Dosimetry in sonochemistry: the use of aqueous terephthalate ion as a fluorescence monitor

The generation of HO radicals by acoustic cavitation in water was monitored by their reaction with terephthalic acid (TA) anion to produce fluorescent hydroxyterephthalate ions using a cleaning bath (38kHz) and a probe system (20, 40 and 60 kHz) as different sources of ultrasound. When using the ultrasonic bath as a source of energy for sonochemical studies, the shape of the reaction vessel is important. In the case of HO production from water (50 cm³), reaction in a conical flask (100 cm³) produces 2.75 times more radicals than a round-bottomed flask of the same capacity. The fluorescence yield (fluorescence intensity/ultrasound dosage) obtained using the conical flask and ultrasonic bath was similar to that for a probe operating at 40 kHz on the same volume of solution. For a probe system operating at 20, 40 and 60 kHz the greatest sonochemical efficiency was attained at the highest of these frequencies (60 kHz). For the probe system the fluorescence yield is directly proportional to power input and the concentration of TA. The fluorescence yield decreases as the temperature is increased.     

盐酸丁卡因与赤藓红的荧光猝灭反应及其分析应用

在pH 4.0的弱酸性介质中,盐酸丁卡因(TA·HCl)与赤藓红(ET)形成1∶1的离子缔合物,导致赤藓红溶液荧光猝灭。当分别于最大激发/最大发射(λ_ex/λem)525 nm/556 nm进行测量时,荧光猝灭值(ΔF)与TA·HCl浓度在0.28～4.8 μg·mL-1范围呈良好的线性关系。该方法灵敏度高,检出限为0.083 μg·mL-1。考察了共存物质的影响,表明方法有良好的选择性。据此发展了一种高灵敏、简便快速测定微量TA·HCl的新荧光分光光度法。该法用于人血清及尿样中盐酸丁卡因的含量测定,结果满意。文章还研究了反应体系的荧光特性,并结合量子化学AM1计算对荧光猝灭机理进行了讨论。     

光谱法研究纳米二氧化硅(SiO_2)催化超声波照射对牛血清白蛋白(BSA)的损伤

利用紫外-可见(Uv-Vis)光谱和荧光光谱研究了超声波照射激活纳米二氧化硅(SiO2)粒子对牛血清白蛋白(BSA)分子的损伤,并考查了超声波照射时间、纳米SiO2粉末加入量、溶液酸度和超声波照射功率等因素对BSA分子损伤程度的影响.结果表明,对于体系温度为(37.0±0.2)℃和浓度为1.0×10-5mol·-1的BSA溶液,UV-Vis光谱显示,随着超声波照射时间,纳米SiO2粉末加入量,溶液pH值和照射功率的增大呈现出越来越明显的增色效应.然而,BSA溶液的荧光光谱却随着上述因素的增大呈现出越来越明显的猝灭现象.此外,还初步探讨了超声波照射激活纳米siO2粒子对BSA分子损伤的机理,认为是声致发光或高热激发使纳米siO2粒子产生·OH自由基,进而损伤溶液中的BSA分子.这一研究结果对声催化方法应用于临床治疗肿瘤以及纳米药物的开发具有一定的指导意义.     

Exploring the effects of pulsed ultrasound at 205 and 616 kHz on the sonochemical degradation of octylbenzene sulfonate

Compared to continuous wave (CW) ultrasound, pulsed wave (PW) ultrasound has been shown to result in enhanced sonochemical degradation of octylbenzene sulfonate (OBS). However, pulsed ultrasound was investigated under limited pulsing conditions. In this study, pulse-enhanced degradation of OBS was investigated over a broad range of pulsing conditions and at two ultrasonic frequencies (616 and 205 kHz). The rate of OBS degradation was compared to the rate of formation of 2-hydroxyterephthalic acid (HTA) following sonolysis of aqueous terephthalic acid (TA) solutions. This study shows that sonication mode and ultrasound frequency affect both OBS degradation and HTA formation rates, but not necessarily in the same way. Unlike TA, OBS, being a surface active solute, alters the cavitation bubble field by adsorbing to the gas/solution interface of cavitation bubbles. Enhanced OBS degradation rates during pulsing are attributed to this adsorption process. However, negative or smaller pulse enhancements compared to enhanced HTA formation rates are attributed to a decrease in the high-energy stable bubble population and a corresponding increase in the transient bubble population. Therefore, sonochemical activity as determined from TA sonolysis cannot be used as a measure of the effect of pulsing on the rate of degradation of surfactants in water. Over relatively long sonolysis times, a decrease in the rate of OBS degradation was observed under CW, but not under PW conditions. We propose that the generation and accumulation of surface active and volatile byproducts on the surface and inside of cavitation bubbles, respectively, during CW sonolysis is a contributing factor to this effect. This result suggests that there are practical applications to the use of pulsed ultrasound as a method to degrade surface active contaminants in water.     

