A parametric review of sonochemistry: Control and augmentation of sonochemical activity in aqueous solutions

In this review the phenomenon of ultrasonic cavitation and associated sonochemistry is presented through system parameters. Primary parameters are defined and considered, namely; pressure amplitude, frequency and reactor design; including transducer type, signal type, vessel-transducer ratio, liquid flow, liquid height, liquid temperature and the presence of a reflective plate. Secondary parameters are similarly characterised and involve the use of gas and liquid additives to influence the chemical and physical environments. Each of the parameters are considered in terms of their effect on bubble characteristics and subsequent impact on sonochemical activity. Evidence suggests that via parametric variation, the reaction products and efficiency may be controlled. This is hypothesised to occur through manipulation of the structural stability of the bubble.     

EPR studies on aqueous sucrose solutions using (Cu(H2O)6)2+ spin probe

EPR investigations using Cu²⁺ ion as a probe have been performed on supersaturated sucrose solution with percent concentration c = 66 as a function of temperature T, and at room temperature as a function of c. The motionally averaged spectrum of [Cu(H₂O)₆]²⁺ was used to monitor the changes in intermolecular interactions that occur as a function of [c, T]. A drastic increase in the line width, symptomatic of increase in the rotational correlation time of [Cu(H₂O)₆]²⁺, is observed between 293 and 288 K. The motionally averaged spectrum disappears below 281 K. The motionally averaged spectrum is also absent in the room temperature spectra of the solution with c= 85. Even in the [c, T] range where [Cu(H₂O)₆]² is found to be nearly static, these molecules appear to have an orientational fluctuation manifesting in the m ₁ dependence of the line width of the parallel component.     

Dissolved organic matter inhibition of sonochemical degradation of aqueous polycyclic aromatic hydrocarbons

Sonochemical degradation of aqueous polycyclic aromatic hydrocarbons (PAHs) was found to be rapid in the absence of other dissolved compounds (k = 0.006-0.015 s-1). In the presence of 20 mg Cl-1 fulvic acid, first-order PAH degradation rate constants decreased from 2.3- to 3.7-fold. Similar results were obtained with added benzoic acid, a crude analog for fulvic acid. In natural waters, PAH degradation was almost completely inhibited. Analysis of the kinetic behavior and reaction products indicates that PAHs are most likely degraded through a radical cation mechanism. Hydroxyl radical appeared to play an insignificant role in the degradation. Inhibited degradation was probably the result of either altered cavitation processes or isolation of the PAH away from cavitation sites.     

Reaction kinetics of sonochemical oxidation of potassium hexacyanoferrate(II) in aqueous solutions

We studied sonochemical reactions resulting from ultrasonic treatment of potassium hexacyanoferrate(II) in aqueous solutions using a custom-built apparatus working at 536 kHz. We concluded that primary reactions are completely dominated by oxidation of Fe(II) to Fe(III) and did not find any evidences for degradation of cyanide. At the highest concentration used in the present study (0.1 M) we detected formation of pentacyanoaquaferrate(II) complex, which is most probably formed in reactions between hexacyanoferrate(III) anions and hydrogen atoms or hydrated electrons formed in sonochemical processes. We also determined that hydroxyl radicals formation rate in our system, (8.7 ± 1.5)∙10⁻⁸ M∙s⁻¹, is relatively high compared to other reported experiments. We attribute this to focusing of the ultrasonic wave in the sample vessel. Finally, we suggest that oxidation rate of hexacyanoferrate(II) anions can be a convenient benchmark of efficiency of sonochemical reactors.     

