical effects are likely not the main mechanism for algal cell disruption. The mechanical resonance frequencies estimated by a shell model, taking into account elastic properties, demonstrated that suitable disruption frequencies for each alga were associated with the cell's mechanical properties. Taken together, we consider here that physical effects of ultrasonication were responsible for algae disruption.

Ultrasound assisted dispersal of a copper nanopowder for electroless copper activation.

This paper describes the ultrasound assisted dispersal of a low wt./vol.% copper nanopowder mixture and determines the optimum conditions for de-agglomeration. A commercially available powder was added to propan-2-ol and dispersed using a magnetic stirrer, a high frequency 850 kHz ultrasonic cell, a standard 40 kHz bath and a 20 kHz ultrasonic probe. The particle size of the powder was characterized using dynamic light scattering (DLS). Z-Average diameters (mean cluster size based on the intensity of scattered light) and intensity, volume and number size distributions were monitored as a function of time and energy input. Low frequency ultrasound was found to be more effective than high frequency ultrasound at de-agglomerating the powder and dispersion with a 20 kHz ultrasonic probe was found to be very effective at breaking apart large agglomerates containing weakly bound clusters of nanoparticles. In general, the breakage of nanoclusters was found to be a factor of ultrasonic intensity, the higher the intensity the greater the de-agglomeration and typically micron sized clusters were reduced to sub 100 nm particles in less than 30 min using optimum conditions. However, there came a point at which the forces generated by ultrasonic cavitation were either insufficient to overcome the cohesive bonds between smaller aggregates or at very high intensities decoupling between the tip and solution occurred. Absorption spectroscopy indicated a copper core structure with a thin oxide shell and the catalytic performance of this dispersion was demonstrated by drop coating onto substrates and subsequent electroless copper metallization. This relatively inexpensive catalytic suspension has the potential to replace precious metal based colloids used in electronics manufacturing.

Ultrasonic cleaning: An historical perspective.

The development of ultrasonic cleaning dates from the middle of the 20th century and has become a method of choice for a range of surface cleaning operations. The reasons why this has happened and the methods of assessing the efficiency of ultrasonic cleaning baths are reviewed.

Combined Effect of Ultrasound and Ozone on Bacteria in Water.

The aim of this study is to assess the synergetic effect of combined ultrasound and ozone treatment on the biological disinfection of water on a large-scale application using viable plate counts and flow cytometry. Escherichia coli B bacteria in saline suspension was treated using a commercially available combined ultrasound and ozone system (USO3 (Ultrasonic Systems Gmbh)) for 16 min. Two analytical methods were used to assess the results in terms of live and dead cells in the bulk liquid: standard viable plate counting recorded in terms of colony forming units per milliliter and flow cytometry. In the latter case 1 mL of bacterial suspension was stained simultaneously with the fluorescent stains SYTO9 and propidium iodide (PI). Transmission electron microscopy was used to generate images identifying the biological effects of different treatments using ultrasound and ozone on bacterial cell walls. Results demonstrated that treatment with ozone alone (1 mg/L) resulted in a significant reduction (93%) in the number of live cells after 16 min treatment whereas ultrasound alone showed only a small reduction (24%). However, a combination of ozone and ultrasound showed a synergistic effect and enhanced the inactivation to 99% after 4 min. A combined ultrasound and ozone treatment of bacterial suspensions using a commercial system affords a promising method for water disinfection that is better than treatment using either method alone. Standard viable plate count analysis is normally used to assess the effectiveness of disinfection treatments; however flow cytometry proved to be a more sensitive method to determine the actual effects in terms of not only live and dead cells but also damaged cells. This type of analysis (cell damage) is difficult if not impossible to achieve using traditional plate counting methodology.

Sonoelectrocatalytic decomposition of methylene blue using Ti/Ta2O5-SnO2 electrodes.