Chain Degradation under Low-Intensity Sonication of Polymer Solutions in the Presence of Filler: Mechanism of Ultrasonic Degradation of Flexible Chain Macromolecules

Routine dispersion of fillers in polymer solutions in a usual ultrasonic cleaning bath has been shown to lead to chain degradation. It is the filler presence, only, that has been demonstrated to provoke chain degradation under low-intensity sonication. A critical analysis of the literature concerned with the effects arising from propagation of acoustic waves in a liquid and an experimental study of ultrasonic degradation of polymers in solution were carried out. Based on these results, the mechanisms of chain degradation were discussed. Our previously proposed universal mechanism of chain degradation in inhomogeneous hydrodynamic fields has been shown to explain the basic facts repeatedly confirmed over the years of studying the ultrasonic degradation: (i) the existence of a limiting molecular weight such that macromolecules with lower molecular weights are not subject to degradation and (ii) the dependences of degradation rate on polymer molecular weight, polymer concentration, and temperature.     

Spectrometric Studies on the Sonodynamic Damage of Protein in the Presence of Levofloxacin

Taking bovine serum albumin (BSA) as typical molecules, the sonodynamic damage of protein in the presence of Levofloxacin (LVFX) and its mechanism were studied by fluorescence and UV-vis spectra. Various influencing factors such as ultrasonic irradiation time, pH value, ionic strength and solution temperature on the damage of BSA were also discussed. The results showed that ultrasound can enhance the damage of LVFX on BSA. The damage degree of BSA was aggravated with the increase of ultrasonic irradiation time, solution temperature and ionic strength, whereas decreased with the increase of solution pH value. Furthermore, the reactive oxygen species (ROS) in reaction system were studied by oxidation and extraction photometry. Experimental results showed that the amounts of superoxide anion radical (·O₂ ^ˉ) and hydroxyl radical (·OH) were significantly more than that of singlet oxygen (¹O₂) in the presence of LVFX under ultrasonic irradiation.     

CdS量子点超声水相制备、表征及与萘的相互作用

在室温条件下,用超声水相制备CdS量子点(QDs),并用透射电镜、X射线衍射、紫外光谱法、荧光光谱法等手段表征.探讨了初始pH、反应物配比、超声时间、熟化时间等因素对CdS量子点制备的影响.初步研究了该方法制备的CdS量子点与萘的相互作用,线性范围为0.002-0.025mg/mL,r<'2>=0.9965.CdS量子...     

Sound wave interaction with Josephson junction and transformation of the contact coherent binding energy into ultrasonic waves

The problem of ultrasonic wave propagation in narrow Josephson junctions at nonzero temperature has been investigated. Using the derived solution of the nonstationary Fokker-Planck equation, the total current flowing through the narrow Josephson junction is calculated, and the coefficient of the ultrasonic wave passage through the Josephson junction is determined. The singularity of this coefficient is studied in the ultrasound amplification mode associated with the transformation of coherent binding energy of the contact into ultrasonic waves, and the possibility of experimental measurement of the lifetime of the Josephson junction in the metastable state under the conditions of maximum ultrasound amplification by the contact is discussed.     

Investigation on damage of DNA molecules under irradiation of low frequency ultrasound in the presence of hematoporphyrin-gallium (HP-Ga) complex

The interaction of deoxyribonucleic acid (DNA) and hematoporphyrin–gallium (HP–Ga) complex and the damage of DNA under ultrasonic irradiation in the presence of HP–Ga complex were studied by means of UV–vis spectrum, fluorescence spectrum and gelatin electrophoresis. In addition, some influence factors such as ultrasonic irradiation time, HP–Ga complex concentration, ionic strength and solution acidity on the damage of DNA were also considered. Under a certain condition, the damage degree of DNA was enhanced with increasing ultrasonic irradiation time, HP–Ga complex concentration and ionic strength. Whether the pH value was too high or too low, it would be disadvantage to the damage of DNA. Perhaps, these results would be significant for driving sonodynamic treatment (SDT) to the clinic application in the future.     

