Monitoring of transient cavitation induced by ultrasound and intense pulsed light in presence of gold nanoparticles

One of the most important challenges in medical treatment is invention of a minimally invasive approach in order to induce lethal damages to cancer cells. Application of high intensity focused ultrasound can be beneficial to achieve this goal via the cavitation process. Existence of the particles and vapor in a liquid decreases the ultrasonic intensity threshold required for cavitation onset. In this study, synergism of intense pulsed light (IPL) and gold nanoparticles (GNPs) has been investigated as a means of providing nucleation sites for acoustic cavitation. Several approaches have been reported with the aim of cavitation monitoring. We conducted the experiments on the basis of sonochemiluminescence (SCL) and chemical dosimetric methods. The acoustic cavitation activity was investigated by determining the integrated SCL signal acquired over polyacrylamide gel phantoms containing luminol in the presence and absence of GNPs in the wavelength range of 400–500 nm using a spectrometer equipped with cooled charged coupled devices (CCD) during irradiation by different intensities of 1 MHz ultrasound and IPL pulses. In order to confirm these results, the terephthalic acid chemical dosimeter was utilized as well. The SCL signal recorded in the gel phantoms containing GNPs at different intensities of ultrasound in the presence of intense pulsed light was higher than the gel phantoms without GNPs. These results have been confirmed by the obtained data from the chemical dosimetry method. Acoustic cavitation in the presence of GNPs and intense pulsed light has been suggested as a new approach designed for decreasing threshold intensity of acoustic cavitation and improving targeted therapeutic effects.     

Effect of gold nanoparticle size on acoustic cavitation using chemical dosimetry method

When a liquid is irradiated with high intensities of ultrasound irradiation, acoustic cavitation occurs. Acoustic cavitation generates free radicals from the breakdown of water and other molecules. Cavitation can be fatal to cells and is utilized to destroy cancer tumors. The existence of particles in liquid provides nucleation sites for cavitation bubbles and leads to decrease the ultrasonic intensity threshold needed for cavitation onset. In the present investigation, the effect of gold nanoparticles with appropriate amount and size on the acoustic cavitation activity has been shown by determining hydroxyl radicals in terephthalic acid solutions containing 15, 20, 28 and 35 nm gold nanoparticles sizes by using 1 MHz low level ultrasound. The effect of sonication intensity in hydroxyl radical production was considered.The recorded fluorescence signal in terephthalic acid solutions containing gold nanoparticles was considerably higher than the terephthalic acid solutions without gold nanoparticles at different intensities of ultrasound irradiation. Also, the results showed that the recorded fluorescence signal intensity in terephthalic acid solution containing finer size of gold nanoparticles was lower than the terephthalic acid solutions containing larger size of gold nanoparticles. Acoustic cavitation in the presence of gold nanoparticles can be used as a way for improving therapeutic effects on the tumors.     

Influence of dissolved gases on sonochemistry and sonoluminescence in a flow reactor

In the present work, the influence of gas addition is investigated on both sonoluminescence (SL) and radical formation at 47 and 248 kHz. The frequencies chosen in this study generate two distinct bubble types, allowing to generalize the conclusions for other ultrasonic reactors. In this case, 47 kHz provides transient bubbles, while stable ones dominate at 248 kHz. For both bubble types, the hydroxyl radical and SL yield under gas addition followed the sequence: Ar > Air > N₂ >> CO₂. A comprehensive interpretation is given for these results, based on a combination of thermal gas properties, chemical reactions occurring within the cavitation bubble, and the amount of bubbles. Furthermore, in the cases where argon, air and nitrogen were bubbled, a reasonable correlation existed between the OH-radical yield and the SL signal, being most pronounced under stable cavitation at 248 kHz. Presuming that SL and OH originate from different bubble populations, the results indicate that both populations respond similarly to a change in acoustic power and dissolved gas. Consequently, in the presence of non-volatile pollutants that do not quench SL, sonoluminescence can be used as an online tool to qualitatively monitor radical formation.     

