Sonocatalysis of the TEMPO-mediated oxidation of glucosides

Ultrasound is shown to increase the rate of the TEMPO-mediated oxidation of methyl - -glucopyranoside or sucrose in the presence of stoichiometric amounts of sodium hypochlorite in basic aqueous medium. The reaction can then occur without the usually necessary sodium bromide, showing that ultrasound acts at the level of the formation of the nitrosonium ion, the active oxidizing species in the catalytic cycle.     

High-performance sono/nano-catalytic system: Fe3O4@Pd/CaCO3-DTT core/shell nanostructures,a suitable alternative for traditional reducing agents for antibodies

Herein, a novel heterogeneous nanoscale reducing agent for antibody cleavage, made of iron oxide nanoparticles, silica network, palladium on calcium carbonate (10%), and dithiothreitol (Fe₃O₄@Pd/CaCO₃-DTT), is presented as a substantial alternative for traditional homogeneous analogues. Conventionally, antibody fragmentation is accomplished using reducing agents and proteases that digest or cleave certain portions of the immunoglobulin protein structure to provide active thiol sites for drug tagging aims. Then, dialysis process is needed to separate excess chemical structures and purify the reduced antibody. In this work, we have made an effort to design a suitable heterogeneous tool for protein cleavage and skip the dialysis process for purification of the reduced antibody. In this regard, firstly, various preparation methods including microwave irradiation, reflux and ultrasonication have been precisely compared, and it has been proven that the best result is obtained through 10 min ultrasound (US) irradiation using an US bath with 50 KHz frequency and 200 W L⁻¹ power density. Then, all the necessary structural analyses have been done and thoroughly interpreted for the final product. Afterward, the catalytic performance of Fe₃O₄@Pd/CaCO₃-DTT nanoscale system in the presence of US waves (50 KHz, 200 W) has been monitored using some disulphide derivatives. The NPs could be conveniently separated from the mixture through their substantial paramagnetic property. Thus, dialysis process in which various types of membranes are used is practically jumped after the reduction process. In this work, this is clearly demonstrated that there is a constructive synergistic effect between US waves and prepared Fe₃O₄@Pd/CaCO₃-DTT nanoscale reducing agent. Ultimately, trastuzumab (anti HER-2) antibody has been used to test the performance of the prepared Fe₃O₄@Pd/CaCO₃-DTT NPs in a real protein reduction reaction.     

Hypothesis about electron quantum tunneling during sonochemical splitting of water molecule

Quantum tunneling in chemistry is often attributed to the processes at low or near room temperatures when the rate of thermal reactions becomes far less than the rate of quantum tunneling. However, in some rapid processes, quantum tunneling can be observed even at high temperatures. Herein, we report the experimental evidence for anomalous H/D kinetic isotope effect (KIE) during sonochemical dissociation of water molecule driven by 20 kHz power ultrasound measured in H₂O/D₂O mixtures saturated with Ar or Xe. Hydrogen released during ultrasonic treatment is enriched by light isotope. The observed H/D KIE (α = 2.15–1.50) is much larger than what is calculated assuming a classical KIE for T_g = 5000 K (α = 1.15) obtained from the sonoluminescence spectra in H₂O and D₂O. Furthermore, the α values sharply decrease with increasing of H₂O content in H₂O/D₂O mixtures reaching a steady-state value close to α = 1.50, which also cannot be explained by O-H/O-D zero-point energy difference. We suggest that these results can be understood in terms of quantum electron tunneling occurring in nonequilibrium picosecond plasma produced at the last stage of cavitation bubble collapse. Thermal homolytic splitting of water molecule is inhibited by extremely short lifetime of such plasma. On the contrary, immensely short traversal time for electron tunneling in water allows H₂O dissociation by quantum tunneling mechanism.     

Mechanisms of effective gold shell on Fe3O4 core nanoparticles formation using sonochemistry method

Sonochemical synthesis (sonochemistry) is one of the most effective techniques of breaking down large clusters of nanoparticles (NPs) into smaller clusters or even individual NPs, which ensures their dispersibility (stability) in a solution over a long duration. This paper demonstrates the potential of sonochemistry becoming a valuable tool for the deposition of gold (Au) shell on iron oxide nanoparticles (Fe₃O₄ NPs) by explaining the underlying complex processes that control the deposition mechanism. This review summarizes the principles of the sonochemistry method and highlights the resulting phenomenon of acoustic cavitation and its associated physical, chemical and thermal effects. The effect of sonochemistry on the deposition of Au NPs on the Fe₃O₄ surface of various sizes is presented and discussed. A Vibra-Cell ultrasonic solid horn with tip size, frequency, power output of ½ inch, 20 kHz and 750 W respectively was used in core@shell synthesis. The sonochemical process was shown to affect the surface and structure of Fe₃O₄ NPs via acoustic cavitation, which prevents the agglomeration of clusters in a solution, resulting in a more stable dispersion. Deciphering the mechanism that governs the formation of Au shell on Fe₃O₄ core NPs has emphasized the potential of sonication in enhancing the chemical activity in solutions.     