Electron paramagnetic resonance of sonicated powder suspensions in organic solvents

The chemical effects of the acoustic cavitation generated by ultrasound translates into the production of highly reactive radicals. Acoustic cavitation is widely explored in aqueous solutions but it remains poorly studied in organic liquids and in particular in liquid/solid media. However, several heterogeneous catalysis reactions take place in organic solvents.Thus, we sonicated trimethylene glycol and propylene glycol in the presence of silica particles (SiO₂) of different sizes (5–15 nm, 0.2–0.3 µm, 12–26 µm) and amounts (0.5 wt% and 3 wt%) at an ultrasound frequency of 20 kHz to quantify the radicals generated. The spin trap 5,5-dimethyl-1-pyrrolin–N-oxide (DMPO) was used to trap the generated radicals for study by electron paramagnetic resonance (EPR) spectroscopy. We identified the trapped radical as the hydroxyalkyl radical adduct of DMPO, and we quantified it using stable radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a quantitation standard. The concentration of DMPO spin adducts in solutions containing silica size 12–26 µm was higher than the solution without particles. The presence of these particles increased the concentration of the acoustically generated radicals by a factor of 1.5 (29 µM for 0.5 wt% of SiO₂ size 12–26 µm vs 19 µM for 0 wt%, after 60 min of sonication). Ultrasound produced fewest radicals in solutions with the smallest particles; the concentration of radical adducts was highest for SiO₂ particle size 12–26 µm at 0.5 wt% loading, reaching 29 µM after 60 min sonication. Ultrasound power of 50.6 W produced more radicals than 24.7 W (23 µM and 18 µM, respectively, at 30 min sonication). Increased temperature during sonication generated more radical adducts in the medium (26 µM at 75 °C and 18 µM at 61 °C after 30 min sonication). Acoustic cavitation, in the presence of silica, increased the production of radical species in the studied organic medium.     

Sonodynamic therapy--a review of the synergistic effects of drugs and ultrasound

Sonodynamic therapy, the ultrasound dependent enhancement of cytotoxic activities of certain compounds (sonosensitizers) in studies with cells in vitro and in tumor bearing animals, is reviewed. The attractive features of this modality for cancer treatment emerges from the ability to focus the ultrasound energy on malignancy sites buried deep in tissues and to locally activate a preloaded sonosensitizer. Possible mechanisms of sonodynamic therapy include generation of sonosensitizer derived radicals which initiate chain peroxidation of membrane lipids via peroxyl and/or alkoxyl radicals, the physical destabilization of the cell membrane by the sonosensitizer thereby rendering the cell more susceptible to shear forces or ultrasound enhanced drug transport across the cell membrane (sonoporation). Evidence against the role of singlet oxygen in sonodynamic therapy is discussed. The mechanism of sonodynamic therapy is probably not governed by a universal mechanism, but may be influenced by multiple factors including the nature of the biological model, the sonosensitizer and the ultrasound parameters. The current review emphasizes the effect of ultrasound induced free radicals in sonodynamic therapy.     

EPR and NMR study of molecular components mobility and organization in goat milk under ultrasound treatment

The effect of ultrasound treatment on molecular mobility and organization of the main components in raw goat milk was studied by EPR and NMR spectroscopies. NMR relaxation studies showed an increase in the spin–lattice T₁ and spin–spin T₂ relaxation times in goat milk products (cream, anhydrous fat) and change in the diffusion of proton-containing molecules during ultrasound treatment. The diffusion became more uniform and could be rather accurately approximated by one effective diffusion coefficient D_eff, which indicates homogenization of goat milk components, dispersion of globular and supermicellar formations under sonication. EPR studies have shown that molecular mobility and organization of hydrophobic regions in goat milk are similar to those observed in micellar formations of surfactants with a hydrocarbon chain length C12–C16. Ultrasound treatment did not affect submicellar and protein globule organization. Free radicals arising under ultrasound impact of milk reacted quickly with components of goat milk (triglycerides, proteins, fatty acids) and were not observed by spin trapping method.     

