Magnetic enzyme reactors for isolation and study of heterogeneous glycoproteins

The newly developed magnetic micro- and nanoparticles with defined hydrophobicity and porosity were used for the preparation of magnetic enzyme reactors. Magnetic particles with immobilized proteolytic enzymes trypsin, chymotrypsin and papain and with enzyme neuraminidase were used to study the structure of heterogeneous glycoproteins. Factors such as the type of carrier, immobilization procedure, operational and storage stability, and experimental conditions were optimized.     

Numerical simulations for sonochemistry

Numerical simulations for sonochemistry are reviewed including single-bubble sonochemistry, influence of ultrasonic frequency and bubble size, acoustic field, and sonochemical synthesis of nanoparticles. The theoretical model of bubble dynamics including the effect of non-equilibrium chemical reactions inside a bubble has been validated from the study of single-bubble sonochemistry. By the numerical simulations, it has been clarified that there is an optimum bubble temperature for the production of oxidants inside an air bubble such as OH radicals and H₂O₂ because at higher temperature oxidants are strongly consumed inside a bubble by oxidizing nitrogen. Unsolved problems are also discussed.     

Sonochemical activity in ultrasonic reactors under heterogeneous conditions

Due to its physical and chemical effects, ultrasound is widely used for industrial purposes, especially in heterogeneous medium. Nevertheless, this heterogeneity can influence the ultrasonic activity. In this study, the effect of the addition of inert glass beads on the sonochemical activity inside an ultrasonic reactor is investigated by monitoring the formation rate of triiodide, and the ultrasonic power is measured by calorimetry and by acoustic radiation. It was found that the sonochemical activity strongly depends on the surface area of the glass beads in the medium: it decreases above a critical area value (around 10⁻² m²), partly due to wave scattering and attenuation. This result is confirmed for a large range of frequencies (from 20 to 1135 kHz) and glass beads diameters (from 8-12 µm to 6 mm). It was also demonstrated that above a given threshold of the surface area, only part of the supplied ultrasonic power is devoted to chemical effects of ultrasound. Finally, the acoustic radiation power appears to describe the influence of solids on sonochemical activity, contrary to the calorimetric power.     

Relevance of sonochemistry or ultrasound (US) as a proficient means for the synthesis of fused heterocycles

Medicinal chemistry has been benefited by combinatorial chemistry and high throughput parallel synthesis. The use of sonochemistry under controlled conditions has been proved beneficial for medicinal chemistry and drug discovery process since it dramatically reduces reaction times, from days or hours to minutes. In addition, sonochemistry synthesis provides higher yields, lower cost, easy workups and greater purity as compared to lower yields, tedious workups, longer reaction times, lesser purity and termination of many by-products in the conventional thermal methods.     

Effect of ultrasound on heterogeneous systems

Examples of sonochemical reactions occuring under heterogeneous conditions are discussed with respect to their mechanism. The activation of a metal surface involves complex phenomena, in which parameters of importance seem to be the hardness and the adhesion of the passivating layer. Some considerations are given on the probable link between sonochemistry and tribochemistry.     

Using sonochemistry for the fabrication of nanomaterials

One of the reasons for the huge interest in nanomaterials originated because of the prohibitive price that commercial companies have to pay for introducing new materials into the market. Nanotechnology enables these companies to obtain new properties using old and recognized materials by just reducing their particle size. For these known materials no government approval has to be obtained. Thus, the interest in nanomaterials has led to the development of many synthetic methods for their fabrication. Sonochemistry is one of the earliest techniques used to prepare nanosized compounds. Suslick, in his original work, sonicated Fe(CO)5 either as a neat liquid or in a decalin solution and obtained 10-20 nm size amorphous iron nanoparticles. A literature search that was conducted by crossing Sono* and Nanop* has found that this area is expanding almost exponentially. It started with two papers published in 1994, two in 1995, and increased to 59 papers in 2002. A few authors have already reviewed the fields of Sono and Nano. It should be mentioned that in 1996, Suslick et al. published an early review on the nanostructured materials generated by ultrasound radiation. Suslick and Price have also reviewed the application of ultrasound to materials science. This review dealt with nanomaterials, but was not directed specifically to this topic. The review concentrated only on the sonochemistry of transition metal carbonyls and catalytic reactions that involve the nanoparticles resulting from their sonochemical decomposition. Grieser and Ashokkumar have also written a review on a similar topic. A former coworker, Zhu, has recently submitted for publication a review article entitled "Novel Methods for Chemical Preparation of Metal Chalcogenide Nanoparticles" in which he reviews three synthetic methods (sonochemistry, sonoelectrochemistry, and microwave heating) and their application in the synthesis of nanosized metal chalcogenides. Although still unpublished, I myself have recently written a review discussing novel methods (sonochemistry, microwave heating, and sonoelectrochemistry) for making nanosized materials. The current review will: (1) Present the four main advantages that sonochemistry has over other methods related to materials science and nanochemistry; (2) concentrate on the more recent (2003) literature that was not reviewed in the previously-mentioned reviews, and (3) focus on a specific question, such as what is the typical shape of products obtained in sonochemistry? This review will not survey the literature related to sonoelectrochemistry.     