Sonoluminescence characterization of inertial cavitation inside a BSA phantom treated by pulsed HIFU

The aim of this study was to investigate the inertial cavitation inside a phantom treated by pulsed HIFU (pHIFU). Basic bovine serum albumin (BSA) phantoms without any inherent ultrasound contrast agents (UCAs) or phase-shift nano-emulsions (PSNEs) were used. During the treatment, sonoluminescence (SL) recordings were performed to characterize the spatial distribution of inertial cavitation adjacent to the focal region. High-speed photographs and thermal coagulations, comparing with the SL results, were also recorded and presented. A series of pulse parameters (pulse duration (PD) was between 1 and 23 cycles and pulse repetition frequency (PRF) was between 0.5 kHz and 100 kHz) were performed to make a systematic investigation under certain acoustic power (APW). Continuous HIFU (cHIFU) investigation was also performed to serve as control group. It was found that, when APW was 19.5 W, pHIFU with short PD was much easier to form SL adjacent to the focal region inside the phantom, while it was difficult for cHIFU to generate cavitation bubbles. With appropriate PD and PRF, the residual bubbles of the previous pulses could be stimulated by the incident pulses to oscillate in a higher level and even violently collapse, resulting to enhanced physical thermogenesis. The experimental results showed that the most violent inertial cavitation occurs when PD was set to 6 cycles (5 μs) and PRF to 10 kHz, while the highest level of thermal coagulation was observed when PD was set to 10 cycles. The cavitational and thermal characteristics were in good correspondence, exhibiting significant potentiality regarding to inject-free cavitation bubble enhanced thermal ablation under lower APW, compared to the conventional thermotherapy.     

Wavelength-dependent Faraday–Tyndall effect on laser-induced microbubble in gold colloid

The cavitation microbubbles in dilute gold colloids of different concentrations (2–10 ppm) induced by a focused nanosecond-pulsed laser beam were measured and characterized at different wavelengths by using the passive and active ultrasound measurements. Three colloids with gold nanoparticles (GNPs) of different sizes (10, 45, and 75 nm) were used for experiment. The results show that the lifespan of the microbubble is reduced as the concentration of GNP increases, particularly at the wavelength of 532 nm, the surface plasmon resonance (SPR) of GNP. In contrast, at the off-resonant wavelength (e.g. 700 nm), the lifespan reduction is relatively small. This wavelength-dependent cavitation is attributed to the Faraday–Tyndall effect, a strong light scattering by GNPs. A slight defocusing of the Gaussian beam in gold colloid was proposed. Hence, the waist of the focused beam increases to reduce the optical breakdown in gold colloid. For simplicity, a linear relation between the incremental waist radius of Gaussian beam and the concentration of GNP was assumed. According to this formulation, the theoretical results are consistent with the experimental ones. In addition, the dynamics of the microbubble in gold colloid measured by the active ultrasound method agree with the Rayleigh–Plesset model.     

Micro- and nano-spheres of low melting point metals and alloys,formed by ultrasonic cavitation

Metals and alloys of low melting points (<430 °C) can be melted in hot silicone oil to form two immiscible liquids. Irradiation of the system with ultrasonic energy induces acoustic cavitation in the oil, which disperses the molten metals into microspheres that solidify rapidly upon cooling. This method has been applied to seven pure metals (Ga, In, Sn, Bi, Pb, Zn, Hg) and two eutectic alloys of gold (Au–Ge and Au–Si). The morphology and composition of the resulting microspheres were examined by SEM and EDS. Eutectic Au–Si formed also crystalline Au nanoparticles, which were separated and studied by HRTEM.     

Spectroscopic study of singlet oxygen photogeneration by lipophilic photosensitiser in liposomes

The time- and spectrally-resolved phosphorescence measurements of protoporphyrin IX (PpIX), haematoporphyrin (HpD) and singlet oxygen in liposomal samples under different oxygen concentrations were performed. We observed two different phosphorescence lifetimes of two distinct groups of photosensitisers (PSs). The group with shorter lifetime is located deep inside the nonpolar lipid bilayer, whereas the group with longer lifetime is exposed to H₂O due to its localisation near the bilayer surface. When the oxygen concentration in H₂O is increased about five times, a significant change in the slower decay component of the group of PS near the surface was observed from 3.8 to 1.3 μs (HpD) and from 3.3 to 1.2 μs (PpIX). On the other hand, the shorter phosphorescence components exhibit less-pronounced changes in lifetimes from 0.42 to 0.39 μs (HpD) and from 0.28 to 0.25 μs (PpIX). The singlet oxygen decay time decreases from 7.3 to 3.5 μs (PpIX) and from 8.0 to 3.5 μs (HpD) in H₂O. The results are discussed in the frame of a model, where an increase of the oxygen concentration in the aqueous medium is accompanied by only a slight increase of the oxygen concentration inside the lipid bilayer.     