Sonophotochemical destruction of aqueous solution of 2,4,6-trichlorophenol

The combination of ultrasound and photochemistry have been used to degrade an aqueous solution of 2,4,6-trichlorophenol. An ultrasonic probe of 22 kHz frequency and a UV tube of 15 W have been used. Anatase grade TiO2 was used as the semiconductor catalyst. The effect of parameters such as ultrasonic intensity, operating conditions, type of ultrasonic equipment, and mode of UV transmission have been studied. The sonophotochemical degradation has been found to be dependent on the intensity of sonication, temperature of the reaction, and the type of ultrasonic equipment used, but was independent of the mode of UV transmission. Enhancement in the degradation rate has been observed at a higher sonication intensity and temperature of the solution.     

罗丹明101的高压荧光特性

 测定了粉末罗丹明101（Rhodamine 101）及其在溶剂（甲醇、乙醇、水的混合液）中的高压荧光光谱。结果表明,粉末样品和溶液样品在高压下的发光性质有很大的区别。对于粉末样品,随着压力的增加,Rhodamine 101的荧光强度下降很快,在大约8 GPa时荧光峰几乎消失;伴随着荧光强度的变化,荧光峰峰位发生了显著红移（8 GPa内红移了近100 nm）。对于溶液样品,其荧光强度随压力的增加降低较慢,到13 GPa时,强度约为常压的10%,荧光峰峰位红移较小（13 GPa内红移约50 nm）。在压力作用下,Rhodamine 101分子结构的变化和特殊的溶剂效应,分别是影响其在粉末状态和溶液中荧光性质的主要因素。     

Ultrasound induced aqueous polycyclic aromatic hydrocarbon reactivity

An investigation to determine the ability of ultrasonic radiation to chemically alter polycyclic aromatic hydrocarbons (PAHs) in aqueous solution has been conducted. The data indicate that chemical alteration of PAHs can be induced under intense ultrasonic treatment. The extent and outcome of reaction is a function of irridation time and aqueous solution parameters. Reaction products were analysed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Reaction products from ultrasonic treatment of aqueous solutions of biphenyl include ortho, meta, and para-1,1 biphenols. The principal product from ultrasonic treatment of aqueous phenanthrene solutions appears to be a phenanthrene-diol. The number and composition of reaction products for both PAHs tested suggest that a free radical mechanism is likely during aqueous high intensity ultrasonic treatment. The use of ultrasound to treat PAH contaminated aqueous solutions in tandem with other methodologies appears promising. However, the toxicity of reaction products produced by treatment remains to be determined.     

超声波在不同浓度NaCl溶液中传播速度的研究

利用超声波声速测定仪测定出超声波在不同浓度NaCl溶液中的传播速度.实验给出,超声波在NaCl溶液中的传播速度与溶液浓度呈线性关系.溶液温度对超声波波速也有影响,并从理论作了分析研究,给出了合理的解释.     

Spectroscopic investigation on the sonodynamic activity of amsacrine (AMSA) to bovine serum albumin (BSA) damage

The sonodynamic damage of bovine serum albumin (BSA) under ultrasonic irradiation in the presence of amsacrine (AMSA) was studied by hyperchromic effect of UV-vis spectra and quenching effect of intrinsic fluorescence. In addition, several influencing factors such as ultrasonic irradiation time, AMSA concentration, system acidity and ionic strength about the damage of BSA molecules were reviewed. The results showed that the damage degree was obviously enhanced with the increase of ultrasonic irradiation time and AMSA concentration, but it was only slightly increased with the increase of solution pH value and ionic strength. Furthermore, the binding and damaging sites to BSA molecules were estimated by synchronous fluorescence spectra. The different chances to damage tryptophan (Trp) and tyrosine (Tyr) residues were found through the ratios of synchronous fluorescence quenching (R_SFQ). At last, the generation of reactive oxygen species (ROS) in sonodynamic process was estimated by the method of oxidation-extraction Spectrometry (OES). And then, several radical scavengers were used to determine the kind of ROS, which includes singlet oxygen (¹O₂) and hydroxyl radicals (·OH). Perhaps, the result would bring a certain guiding significance to use sonosensitive drugs in the fields of tumor treatment.     