Comparison of two different ultrasound reactors for the treatment of cellulose fibers

The pulp and paper industry is in continuous need for energy-efficient production processes. In the refining process of mechanical pulp, fibrillation is one of the essential unit operations that count for up to 80% of the total energy use. This initial study explores the potential and development of new type of scalable ultrasound reactor for energy efficient mechanical pulping. The developed reactor is of continuous flow type and based on both hydrodynamic and acoustic cavitation in order to modify the mechanical properties of cellulose fibers. A comparison of the prototype tube reactor is made with a batch reactor type where the ultrasonic horn is inserted in the fluid. The pulp samples were sonicated by high-intensity ultrasound, using tuned sonotrodes enhancing the sound pressure and cavitation intensity by a controlled resonance in the contained fluid. The resonant frequency of the batch reactor is 20.8 kHz and for the tube reactor it is 22.8 kHz. The power conversion efficiency for the beaker setup is 25% and 36% in case of the tube reactor in stationary mode. The objective is to verify the benefit of resonance enhanced cavitation intensity when avoiding the effect of Bjerkenes forces. The setup used enables to keep the fibers in the pressure antinodes of the contained fluid. In case of the continuous flow reactor the effect of hydrodynamic cavitation is also induced. The intensity of the ultrasound in both reactors was found to be high enough to produce cavitation in the fluid suspension to enhance the fiber wall treatment. Results show that the mechanical properties of the fibers were changed by the sonification in all tests. The continuous flow type was approximately 50% more efficient than the beaker. The effect of keeping fibers in the antinode of the resonant mode shape of the irradiation frequency was also significant. The effect on fiber properties for the tested mass fraction was determined by a low-intensity ultrasound pulse-echo based measurement method, and by a standard pulp analyzer.     

Educational aspects of sonochemistry: The role of sonochemistry at high school level

The applications of sonochemistry have attracted a great deal of attention. However, conventional chemistry textbooks used in universities and high schools cover traditional chemistry plus thermo,- photo- and electrochemistry. The effect of sound on chemical systems has completely been ignored. Although the mechanisms of many sonochemical reactions remain unresolved, the rapid expansion of knowledge in sonochemistry has already justified its inclusion in present chemistry curricula. Moreover, the interesting and unusual phenomena encountered under sonication conditions can be used for motivation purposes. Furthermore, exploring and equipping students with a new tool for investigating chemistry is also important based on educational principles. This paper examines some chemical systems (in a high school chemistry syllabus) which are affected by sound energy. It is hoped that these sonochemical applications will facilitate the learning of chemistry in terms of cognitive, psychomotor and affective domains.     

Experimental study of the ultrasound attenuation in chemical reactors

Ultrasound is used in different domains, and in sonochemistry particularly, for different purposes and in various flow configurations: monophasic, two-phase and polyphasic reactors. In order to optimize and to design sonochemical reactors, it is important to describe the ultrasonic intensity space and time distribution. In addition, it is important to study the different parameters influencing the intensity profiles of the ultrasonic wave. In this work, a thermoelectric probe has been used to measure the ultrasonic intensity. This procedure has shown that the ultrasound propagation is influenced by the presence of cavitation bubbles, the flow regime and the presence of solid particles.     

Investigation of design parameters in ultrasound reactors with confined channels

This paper presents a three-dimensional numercial simulation of sonochemical degradation upon cavitational activity. The model relates the simulation of the acoustic pressure distribution to the sonochemical reaction rate. As a case study, the thermal degradation of carbon tetrachloride during sonication is studied in a tubular milliscale reactor. The model is used to optimize the reactor diameter, ultrasound frequency and power dissipated to the ultrasound transducers. The results indicate that multiple transducers at a moderate power level are more efficient than one transducer with high power level. Furthermore, the average cavity volume fraction is proposed as a reaction independent parameter to estimate the optimal reactor design. Within the results obtained in this paper, it appears possible to optimise reactor design based on this parameter.     