Phase transitions and kinetic properties of gold nanoparticles confined between two-layer graphene nanosheets

The thermodynamic and kinetic behaviors of gold nanoparticles confined between two-layer graphene nanosheets (two-layer-GNSs) are examined and investigated during heating and cooling processes via molecular dynamics (MD) simulation technique. An EAM potential is applied to represent the gold–gold interactions while a Lennard–Jones (L–J) potential is used to describe the gold–GNS interactions. The MD melting temperature of 1345 K for bulk gold is close to the experimental value (1337 K), confirming that the EAM potential used to describe gold–gold interactions is reliable. On the other hand, the melting temperatures of gold clusters supported on graphite bilayer are corrected to the corresponding experimental values by adjusting the ε_Au–C value. Therefore, the subsequent results from current work are reliable. The gold nanoparticles confined within two-layer GNSs exhibit face center cubic structures, which is similar to those of free gold clusters and bulk gold. The melting points, heats of fusion, and heat capacities of the confined gold nanoparticles are predicted based on the plots of total energies against temperature. The density distribution perpendicular to GNS suggests that the freezing of confined gold nanoparticles starts from outermost layers. The confined gold clusters exhibit layering phenomenon even in liquid state. The transition of order–disorder in each layer is an essential characteristic in structure for the freezing phase transition of the confined gold clusters. Additionally, some vital kinetic data are obtained in terms of classical nucleation theory.     

Probing the interaction of Au,Rh and bimetallic Au–Rh clusters with the TiO2 nanowire and nanotube support

Gold, rhodium and their coadsorbed layers were prepared on titanate nanowires and nanotubes and characterized by X-ray photoelectron spectroscopy (XPS), low energy ion scattering spectroscopy (LEIS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). On titanate nanowire and tube supports the gold 4f_7/2 XP emission appeared after reduction at 83.7 eV and 85.6 eV indicating two different sizes or chemical environments of gold nanoclusters. The titanate nanostructures stabilize the nearly atomically dispersed state of gold (85.6 eV peaks in XPS). Small clusters also developed in rhodium containing samples besides the pure metallic state. Upon CO adsorption on Rh/titanate nanostructures the IR stretching frequencies characteristic of twin form were dominant, whereas bimetallic nanosystems featured a pronounced linear stretching vibration. By performing careful XPS, LEIS and SEM experiments, it was found that, for appropriate Au and Rh coverage, the Au almost completely covers the Rh nanoparticles. CO adsorbed on this surface may induce the surface reconstruction.     

The adsorption of acetic acid on clean and oxygen-covered Au/Pd(100) alloy surfaces

The adsorption of acetic acid is studied on clean and oxygen-covered Au/Pd(100) alloys as a function of gold content by temperature-programmed desorption and reflection–absorption infrared spectroscopy. Au/Pd(100) forms ordered alloys such that, for gold coverages above ~ 0.5 monolayers, only isolated palladium atoms surrounded by gold nearest neighbors are present. Predominantly molecular acetic acid forms on Au/Pd(100) alloy surfaces for gold coverages greater than ~ 0.56 ML, and desorbs with an activation energy of ~ 59 kJ/mol. Heating this surface also forms some η¹-acetate species which decompose to form CO and hydrogen. On alloy surfaces with palladium–palladium bridge sites, η¹-acetate species initially form, but rapidly convert into η²-species. They thermally decompose to form CO and hydrogen, with a small portion rehydrogenating to form acetic acid between 280 and 321 K depending on gold coverage. The presence of oxygen on both Pd(100) and Au/Pd(100) alloys facilitates acetate dehydrogenation so that only η²-acetate species form on these surfaces. The presence of oxygen also serves to stabilize the acetate species.     