Recent studies in thermal activation and spin waves

Some recent results in computational approaches to thermally activated fast reversal in magnetic recording media are reviewed. In particular, recent results reported in the simulation of pulsed-field-induced magnetisation reversal and thermal activation of spin waves are described. The short time scale breakdown of the Arrhenius–Néel law for a single moment is demonstrated and explained in terms of the dynamics of the precessional motion. The variation in response as a function of the damping parameter is found to be an important factor determining the remanent magnetisation for a given pulse width. The effects of interactions between moments are described, including the apparent increase in effective damping. It is shown that interactions between moments can be described in terms of thermally excited spin waves. The spectrum of relaxation times for systems consisting of coupled moments is explained in terms of the thermal excitation of spin waves.     

Saturation recovery EPR and ELDOR at W-band for spin labels

A reference arm W-band (94 GHz) microwave bridge with two sample-irradiation arms for saturation recovery (SR) EPR and ELDOR experiments is described. Frequencies in each arm are derived from 2 GHz synthesizers that have a common time-base and are translated to 94 GHz in steps of 33 and 59 GHz. Intended applications are to nitroxide radical spin labels and spin probes in the liquid phase. An enabling technology is the use of a W-band loop-gap resonator (LGR) [J.W. Sidabras, R.R. Mett, W. Froncisz, T.G. Camenisch, J.R. Anderson, J.S. Hyde, Multipurpose EPR loop-gap resonator and cylindrical TE₀₁₁ cavity for aqueous samples at 94 GHz, Rev. Sci. Instrum. 78 (2007) 034701]. The high efficiency parameter (8.2 GW^−1/2 with sample) permits the saturating pump pulse level to be just 5 mW or less. Applications of SR EPR and ELDOR to the hydrophilic spin labels 3-carbamoyl-2,2,5,5-tetra-methyl-3-pyrroline-1-yloxyl (CTPO) and 2,2,6,6,-tetramethyl-4-piperidone-1-oxyl (TEMPONE) are described in detail. In the SR ELDOR experiment, nitrogen nuclear relaxation as well as Heisenberg exchange transfer saturation from pumped to observed hyperfine transitions. SR ELDOR was found to be an essential method for measurements of saturation transfer rates for small molecules such as TEMPONE. Free induction decay (FID) signals for small nitroxides at W-band are also reported. Results are compared with multifrequency measurements of T_1e previously reported for these molecules in the range of 2–35 GHz [J.S. Hyde, J.-J. Yin, W.K. Subczynski, T.G. Camenisch, J.J. Ratke, W. Froncisz, Spin label EPR T₁ values using saturation recovery from 2 to 35 GHz. J. Phys. Chem. B 108 (2004) 9524–9529]. The values of T_1e decrease at 94 GHz relative to values at 35 GHz.     

Sonochemistry of volatile and non-volatile solutes in aqueous solutions: e.p.r. and spin trapping studies

Recent spin trapping studies of the free radical intermediates generated by the sonolysis of aqueous solutions are reviewed. Studies of rare gas saturated solutions of volatile solutes (e.g., methanol and ethanol) and of non-volatile solutes (acetate, amino acids, sugars, pyrimidines, nucleotides and surfactants) are consistent with the theory of three reaction zones in aqueous sonochemistry. The very high temperatures and pressures induced by acoustic cavitation in collapsing gas bubbles in aqueous solutions lead to the thermal dissociation of water vapour into hydrogen atoms and hydroxyl radicals. Reactions take place in the gas phase (pyrolysis reactions), in the region of the gas-liquid interface, and in the bulk of the solution at ambient temperature (similar to radiation chemistry reactions). By use of the rare gases with different thermal conductivities, the contributions of individual reaction steps with widely different energies of activation can be evaluated.     

