The use of dosimeters to measure radical production in aqueous sonochemical systems

The use of two dosimeter systems for quantifying radical production during aqueous sonochemical processes has been investigated. The Fricke (Fe²⁺/Fe³⁺) system was found to be useful at higher concentrations but care must be taken in interpreting the results since radical production is not the only process taking place. There is some reaction even in the absence of ultrasound and this involves dissolved oxygen gas. The concentration of hydroxyl radicals formed was accurately monitored at low concentrations using the terephthalate dosimeter and the limits of its applicability were found. Both systems were used to investigate the effect of varying the ultrasound intensity.     

Ultrasound-enhanced diffusion through isolated frog skin

The effect of ultrasound on the transport of oxygen across excised frog abdominal skin has been studied. Samples were mounted in an exposure chamber in which the Ringer's solution on one side was saturated with oxygen while the other side of the skin had a low initial oxygen concentration. They were treated with ultrasound at 1, 1.5 and 2 W cm⁻² SATA c.w., respectively, and increases in the rate of oxygen transport were observed at all intensities. These increases ranged from 38 ± 4% at 1 W cm⁻² to 55 ± 8% at 2 W cm⁻². Variation in the pulse lengths from 25 to 200 ms and a constant average intensity did not affect the rate of transport significantly provided that the temporal intensity was constant. Since the peak acoustic pressure within the pulse increased with decreasing pulse length and increasing acoustic pressure increases the probability of cavitation occurring, the mechanism responsible for this phenomenon is probably not cavitation.     

Sonochemistry of cytochrome c. Evidence for superoxide formation by ultrasound in argon-saturated aqueous solution

Formation of superoxide anion radicals (O₂^·−) induced by 50 kHz ultrasound in argon (Ar)-saturated aqueous solution was studied. Although EPR-spin trapping study with 5,5-dimethyl-1-pyrroline N-oxide (DMPO;100 mM) revealed the formation of DMPO-adducts of hydroxyl radicals (^·OH) and hydroperoxy radicals (HO₂^·; acid form of O2^·−) in O₂-saturated solution after sonication, no evidence of HO₂^· was found in Ar-saturated solution. When ferricytochrome c (cytochrome c) in Ar-saturated aqueous solution was sonicated, the reduced form of cytochrome c was observed and 80% of its formation was inhibited by the addition of superoxide dismutase (SOD). Sodium formate enhanced the production of the reduced form of cytochrome c. The % inhibition by SOD for the reduction increased in the order of Xe > Ar > He in accord with the higher temperatures of the cavitation bubbles. These results indicate that the O₂^·− is formed by directly by the sonolysis of water in the absence of O₂ when the temperature of cavitation bubble collapse is sufficiently high.     

Quantification of ultrasonic intensity based on the decomposition reaction of porphyrin

A simple method is proposed for quantification of the effective ultrasonic intensity in the reaction vessel based on the decomposition reaction of 5,10,15,20-tetrakis(4-sulfotophenyl) porphyrin (H₂TPPS⁴⁻). The change of concentration of porphyrin in solution irradiated by the ultrasound wave depends on the irradiation time and the output power of ultrasound generator. The decomposition ratio of porphyrin is defined as the ratio of the concentration of porphyrin after ultrasonic irradiation to that before ultrasonic irradiation. A linear relationship between the decomposition ratio of porphyrin and the concentration Fe³⁺ in the Fricke solution under sonication was obtained. The decomposition ratio was related to the absorption dose in radiation chemistry.     

Ultrasonic absorption frequency dependence of two widely used anti-cancer drugs: doxorubicin and daunorubicin

Low intensity ultrasound (approximately 10⁻⁶ W cm⁻²) in the frequency range 0.5–6.0 MHz was employed to investigate the ultrasound absorption properties of doxorubicin (DOX) at several temperatures. At physiological temperatures, we found enhanced ultrasound absorption from DOX, and its closely related analogue daunorubicin (DNR), in the upper kilohertz frequency range. The findings do not conform to classical theory of ultrasound absorption, thus suggesting an ultrasound coupling with the drug molecules via structural and/or chemical relaxation processes. The absorption spectra are analysed from the point of view of the non-classical theory of sound absorption due to physical and/or chemical relaxations. Only one spectral difference between the two anti-cancer agents is observed, around 2 MHz, and may be attributed to the sole difference in the chemical make-up of the side chain of the two antibiotics.     

Femtosecond laser micro-structuring of aluminium under helium

The interaction of 180 fs, 775 nm laser pulses with aluminium under a flowing stream of helium at ambient pressure have been used to study the material re-deposition, ablation rate and residual surface roughness. Threshold fluence F_th0.4 J cm⁻² and the volume ablation rate was measured to be 30<V<450 μm³ per pulse in the fluence range 1.4<F<21 J cm⁻². The presence of helium avoids gas breakdown above the substrate and leads to improved surface micro-structure by minimising surface oxidation and debris re-deposition. At 1 kHz rep. rate, with fluence F>7 J cm⁻² and >85 W cm⁻² average power density, residual thermal effects result in melt and debris formation producing poor surface micro-structure. On the contrary, surface micro-machining at low fluence F1.4 J cm⁻² with low power density, 3 W cm⁻² produces much superior surface micro-structuring with minimum melt and measured surface roughness R_a1.1±0.1 μm at a depth D50 μm. By varying the combination of fluence/scan speed during ultra-fast ablation of aluminium at 1 kHz rep. rate, results suggest that maintaining average scanned power density to <5 W cm⁻² combined with single pulse fluence <4 J cm⁻² produces near optimum micro-structuring. The debris under these conditions contains pure aluminium nanoparticles carried with the helium stream.     