Electrical properties of a nanoparticle-networked film

We have developed a new technique for the preparation of conducting nanoparticle films, which consisted of gold nanoparticles networked with binding molecules such as butanethiol, pentanehtiol, hexanethiol, and heptanethiol, on a polystyrene substrate through a one-step straightforward procedure. The film conductivity became significantly higher with a decrease in the alkylchain length, depending on the number of carbon atoms (n) of the binder molecule between adjacent Au nanoparticles, in which it was changed from an insulator (n > 10) to conductor (n = 4). The film resistivity (2.1 μΩ cm) prepared using butanethiol corresponds to that of planar gold (1.3 μΩ cm).     

Towards an understanding and control of cavitation activity in 1 MHz ultrasound fields

Various industrial processes such as sonochemical processing and ultrasonic cleaning strongly rely on the phenomenon of acoustic cavitation. As the occurrence of acoustic cavitation is incorporating a multitude of interdependent effects, the amount of cavitation activity in a vessel is strongly depending on the ultrasonic process conditions. It is therefore crucial to quantify cavitation activity as a function of the process parameters. At 1 MHz, the active cavitation bubbles are so small that it is becoming difficult to observe them in a direct way. Hence, another metrology based on secondary effects of acoustic cavitation is more suitable to study cavitation activity. In this paper we present a detailed analysis of acoustic cavitation phenomena at 1 MHz ultrasound by means of time-resolved measurements of sonoluminescence, cavitation noise, and synchronized high-speed stroboscopic Schlieren imaging. It is shown that a correlation exists between sonoluminescence, and the ultraharmonic and broadband signals extracted from the cavitation noise spectra. The signals can be utilized to characterize different regimes of cavitation activity at different acoustic power densities. When cavitation activity sets on, the aforementioned signals correlate to fluctuations in the Schlieren contrast as well as the number of nucleated bubbles extracted from the Schlieren Images. This additionally proves that signals extracted from cavitation noise spectra truly represent a measure for cavitation activity. The cyclic behavior of cavitation activity is investigated and related to the evolution of the bubble populations in the ultrasonic tank. It is shown that cavitation activity is strongly linked to the occurrence of fast-moving bubbles. The origin of this “bubble streamers” is investigated and their role in the initialization and propagation of cavitation activity throughout the sonicated liquid is discussed. Finally, it is shown that bubble activity can be stabilized and enhanced by the use of pulsed ultrasound by conserving and recycling active bubbles between subsequent pulsing cycles.     

Facile strategy for stability control of gold nanoparticles synthesized by aqueous reduction method

A facile strategy for controlling sizes and stabilities of gold nanoparticles synthesized by aqueous reduction method was experimentally examined and reported. When pH of the solution of HAuCl₄ and Na₃C₆H₅O₇ was controlled by introducing either NaOH or HCl with different concentration, the zeta potential of suspension of gold nanoparticles changed accordingly. With the strategy using a control of pH in a range of 5–9, the zeta potential of synthesized gold nanoparticles was regulated in a range of −60 to −40 mV, resulting in a stable red suspension of gold nanoparticles. Under a condition with pH < 5.0, gold nanoparticles could agglomerate after being kept quiescently for a day due to an adsorption of H⁺ on their surface, which in turn enhanced the attractive van der Waals interaction. On the other hand, synthesis of gold nanoparticles with pH > 9.1 would provide a lower amount of gold nanoparticles due to the formation of NaAuO₂. Based on these results, a potential mechanism of gold nanoparticle synthesis was also discussed.     

Diffraction patterns and nonlinear optical properties of gold nanoparticles

Stable gold nanoparticles have been prepared by using soluble starch as both the reducing and stabilizing agents; this reaction was carried out at 40 °C for 5 h. The obtained gold nanoparticles were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM) and z-scan technique. The size of these nanoparticles was found to be in the range of 12–22 nm as analyzed using transmission electron micrographs. The optical properties of gold nanoparticles have been measured showing the surface plasmon resonance. The second-order nonlinear optical (NLO) properties were investigated by using a continuous-wave (CW) He–Ne laser beam with a wavelength of 632.8 nm at three different incident intensities by means of single beam techniques. The nonlinear refractive indices of gold nanoparticles were obtained from close aperture z-scan in order of 10^?7 cm²/W. Then, they were compared with diffraction patterns observed in far-field. The nonlinear absorption of these nanoparticles was obtained from open aperture z-scan technique. The values of nonlinear absorption coefficient are obtained in order of 10^?1 cm/W.     