Membrane fluidity altering and enzyme inactivating in sarcoma 180 cells post the exposure to sonoactivated hematoporphyrin in vitro

Sonodynamic therapy (SDT) is a novel tumor therapy method. We investigated membrane fluidity, activity of the enzymes and membrane morphology in vitro post hematoporphyrin-SDT treatment. Furthermore, the potential mechanisms behind the changes in membrane fluidity and enzymic activity were discussed. Tumor cells were exposed to ultrasound at 1.75 MHz for up to 3 min in the presence and absence of hematoporphyrin. Fluorescence polarization, contents of Malonaldehyde, and levels of free fatty acid were assessed. Activity of enzymes was checked by the plumbic nitrate detection method. For the morphologic study, a scanning electron microscope was used to observe the cellular surface. Ultrasonically induced cell damage increased in the presence of HPD (from 15% to 24%). Compared with ultrasound treatment alone, the fluidity decreased from 5.037 to 3.908, malonaldehyde content and free fatty acid level increased from 0.743 nmol/mL to 0.979 nmol/mL and from 237.180 μmol/L to 730.769 μmol/L, respectively, post ultrasound combined with HPD treatment. Inactivity of adenylate cyclase and guanylate cyclase and significant deformation of the cellular surface were also observed post SDT treatment. Our results suggested that alterations in membrane modality and lipid composition played important roles in SDT-mediated inhibition of tumor growth, even inducing tumor cell death, which might be attributed to a sono-chemical activation mechanism.     

The role of p53 in the response of tumor cells to sonodynamic therapy in vitro

p53 plays a pivotal role in apoptosis. In addition, p53 is currently extensively investigated as a promising strategy for highly specific anticancer therapy in chemotherapeutics and photodynamic therapy. However, the role of p53 in the response of tumor cells to sonodynamic therapy treatment is still unclear. In this study, we aim to investigate the activation of p53 in sonodynamic therapy. Three murine tumor models with distinct aggressiveness (S180, H-22 and EAC) were treated with 1.75 MHz continuous ultrasound at an acoustic intensity (I_SATA) of 1.4 W for 3 min in the presence of 20 μg/ml hematoporphyrin. The DNA fragment and nuclear damage were observed by TUNEL and single cell gel electrophoresis. Western blotting and RT-PCR were used to analyze the expression of p53, PUMA, Bax and Fas. Then we checked the translocation of p53 by confocal microscopy. DNA sequencing was used to determine the status of p53 gene in three tumor cell lines. Our results indicated that the level of p53 protein and mRNA increased significantly, and p53 activated the expression of its downstream pro-apoptosis gene PUMA, Bax and Fas in the S180 and H-22 cells. Meanwhile, p53 protein translocated onto mitochondria. In the EAC cells, expression and translocation of p53 was not found; the level of PUMA, Bax and Fas remained unaltered. The S180 cells showed most serious DNA fragment and nuclear damage with 77.43% TDNA; H-22 cells in the middle with 58.85% TDNA; whereas EAC cells appeared less nuclear material lost with just 15.82% TDNA. The results of DNA sequencing showed that the sequences of exons 5-8 of the p53 gene of S180, H-22 and EAC cells were the same with the sequences of wild-type p53 provided by NCBI. These results primarily demonstrated that: (1) p53 was activated to promote SDT-induced apoptosis through extrinsic and intrinsic signaling pathways in the S180 and H-22 cells; (2) cellular responses of different cells to SDT were distinct, the aggressive S180 cells were much more sensitive than H-22, whereas EAC cells were relatively less sensitive. The discrepancy among the cell lines may be due to different activation time of p53 protein.     

电子俘获材料的研究现状及在红外检测方面的应用

电子俘获材料在辐射剂量测定、光信息处理、光存储、红外光检测等许多技术领域具有广泛的应用。本文详细介绍了电子俘获材料的发光原理、材料种类、制备方法以及研究现状,并针对该材料在红外光检测方面的应用,提出了在室温下该材料存在红外光检测上限的观点。针对电子俘获材料存在性质不稳定及在制备过程中需用到硫化类材料易造成污染等问题,建议进一步改进材料制备方法。最后,文中指出玻璃陶瓷类电子俘获材料会有很好的发展前景,并对该种材料未来的发展前景进行了展望。     

Ultrasound exposure in the presence of hematoporphyrin induced loss of membrane integral proteins and inactivity of cell proliferation associated enzymes in sarcoma 180 cells in vitro