Sonochemie Über den Einfluß von Ultraschall auf einige Siloxane

Sonochemistry The Influence of Ultrasound on some Siloxanes Ultrasound impact on some cyclo-methylsiloxanes (e. g. Si₃O₃Me₆ and Si₄O₄Me₈ (Me = CH₃)) in the presence of the lewis acid AlCl₃ show ring enlargement in the case of Si₃O₃Me₆. Si₄O₄Me₈ however leads under the same conditions besides ring enlargement to ring fission and formation of catena-dichloromethylsiloxanes. Perchlorosiloxanes do not react under the same conditions.     

Green and rapid preparation of long-term stable aqueous dispersions of fullerenes and endohedral fullerenes: The pros and cons of an ultrasonic probe

A green, scalable, and sustainable approach to prepare aqueous fullerene dispersions (AFD) C₆₀, C₇₀, endohedral metallofullerene Gd@C₈₂, and their derivatives C₆₀Cl₆, C₇₀Cl₁₀, and supramolecular and ester-like derivatives, 10 fullerene species total, is proposed. For the first time, an immersed ultrasonic probe was used to preparing dispersions for pristine fullerenes without addends. Both ultrasound-assisted solvent-exchange and direct sonication techniques for AFD preparation using an immersed probe were tested. The average time for AFD preparation decreases 10–15 times compared to an ultrasound-bath-assisted technique, while final fullerene concentrations in AFDs remained at tens of ppm (up to 80 ppm). The aqueous dispersions showed long-term stability, a negatively charged surface with a zeta potential up to –32 mV with an average nanocluster diameter of no more than 180 nm. The total anionic and cationic compositions of samples were found by inductively coupled plasma atomic emission spectroscopy and chromatographic techniques. The highlights and challenges of using an ultrasound probe for AFD production are discussed.     

Effect of ultrasonic irradiation power on sonochemical synthesis of gold nanoparticles

In this work, optimized size distribution and optical properties in the colloidal synthesis of gold nanoparticles (GNPs) were obtained using a proposed ultrasonic irradiation assisted Turkevich-Frens method. The effect of three nominal ultrasound (20 kHz) irradiation powers: 60, 150, and 210 W have been analyzed as size and shape control parameters. The GNPs colloidal solutions were obtained from chloroauric acid (HAuCl₄) and trisodium citrate (C₆H₅Na₃O₇·2H₂O) under continuous irradiation for 1 h without any additional heat or stirring. The surface plasmon resonance (SPR) was monitored in the UV–Vis spectra every 10 min to found the optimal time for localized SPR wavelength (${\lambda }_{\mathrm{L}\mathrm{S}\mathrm{P}\mathrm{R}}$), and the 210 sample procedure has reduced the ${\lambda }_{\mathrm{L}\mathrm{S}\mathrm{P}\mathrm{R}}$ localization at 20 min, while 150 and 60 samples have showed ${\lambda }_{\mathrm{L}\mathrm{S}\mathrm{P}\mathrm{R}}$ at 60 min. The nucleation and growth of GNPs showed changes in shape and size distribution associated with physical (cavitation, temperature) and chemical (radical generation, pH) conditions in the aqueous solution. The results showed quasi-spherical GNPs as pentakis dodecahedron (${\lambda }_{\mathrm{L}\mathrm{S}\mathrm{P}\mathrm{R}}$ = 560 nm), triakis icosahedron (${\lambda }_{\mathrm{L}\mathrm{S}\mathrm{P}\mathrm{R}}$ = 535 nm), and tetrakis hexahedron (${\lambda }_{\mathrm{L}\mathrm{S}\mathrm{P}\mathrm{R}}$ = 525 nm) in a size range from 12 to 16 nm. Chemical effects of ultrasound irradiation were suggested in the disproportionation process, electrons of AuCl₂⁻ are rapidly exchanged through the gold surface. After AuCl₄⁻ and Cl⁻ were desorbed, a tetrachloroaurate complex was recycled for the two-electron reduction by citrate, aurophilic interaction between complexes AuCl₂⁻, electrons exchange, and gold seeds, the deposition of new gold atoms on the surface promoting the growth of GNPs. These mechanisms are enhanced by the effects of ultrasound, such as cavitation and transmitted energy into the solution. These results show that the plasmonic response from the reported GNPs can be tuned using a simple methodology with minimum infrastructure requirements. Moreover, the production method could be easily scalable to meet industrial manufacturing needs.     