水处理用声化学反应器研究进展

介绍了在水处理中采用的液哨式、清洗槽式、变幅杆式、杯式、平行板、管型等声化学反应器的研究进展和应用现状。指出要在实际水处理工程中采用超声技术，必须尽快开展高效、大批量处理或流水式连续运行的声学反应器的基础研究与应用开发。     

Comparison of ultrasound effects in different reactors at 20 kHz

To compare the performances of three power ultrasonic devices at 20 kHz: a horn, a cup horn and a tube, the local intensity distributions of local effects of cavitation have been investigated. The sensor is an electrochemical probe, measuring the solid-liquid mass transfer rate, related to the cavitation intensity. The axial and radial profiles of mass transfer coefficients have been investigated in three devices, at various power inputs. In all these equipments very strong heterogeneities have been characterized, whether a standing wave appears or not.     

Using sonochemistry for the fabrication of hollow ZnO microspheres

Hollow ZnO microspheres assembled by nanoparticles have been prepared by a sonochemical synthesis at room temperature using carbon spheres as template. The growth process of the precursor was investigated. The prepared hollow spheres were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM). The diameter of the obtained hollow spheres is about 500 nm, and the walls are composed of numerous ZnO aggregate nanocrystallines with diameters of 90 nm. A possible growth mechanism for the formation of ZnO microspheres has been proposed, in which carbon spheres play a crucial role in the formation of the wurtzite hollow ZnO microspheres. The specific structure of the hollow spheres may find applications in nanoelectronics, nanophotonics and nanomedicine.     

An ellipsometric method for the characterization of macroscopically heterogeneous films

In conventional compensating ellipsometry one usually measures a polarizer and an analyzer angle and computes from them two optical parameters of a layered structure, provided the individual layers are laterally homogeneous. In order to study a macroscopically heterogeneous thin layer with domains larger in lateral dimension than the wavelength of light, we suggest that furthermore the light intensity be measured at compensation. The additional light intensity, δI, exceeding the value for a homogeneous layer, results from the incoherent superposition of the light reflected from the different domains. From the polarizer and analyzer angles at compensation one obtains the arithmetical average of the optical single domain properties, whereas δI quantifies the heterogeneity, i.e. the relative areas of the domains and the differences in their optical thickness. In special cases this allows for the determination of the optical properties of the domains separately. The model is tested with films composed of two phases, the difference being a fatty acid bilayer of 5.6 nm in thickness. Applications of the model include the study of phase transitions in lipid monolayers.     

Fundamental problems of sonochemistry and cavitation

This paper discusses the problems of cavitation which are associated with sonochemistry. It is concluded that the hot-spot theory is not sufficient to accommodate all experimental data and the alternative is a new electrical theory of cavitation phenomena.     

Window-modulated compounding Nakagami imaging for ultrasound tissue characterization

Ultrasound Nakagami parametric imaging is a useful tool for tissue characterization. Previous literature has suggested using a square with side lengths corresponding to 3 times the transducer pulse length as the minimum window for constructing the Nakagami image. This criterion does not produce sufficiently smooth images for the Nakagami image to characterize homogeneous tissues. To improve image smoothness, we proposed window-modulated compounding (WMC) Nakagami imaging based on summing and averaging the Nakagami images formed using sliding windows with varying window side lengths from 1 to N times the transducer pulse length in 1 pulse length step. Simulations (the number densities of scatterers: 2–16 scatterers/mm²) and experiments on fully developed speckle phantoms (the scatterer diameters: 20–106 μm) were conducted to suggest an appropriate number of frames N and to evaluate the image smoothness and resolution by analyzing the full width at half maximum (FWHM) of the parameter distribution and the widths of the image autocorrelation function (ACF), respectively. In vivo ultrasound measurements on rat livers without and with cirrhosis were performed to validate the practical performance of the WMC Nakagami image in tissue characterization. The simulation results showed that using a range of N from 7 to 10 as the number of frames for image compounding reduces the estimation error to less than 5%. Based on this criterion, the Nakagami parameter obtained from the WMC Nakagami image increased from 0.45 to 0.95 after increasing the number densities of scatterers from 2 to 16 scatterers/mm². The FWHM of the parameter distribution (bins = 40) was 13.5 ± 1.4 for the Nakagami image and 9.1 ± 1.43 for the WMC Nakagami image, respectively (p-value < .05). The widths of the ACF for the Nakagami and WMC Nakagami images were 454 ± 5.36 and 458 ± 4.33, respectively (p-value > .05). In the phantom experiments, we also found that the FWHM of the parameter distribution for the WMC Nakagami image was smaller than that of the conventional Nakagami image (p-value < .05), and there was no significant difference of the ACF width between the Nakagami and WMC Nakagami images (p-value > .05). In the animal experiments, the Nakagami parameters obtained from the WMC Nakagami image for normal and cirrhotic rat livers were 0.62 ± 0.08 and 0.92 ± 0.07, respectively (p-value < .05). The results demonstrated that the WMC technique significantly improved the image smoothness of Nakagami imaging without resolution degradation, giving Nakagami model-based imaging the ability to visualize scatterer properties with enhanced image quality.     