Ultrasonically induced effects of hematoporphyrin (HPD) on cell damage and membrane protein alteration of S180 isolated tumor cells in vitro were investigated, and the potential mechanisms of sonodynamic therapy (SDT) inhibiting tumor growth were discussed. Tumor cells suspended in air-saturated PBS (pH 7.2) were exposed to ultrasound at 1.8 MHz for up to 180 s in the presence and absence of HPD. The viability of cells was determined by a trypan blue exclusion test. To estimate the damage effects of SDT on plasma membrane of tumor cells primarily, membrane integral proteins (EGFR, Ras, Fas, FasL) and cell proliferation associated enzymes (adenylate cyclase and guanylate cyclase) were checked with immunochemical methods. The results indicated that the intensity threshold for ultrasonically induced cell damage at 1.8 MHz was 3 W/cm². At this condition, the expression of the integral proteins was obviously inhibited and the activity of the enzymes was decreased post ultrasound treatment in the presence of 20 μg/ml HPD. Loss of the membrane proteins and inactivity of AC and GC post SDT was time-dependent. This paper reveals SDT can cause the loss of tumor cell membrane integral proteins and inactivity of the enzymes associated with cell proliferation which might be attributed to a sonochemical activation mechanism. The mechanisms by that tumor growth is inhibited by SDT can be understood as that the growth signaling pathway is partially interdicted and the resistance of tumor cells to the specifically activated immune cells is weakened.     

Effect of potassium monopersulfate (oxone) and operating parameters on sonochemical degradation of cationic dye in an aqueous solution

In this study, removal of Cresol Red (CR), a cationic triphenylmethane dye, by 300 kHz ultrasound was investigated. The effect of additive such as potassium monopersulfate (oxone) was studied. Additionally, sonolytic degradation of CR was investigated at varying power and initial pH. RC can be readily eliminated by the ultrasound process. The obtained results showed that. Sonochemical degradation of CR was strongly affected by ultrasonic power and pH. The degradation rate of the dye increased substantially with increasing ultrasonic power in the range of 20–80 W. This improvement could be explained by the increase in the number of active cavitation bubbles. The significant degradation was achieved in acidic conditions (pH = 2) where the color removal was 99% higher than those observed in higher pH aqueous solutions. The ultrasonic degradation of dye was enhanced by potassium monopersulfate (oxone) addition. It was found that the degradation of the dye was accelerated with increased concentrations of oxone for a reaction time of 75 min.     

Kinetics and mechanisms of ultrasonic degradation of volatile chlorinated aromatics in aqueous solutions

Ultrasonic decompositions of chlorobenzene (ClBz), 1,4-dichlorobenzene and 1-chloronaphthalene were investigated at 500 kHz in order to gain insight into the kinetics and mechanisms of the decomposition process. The disappearance of ClBz on sonication is almost simultaneously accompanied by the release of chloride ions as a result of the rapid cleavage of carbon–chlorine bonds with a concomitant release of CO, C₂H₂, CH₄ and CO₂. The intermediates resulting from attack of HO^√ radicals were detected but in a quite low yield (less than 2 μM). The generation of H₂O₂ on sonolysis is not significantly affected by the presence of aqueous ClBz while the generation of NO₂⁻ and NO₃⁻ is inhibited initially due to the presence of ClBz which diffuses into the gas–bubble interfaces and inhibits the interactions between free radicals and nitrogen. Moreover, brown carbonaceous particles are present throughout the ultrasonic irradiation process, which are consistent with soot formation under pyrolytic conditions. These important features suggest that, at the relatively high initial substrate concentrations used in this study, ultrasonic degradation of ClBz takes place predominantly both within the bubbles and within the liquid–gas interfaces of bubbles where it undergoes high-temperature combustion. Under these conditions, the oxidation of ClBz by free radical HO^√ outside of bubbles is a minor factor (though results of recent studies suggest that attack by HO^√ is more important at lower initial substrate concentrations). The sonochemical decomposition of volatiles follows pseudo-first-order reaction kinetics but the degradation rates are affected by operating conditions, particularly initial substrate concentration and ultrasonic intensity.     