The optimisation of ultrasonic cleaning procedures for dairy fouled ultrafiltration membranes

Ultrafiltration (UF) of whey is a major membrane based process in the dairy industry. However, commercialization of this application has been limited by membrane fouling, which has a detrimental influence on the permeation rate. There are a number of different chemical and physical cleaning methods currently used for cleaning a fouled membrane. It has been suggested that the cleaning frequency and the severity of such cleaning procedures control the membrane lifetime. The development of an optimal cleaning strategy should therefore have a direct implication on the process economics. Recently, the use of ultrasound has attracted considerable interest as an alternative approach to the conventional methods. In the present study, we have studied the ultrasonic cleaning of polysulfone ultrafiltration membranes fouled with dairy whey solutions. The effects of a number of cleaning process parameters have been examined in the presence of ultrasound and results compared with the conventional operation. Experiments were conducted using a small single sheet membrane unit that was immersed totally within an ultrasonic bath. Results show that ultrasonic cleaning improves the cleaning efficiency under all experimental conditions. The ultrasonic effect is more significant in the absence of surfactant, but is less influenced by temperature and transmembrane pressure. Our results suggest that the ultrasonic energy acts primarily by increasing the turbulence within the cleaning solution.     

Fluorescence Quenching of 1,4-Dihydroxy-2,3-Dimethyl-9,10-Anthraquinone by Silver Nanoparticles: Size Effect

Size effect of silver nano particles on the photophysical properties of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone (DHDMAQ) have been investigated using optical absorption and fluorescence emission techniques. Silver nanoparticles of different sizes have been prepared by Creighton method using magnetic stirrer and ultrasonic field. Quenching of fluorescence of DHDMAQ has been found to increase with decrease in the size of the silver nanoparticles. Stern–Volmer quenching constants have also been calculated.     

Ultrasound-assisted thiocyanation of aromatic and heteroaromatic compounds using ammonium thiocyanate and DDQ

Thiocyanation of various aromatic and heteroaromatic compounds has been achieved in the presence of ammonium thiocyanate (NH(4)SCN) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in methanol solution under ultrasound irradiation. An ultrasonic probe of 24 kHz frequency has been used for this study. Whereas the use of ultrasound increases the rate of reactions compared with reactions at reflux conditions, the electron-donor ability of aromatic nucleus enhances also the rate of reaction.     

The effect of grain size distribution on the frequency dependence of the ultrasonic attenuation in polycrystalline materials

An expression has been derived for the effect of the grain size distribution in polycrystalline materials on the frequency dependence of the ultrasonic attenuation. It has been shown that two specimens with the same mean grain size can have significantly different ultrasonic attenuations if their grain size distributions are different and that no unique solution in terms of the grain size exists for a particular ultrasonic attenuation against frequency curve. Qualitative agreement has been found between the theory and some of the experimental data available.     

A study of nanosized zinc oxide and its nanofluid

The synthesis and characterization of nanosized zinc oxide and its nanofluid in a polyvinyl alcohol (PVA) matrix have been done in the present investigation. Crystalline zinc oxide nanoparticles are synthesized using single-step chemical method while the nanofluids are prepared by the dispersion of nanoparticles in PVA solution using an ultrasonicator. The prepared nanoparticles are characterized using X-ray diffraction, SEM?CEDX and UV?Cvisible spectrum. The particle size distribution measurement is carried out by acoustic particle sizer. The ultrasonic velocities are measured in the synthesized nanofluid under different physical conditions using an ultrasonic interferometer. It is found that the degree of crystallinity of nanoparticles depends on the evaporation rate during its synthesis and ultrasonic velocity has non-linear relation with temperature for the present nanofluid.     

Effect of ultrasonic treatment on the structure and functional properties of mantle proteins from scallops (Patinopecten yessoensis)

In this study, scallop mantle protein was treated by ultrasound at different powers, and then analyzed by ANS fluorescent probes, circular dichroism spectroscopy, endogenous fluorescence spectrum, DNTB colorimetry and in-vitro digestion model to elucidate the structure–function relationship. The results indicated that ultrasound can significantly affect the secondary structure of scallop mantle protein like enhancing hydrophobicity, lowering the particle size, increasing the relative contents of α-helix and decreasing contents of β-pleated sheet, β-turn and random coil, as well as altering intrinsic fluorescence intensity with blue shift of maximum fluorescence peak. But ultrasound had no effect on its primary structure. Moreover, the functions of scallop mantle protein were regulated by modifying its structures by ultrasound. Specifically, the protein had the highest performance in foaming property and in-vitro digestibility under ultrasonic power of 100 W, oil binding capacity under 100 W, water binding capacity under 300 W, solubility and emulsification capacity under 400 W, and emulsion stability under 600 W. These results prove ultrasonic treatment has the potential to effectively improve functional properties and quality of scallop mantle protein, benefiting in comprehensive utilization of scallop mantles.