Sonoelectrochemical decomposition of organic compounds is a developing technique among advanced oxidation processes (AOPs). It has the advantage over sonication alone that it increases the efficiency of the process in terms of a more rapid decrease in chemical oxygen demand (COD) and in total organic carbon (TOC) and accelerates electrochemical oxidation which normally requires a lengthy period of time to achieve significant mineralisation. Moreover the use of an electrocatalytic electrode in the process further accelerates the oxidation reaction rates. The aim of this study was to improve the decomposition efficiency of methylene blue (MB) dye by sonoelectrochemical decomposition using environmentally friendly and cost-effective Ti/Ta2O5-SnO2 electrodes. Decolourisation was used to assess the initial stages of decomposition and COD together with TOC was used as a measure of total degradation. The effect of a range of sonication frequencies 20, 40, 380, 850, 1000 and 1176 kHz at different powers on the decolourisation efficiency of MB is reported. Frequencies of 850 and 380 kHz and the use of higher powers were found more effective towards dye decolourisation. The time for complete MB degradation was reduced from 180 min using electrolysis and from 90 min while carrying out sonolysis to 45 min when conducting a combined sonoelectrocatalytic experiments. The COD reduction of 85.4% was achieved after 2 h of combined sonication and electrolysis which is a slightly higher than after a single electrolysis (78.9%) and twice that of sonolysis (40.4%). A dramatic improvement of mineralisation values were observed within 2h of sonoelectrocatalytic MB degradation. The TOC removal efficiency increased by a factor of 10.7 comparing to sonication alone and by a factor of 1.5 comparing to the electrolytic process. The energy consumption (kWh/m(3)) required for the complete degradation of MB was evaluated.

Sonochemical approaches to enhanced oil recovery.

Oil production from wells reduces with time and the well becomes uneconomic unless enhanced oil recovery (EOR) methods are applied. There are a number of methods currently available and each has specific advantages and disadvantages depending on conditions. Currently there is a big demand for new or improved technologies in this field, the hope is that these might also be applicable to wells which have already been the subject of EOR. The sonochemical method of EOR is one of the most promising methods and is important in that it can also be applied for the treatment of horizontal wells. The present article reports the theoretical background of the developed sonochemical technology for EOR in horizontal wells; describes the requirements to the equipment needed to embody the technology. The results of the first field tests of the technology are reported.

Some neglected or rejected paths in sonochemistry--a very personal view.

Sonochemistry is a very broad subject and nowadays it involves a wide range of disciplines and provides a forum for the cross-fertilization of ideas. In the early days this was not quite the situation and so a number of ideas that came forward were outside of main-line classical thinking in science. These concepts were often rejected out of hand and sometimes even ridiculed. This paper revisits some of these ideas for those of you who might be interested in the more unusual effects in sonochemistry.

Effect of ultrasonic frequency and power on the disruption of algal cells.

In this work the effect of ultrasonic waves on suspensions of Chlamydomonas concordia and Dunaliella salina have been investigated at frequencies of 20, 585, 864 and 1146 kHz and at different acoustic powers. Results showed that the reduction in algal numbers was dependent on both frequency and acoustic power. The order of efficiency of the ultrasonic disruption of C. concordia at different frequencies was 20 < 580 < 864 < 1146 kHz, and for D. salina was 20< 580 ≅ 864 ⩽ 1146 kHz. It is clear that high-frequency sonication is more effective than conventional low-frequency sonication for the disruption of cells for both species. Results showed that suitable disruption frequencies for each algae were associated with the mechanical properties of the cell. The frequency dependence of the efficiency of algae disruption on the mechanical resonances of both the algae cell is discussed in terms of bubble oscillation in an ultrasonic field.

The sonochemical decolourisation of textile azo dye Orange II: effects of Fenton type reagents and UV light.

The removal of Orange II (O-II) from aqueous solution under irradiation at 850 kHz has been studied. The effects of both homogeneous (with FeSO4/H2O2), and heterogeneous (Fe containing ZSM-5 zeolite/H2O2) Fenton type reagents are reported together with the effect of UV irradiation in combination with ultrasound both alone and with homogeneous Fenton-type reagent. Degrees of decolourisation of 6.5% and 28.9% were observed using UV radiation and ultrasound, respectively, whereas under the simultaneous irradiation of ultrasound and UV light, the decolourisation degree reached 47.8%, indicating a synergetic effect of ultrasound and UV light. The decolourisation was increased with the addition of Fenton's reagent with an optimal Fenton molar reagent ratio, Fe(2+):H2O2 of 1:50. In the combined process of ultrasound and UV light with the homogeneous Fenton system 80.8% decolourisation could be achieved after 2h indicating that UV improves this type of Orange II degradation. The degree of decolourisation obtained using the heterogeneous sono-Fenton system (Fe containing ZSM-5 zeolite catalysts+H2O2+ultrasound) were consistently lower than the traditional homogeneous ultrasound Fenton system. This can be attributed to the greater difficulty of the reaction between Fe ions and hydrogen peroxide. In all cases the Orange II ultrasonic decolourisation was found to follow first order kinetics.