Sonosynthesis of gold nanoparticles from a geranium leaf extract

A rapid in situ biosynthesis of gold nanoparticles (AuNPs) is proposed in which a geranium (Pelargonium zonale) leaf extract was used as a non-toxic reducing and stabilizing agent in a sonocatalysis process based on high-power ultrasound. The synthesis process took only 3.5 min in aqueous solution under ambient conditions. The stability of the nanoparticles was studied by UV–Vis absorption spectroscopy with reference to the surface plasmon resonance (SPR) band. AuNPs have an average lifetime of about 8 weeks at 4 °C in the absence of light. The morphology and crystalline phase of the gold nanoparticles were characterized by transmission electron microscopy (TEM). The composition of the nanoparticles was evaluated by electron diffraction and X-ray energy dispersive spectroscopy (EDS). A total of 80% of the gold nanoparticles obtained in this way have a diameter in the range 8–20 nm, with an average size of 12 ± 3 nm. Fourier transform infrared spectroscopy (FTIR) indicated the presence of biomolecules that could be responsible for reducing and capping the biosynthesized gold nanoparticles. A hypothesis concerning the type of organic molecules involved in this process is also given. Experimental design linked to the simplex method was used to optimize the experimental conditions for this green synthesis route. To the best of our knowledge, this is the first time that a high-power ultrasound-based sonocatalytic process and experimental design coupled to a simplex optimization process has been used in the biosynthesis of AuNPs.     

Performance improvement of ZnO/P3HT hybrid UV photo-detector by interfacial Au nanolayer

In this study, a hybrid ultraviolet (UV) photo detector comprising of hydrothermally grown highly oriented Zinc Oxide nanorod arrays (ZnO NRAs) and Poly(3-hexylthiophene-2,5-diyl) (P3HT) as an active layer was fabricated and characterized. These hybrid photo detectors demonstrated a high rectification ratio (∼117) and responsivity of 10.7 A/W at −2  V under incident light of wavelength 325 nm. Further to investigate the effect of surface plasmon property of metal nanoparticles on the performance of hybrid UV photo detectors, ZnO NRAs were capped with dc sputtered gold (Au) metal nanolayer (∼5 nm) at the ZnO-P3HT interface, prior to coating P3HT layer on top of it. It was found out that upon Au coating the absorption of the ZnO was enhanced partly in the ultraviolet and visible region. In consequence the rectification ratio and responsivity of the hybrid photo detector was enhanced drastically from 117 to 1167 and 10.7 to 17.7 A/W respectively. Interestingly the reduction in dark current was observed on Au coating and it was revealed that Au nanoparticles play a key role in enhancing the performance of the hybrid photo detectors.     

A comparison of the dosimetric characteristics of a glass rod dosimeter and a thermoluminescent dosimeter for mailed dosimeter

A radiophotoluminescent glass rod dosimeter (RPL-GRD) system has recently become commercially available. The purpose of this study was to investigate the dosimetric characteristics (reproducibility, linearity, fading, energy dependence and angular dependence) of the RPL-GRD for a mailed dosimeter and to compare it with LiF-TLD powder. In this study, the model GD-301 GRD and TLD-700 were powder type used. All measurements with the exception of angular dependence were performed in a water phantom using a holder stand. The RPL-GRD has better reproducibility than the TLD for the Co-60 beam as well as for the clinical photon beam. The RPL-GRD signal was linear as a function of applied dose in the range of 0.5–3 Gy for the Co-60 gamma rays. The fading of the RPL-GRD after a received dose of 2 Gy was initially found to be within 1.7% for five months. The energy dependence of both dosimeters was found to be less than 1.6% for photon beams, but was less than 5.0% for electron beams, which was in agreement with published data. The angular dependence of the RPL-GRD was measured to be approximately 1.4% for angles ranging ±90° from the beam axis using a spherical polystyrene phantom. The measurements comparing RPL-GRD and TLD dosimetric characteristics demonstrated that the RPL-GRD is suitable for mailed dosimetry in a quality assurance (QA) audit program.     