Insight into the impact of excluding mass transport,heat exchange and chemical reactions heat on the sonochemical bubble yield: Bubble size-dependency

Numerical simulations have been performed on a range of ambient bubble radii, in order to reveal the effect of mass transport, heat exchange and chemical reactions heat on the chemical bubble yield of single acoustic bubble. The results of each of these energy mechanisms were compared to the normal model in which all these processes (mass transport, thermal conduction, and reactions heat) are taken into account. This theoretical work was carried out for various frequencies (f: 200, 355, 515 and 1000 kHz) and different acoustic amplitudes (P_A: 1.5, 2 and 3 atm). The effect of thermal conduction was found to be of a great importance within the bubble internal energy balance, where the higher rates of production (for all acoustic amplitudes and wave frequencies) are observed for this model (without heat exchange). Similarly, the ignorance of the chemical reactions heat (model without reactions heat) shows the weight of this process into the bubble internal energy, where the yield of the main species (OH, H, O and H₂) for this model was accelerated notably compared to the complete model for the acoustic amplitudes greater than 1.5 atm (for f = 500 kHz). However, the lowest production rates were registered for the model without mass transport compared to the normal model, for the acoustic amplitudes greater than 1.5 atm (f = 500 kHz). This is observed even when the temperature inside bubble for this model is greater than those retrieved for the other models. On the other hand, it has been shown that, at the acoustic amplitude of 1.5 atm, the maximal production rates of the main species (OH, H, O and H₂) for all the adopted models appear at the same optimum ambient-bubble size (R₀ ~ 3, 2.5 and 2 µm for, respectively, 355, 500 and 1000 kHz). For P_A = 2 and 3 atm (f = 500 kHz), the range of the maximal yield of OH radicals is observed at the range of R₀ where the production of OH, O and H₂ is the lowest, which corresponds to the bubble temperature at around 5500 K. The maximal production rate of H, O and H₂ is shifted toward the range of ambient bubble radii corresponding to the bubble temperatures greater than 5500 K. The ambient bubble radius of the maximal response (maximal production rate) is shifted toward the smaller bubble sizes when the acoustic amplitude (wave frequency is fixed) or the ultrasound frequency (acoustic power is fixed) is increased. In addition, it is observed that the increase of wave frequency or the acoustic amplitude decrease cause the range of active bubbles to be narrowed (scenario observation for the four investigated models).     

Sonochemical growth of antimony selenoiodide in multiwalled carbon nanotube

This paper presents, for the first time, the nanocrystalline, semiconducting antimony selenoiodide (SbSeI) grown in multi-walled carbon nanotubes (CNTs). It was prepared sonochemically using elemental Sb, Se, and I in the presence of ethanol under ultrasonic irradiation (35 kHz, 2.6 W/cm²) at 323 K for 3 h. The CNTs filled with SbSeI were characterized by using techniques such as powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, high-resolution transmission electron microscopy, selected area electron diffraction, and optical diffuse reflection spectroscopy. These investigations exhibit that the SbSeI filling the CNTs is single crystalline in nature and in the form of nanowires. It has indirect allowed energy band gap E_gIf = 1.61(6) eV.     

Ultrasound promoted Wurtz coupling of alkyl bromides and dibromides

Sonochemically enhanced Wurtz coupling using lithium metal has been investigated for a number of isomeric alkyl bromides under a variety conditions. The products result from direct coupling of short lived radicals formed at the metal surface rather than the secondary radicals which can be formed during coupling of aromatic halides and thus give rise to a single major product. Coupling has been extended to dibrominated aryl and alkyl compounds as well as showing that aryl-alkyl coupling is possible. Dibrominated alkyls were found to give low molecular weight oligomers although no reaction occurred for 1,2-isomers. The growth of oligomers in THF may be solubility limited. A simple model is proposed to explain these findings.