Transmission of electrons through ferromagnetic material and applications to detection of electron spin polarization

The salient features of the total low energy inelastic electron scattering cross section in transition metals are described by a constant term σ₀ plus a term σ_d that is proportional to the number of unoccupied d-orbitals. This simple model predicts that low energy electrons transmitted through a ferromagnetic ultrathin film acquire a transport spin polarization a(χ). Using the ratio σ₀/σ_d as the only adjustable parameter, the model predicts the enhancement of the spin polarization of the low energy cascade electrons as well as a(χ) in reasonable agreement with the existing observations on Fe, Co and Ni. A detector for electron spin polarization P based on the spin dependent transmission of electrons through ferromagnetic material is proposed which should be superior to existing P-detectors by 1–2 orders of magnitude.     

Sonochemical synthesis of nanocrystalline mercury sulfide, selenide and telluride in aqueous solutions

Nanocrystalline mercury chalcogenides HgE (E = S, Se, Te) were synthesized in a single step by a convenient, simple sonochemical method. Mercury nitrate, Hg(NO₃)₂, dissolved in 0.1 M ethylenediamine tetraacetic acid (EDTA), was used as the source of mercury and elemental chalcogenes, dissolved in a NaOH solution, as the sources of chalcogenide. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDAX). The synthesis procedure is simple and uses less toxic reagents than the previously reported methods. The results showed that the complexing agent EDTA plays a crucial role in the process.     

A novel approach to the simulation of nitroxide spin label EPR spectra from a single truncated dynamical trajectory

A simple effective method for calculation of EPR spectra from a single truncated dynamical trajectory of spin probe orientations is reported. It is shown that an accurate simulation can be achieved from the small initial fraction of a dynamical trajectory until the point when the autocorrelation function of re-orientational motion of spin label has relaxed. This substantially reduces the amount of time for spectra simulation compared to previous approaches, which require multiple full length trajectories (normally of several microseconds) to achieve the desired resolution of EPR spectra. Our method is applicable to trajectories generated from both Brownian dynamics and molecular dynamics (MD) calculations. Simulations of EPR spectra from Brownian dynamical trajectories under a variety of motional conditions including bi-modal dynamics with different hopping rates between the modes are compared to those performed by conventional method. Since the relatively short timescales of spin label motions are realistically accessible by modern MD computational methods, our approach, for the first time, opens the prospect of the simulation of EPR spectra entirely from MD trajectories of real proteins structures.     

电子顺磁共振法(EPR)对银杏叶提取物及其卷烟捕获自由基能力研究

自由基存在于人体和卷烟烟气中,会引起人体病理反应和氧化损伤,种类和形态多样,如：O-·₂,HO·,R·,RO·,ROO·。电子顺磁共振法(EPR)是检测和定量分析自由基的重要方法之一。银杏叶提取物(EGB)是由黄酮、内酯、原花青素类成分组成的植物药,具有较好清除自由基和抗氧化能力。本文以槲皮素、芦丁、原花青素等化合物为对照,运用EPR法结合自旋捕集技术研究EGB和EGB卷烟对DPPH,HO·,O2-·、烟气气相自由基、烟气粒相自由基的抑制水平。结果表明,EGB能够有效抑制化学/生物系统和卷烟烟气产生的自由基。尽管抑制自由基整体水平比黄酮单体和原花青素弱,但EGB提取方法简单容易得到,可作为天然抗氧化剂和自由基清除剂用于食品和烟草等行业。EPR法灵敏度高,稳定性好,是用于自由基研究的可靠方法。捕集剂DEPMPO捕集O2-·更加高效,PBN捕集烟气气相自由基比DMPO更有优势。该研究讨论了EGB清除自由基的机理,丰富的酚羟基结构是其抗氧化作用的主要原因。