Precise spatial control of cavitation erosion in a vessel phantom by using an ultrasonic standing wave

In atherosclerotic inducement in animal models, the conventionally used balloon injury is invasive, produces excessive vessel injuries at unpredictable locations and is inconvenient in arterioles. Fortunately, cavitation erosion, which plays an important role in therapeutic ultrasound in blood vessels, has the potential to induce atherosclerosis noninvasively at predictable sites. In this study, precise spatial control of cavitation erosion for superficial lesions in a vessel phantom was realised by using an ultrasonic standing wave (USW) with the participation of cavitation nuclei and medium-intensity ultrasound pulses. The superficial vessel erosions were restricted between adjacent pressure nodes, which were 0.87 mm apart in the USW field of 1 MHz. The erosion positions could be shifted along the vessel by nodal modulation under a submillimetre-scale accuracy without moving the ultrasound transducers. Moreover, the cavitation erosion of the proximal or distal wall could be determined by the types of cavitation nuclei and their corresponding cavitation pulses, i.e., phase-change microbubbles with cavitation pulses of 5 MHz and SonoVue microbubbles with cavitation pulses of 1 MHz. Effects of acoustic parameters of the cavitation pulses on the cavitation erosions were investigated. The flow conditions in the experiments were considered and discussed. Compared to only using travelling waves, the proposed method in this paper improves the controllability of the cavitation erosion and reduces the erosion depth, providing a more suitable approach for vessel endothelial injury while avoiding haemorrhage.     

Dosimetric evaluation of alanine-in-glass dosimeters at clinical dose levels using high-energy X-rays from a linear accelerator

This study presents the first dosimetric evaluation of the alanine-in-glass dosimeter in radiation therapy. The dosimeter is composed of a Pyrex glass tube filled with pure polycrystalline alanine. 6 MV X-ray beams from a linear accelerator were used to irradiate the dosimeter in a solid water phantom to therapy-level doses ranging from 0 to 30 Gy. An X-band electron paramagnetic resonance (EPR) spectrometer was utilized to measure the absorbed dose of the dosimeter. The doses measured by the dosimeter were compared to those from ion chamber dosimetry. It was found that the dosimeter exhibited a linear response in the dose range from 0.1 to 30 Gy. The deviation between measured and delivered doses was 0.11% over the 0.5–30 Gy range, whereas the deviation increased to about 25% at 0.1 Gy. The lowest detectable dose with an acceptable deviation limit of 5% or less was found to be 0.3 Gy. The inaccuracy in measurements at low doses can be attributed to background signals and instrument noise. The accuracy can be improved by proper selection of measurement conditions and better optimization of equipment. The findings of this study show that the alanine-in-glass dosimeter is suitable for dose measurements with acceptable accuracy down to 0.3 Gy. The dosimeter is therefore has the potential to be employed in radiotherapy applications and quality control procedures.     

Sonoluminescence quenching and cavitation bubble temperature measurements in an ionic liquid

A comparison between the temperatures within imploding acoustic cavitation bubbles and the extent of sonoluminescence (SL) quenching by C₁–C₅ aliphatic alcohols in 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO₄], a well known imidazolium based room temperature ionic liquid (RTIL)), has been made at an ultrasound frequency of 213 kHz. The temperatures obtained ranged from 3500 ± 200 K, in neat [EMIM][EtSO₄], to about 3200 ± 200 K in RTIL-alcohol containing solutions. It was also found that the SL intensity decreased with increasing concentration (up to 1 M) of the alcohols to a greater extent compared with the relative changes to the bubble temperatures. Both the extent of the reduction in the bubble temperatures and the SL quenching were much smaller than those obtained in comparable aqueous solutions containing aliphatic alcohols. Possible reasons for the differences in the observed trends between water/alcohol and [EMIM][EtSO₄]/alcohol systems under sonication at 213 kHz are discussed.