Importance of acoustic shielding in sonochemistry

It is well known that sonochemistry is less efficient at high acoustic intensities. Many authors have attributed this effect to decoupling losses and shielding of the acoustic wave. In this study we investigate both phenomena for a 20 kHz ultrasound field with an intensity ranging from 40 to 150 W/cm2. Visualization of the bubble cloud has demonstrated that the void fraction below the ultrasound horn increases more than proportional with increasing power input. Nevertheless, the energy coupling between the horn and the liquid remains constant; this implies that decoupling losses are not reinforced for larger bubble clouds. On the contrary, microphone measurements have shown that due to the larger bubble cloud a substantial part of the supplied energy is lost at high power inputs. In striving towards more efficient sonochemistry, reduction of shielding appears as one of the major challenges.     

Influence of dissolved-air concentration on spatial distribution of bubbles for sonochemistry

The pulsation of ultrasonic cavitation bubbles at various dissolved-air concentration in a sonochemical reaction field of standing-wave type is investigated experimentally by laser-light scattering. When a thin light sheet, finer than half the wavelength of sound, is introduced into the cavitation bubbles at an antinode of sound pressure, the scattered light intensity oscillates. The peak-to-trough light intensity is correlated with the number of bubbles that contribute to the sonochemical reaction. It is shown that as the dissolved air concentration becomes higher, the weighted center of the spatial distribution of the peak-to-trough intensity tends to shift towards the liquid surface. At higher concentration of the dissolved air, a great deal of bubbles with size distribution generated due to coalescence between bubbles disturbs sound propagation to change the sound phase easily. A standing wave to trap tiny oscillating bubbles is established only at the side which is nearer to the liquid surface. Also at higher concentration, liquid flow induced by drag motion of bubbles by the action of radiation force becomes apparent and position-unstable region of bubble is enlarged from the side of sound source towards the liquid surface. Therefore, the position of oscillating bubbles active for sonochemical reaction is limited at the side which is nearer to the liquid surface at higher concentration of the dissolved air.     

Characterization of HIFU transducers designed for sonochemistry application: Acoustic streaming

Cavitation distribution in a High Intensity Focused Ultrasound sonoreactors (HIFU) has been extensively described in the recent literature, including quantification by an optical method (Sonochemiluminescence SCL). The present paper provides complementary measurements through the study of acoustic streaming generated by the same kind of HIFU transducers. To this end, results of mass transfer measurements (electrodiffusional method) were compared to optical method ones (Particle Image Velocimetry). This last one was used in various configurations: with or without an electrode in the acoustic field in order to have the same perturbation of the wave propagation. Results show that the maximum velocity is not located at the focal but shifted near the transducer, and that this shift is greater for high powers. The two cavitation modes (stationary and moving bubbles) are greatly affect the hydrodynamic behavior of our sonoreactors: acoustic streaming and the fluid generated by bubble motion. The results obtained by electrochemical measurements show the same low hydrodynamic activity in the transducer vicinity, the same shift of the active focal toward the transducer, and the same absence of activity in the post-focal axial zone. The comparison with theoretical Eckart’s velocities (acoustic streaming in non-cavitating media) confirms a very high activity at the “sonochemical focal”, accounted for by wave distortion, which induced greater absorption coefficients. Moreover, the equivalent liquid velocities are one order of magnitude larger than the ones measured by PIV, confirming the enhancement of mass transfer by bubbles oscillation and collapse close to the surface, rather than from a pure streaming effect.     

On the origin of sonoluminescence and sonochemistry

Recent experimental results on the origins of sonoluminescence and sonochemistry are reviewed and the conclusion reached that most observed effects originate from thermal processes associated with a localized hot-spot created by acoustic cavitation. Sonoluminescence is definitively due to chemiluminescence from species produced thermally during cavitational collapse and is not attributable to electric microdischarge. Homogenous sonochemistry follows the behaviour expected for high temperature thermal reactions. Ultrasonic irradiation of liquids containing solid powders dramatically increases their chemical reactivity and improves chemical yields for a wide range of synthetically useful heterogenous reactions. Shock waves generated from the cavitational hot-spot cause high velocity interparticle collisions in such slurries. Brittle solids are shock fragmented, which increases surface area. This increase in reactive surface provides for substantial increases in chemical reactivity. For malleable metal powders, these collisions are sufficiently violent to remove surface oxide coatings and to induce local melting at the site of impact for most metals.