TEA-CO2 laser generation of ultrasound in non-metals

An industrial TEA-CO₂ laser, operating at a wavelength of 10.6 μm, has been used to produced broadband ultrasonic pulses in polymers. The generation mechanism falls into three categories. At low power densities ≤ 10⁷ W cm⁻² a thermoelastic regime predominates. As the power density is increased in the range (1–5) × 10⁷ W cm⁻² ablation of the material surface plays an increasingly important role in the acoustic generation. Thirdly, at greater power densities, plasma breakdown just above the material surface serves as the means of generation. This paper describes the acoustic sources for these types of generation mechanism and presents theoretically calculated acoustic waveforms to match those recorded experimentally.     

A passive radon dosimeter based on the combination of a track etch detector and activated charcoal

The aim of this work is to test a combination of a Makrofol track detector with a new type of charcoal (Carboxen-564) to design a personal radon dosimeter. The intention is to use this dosimeter as a personal radon dosimeter to measure the monthly radon exposure in workplaces, especially when the occupancy is not ecactly known. The proposed combination was exposed to low and high concentrations of radon in a large range of relative humidity (RH). For the optimal layer thickness, a charcoal bed of 2.2 mm, a specific track density of 5.1 tracks cm⁻²/kBq h m⁻³ was obtained. For a monthly working exposure (170 h) at an average radon concentration of 100 Bq/m³, this means 87 tracks/cm² or 10 times the background of the Makrofol detector, with a statistical uncertainty of 15%.     

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm⁻² under an argon atmosphere. 80–90% of initial amount of these compounds were degraded by 30–60 min of sonication when the initial concentrations were 10–100 μmol l⁻¹. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.     

Vibrational study of silicon oxidation: H2O on Si(100)

The vibrational spectrum of water dissociatively adsorbed on Si(100) surfaces is obtained with surface infrared absorption spectroscopy. Low frequency spectra (< 1450 cm⁻¹ are acquired using a buried CoSi₂ layer as an internal mirror to perform external reflection spectroscopy. On clean Si(100), water dissociates into H and OH surface species as evidenced by EELS results [1] in the literature which show a Si---H stretching vibration (2082 cm⁻¹), and SiO---H vibrations (O---H stretch at 3660 cm⁻¹ and the Si---O---H bend and Si---O stretch of the hydroxyl group centered around 820 cm⁻¹). In this paper, infrared (IR) measurements are presented which confirm and resolve the issue of a puzzling isotopic shift for the Si---O mode of the surface hydroxyl group, namely, that the Si---O stretch of the O---H surface species formed upon H₂O exposure occurs at 825 cm⁻¹, while the Si---O stretch of the ---OD surface species formed upon D₂O exposure shifts to 840 cm⁻¹, contrary to what is expected for simple reduced mass arguments. The higher resolution of IR measurements versus typical EELS measurements makes it possible to identify a new mode at 898 cm⁻¹, which is an important piece of evidence in understanding the anomalous frequency shift. By comparing the results of measurements for adsorption of H¹⁶₂O, H¹⁸₂O and D₂O with the results from recently performed first-principles calculations, it can be shown that a strong vibrational interaction between the Si---O stretching and Si---O---H bending functional group vibrations of the hydroxyl group accounts for the observed isotopic shifts.     

Degradation of Acid Blue 25 in aqueous media using 1700 kHz ultrasonic irradiation: ultrasound/Fe(II) and ultrasound/H2O2 combinations

In this work, the sonolytic degradation of an anthraquinonic dye, C.I. Acid Blue 25 (AB25), in aqueous phase using high frequency ultrasound waves (1700 kHz) for an acoustic power of 14 W was investigated. The sonochemical efficiency of the reactor was evaluated by potassium iodide dosimeter, Fricke reaction and hydrogen peroxide production yield. The three investigated methods clearly show the production of oxidizing species during sonication and well reflect the sonochemical effects of high frequency ultrasonic irradiation. The effect of operational conditions such as the initial AB25 concentration, solution temperature and pH on the degradation of AB25 was studied. Additionally, the influence of addition of salts on the degradation of dye was examined. The rate of AB25 degradation was dependent on initial dye concentration, pH and temperature. Addition of salts increased the degradation of dye. Experiments conducted using distilled and natural waters demonstrated that the degradation was more efficient in the natural water compared to distilled water. To increase the efficiency of AB25 degradation, experiments combining ultrasound with Fe(II) or H₂O₂ were conducted. Fe(II) induced the dissociation of ultrasonically produced hydrogen peroxide, leading to additional OH radicals which enhance the degradation of dye. The combination of ultrasound with hydrogen peroxide looks to be a promising option to increase the generation of free radicals. The concentration of hydrogen peroxide plays a crucial role in deciding the extent of enhancement obtained for the combined process. The results of the present work indicate that ultrasound/H₂O₂ and ultrasound/Fe(II) processes are efficient for the degradation of AB25 in aqueous solutions by high frequency ultrasonic irradiation.     

Dependence of the excitation wavelength on the Raman-active phonons of YBa2Cu3O7 Search for Landau damping in single-domain crystals

In single-domain crystals of YBa₂Cu₃O₇, we examine the dependence of phonon linewidth on wavevector by varying the wavelength of the exciting laser. In three crystals, we find the linewidths of the Raman-active phonons at 120 and 150 cm⁻¹ to be nearly invariant for excitation wavelengths between 647 and 413 nm. That is, we find no broadening of the phonon linewidths with increasing phonon wavevector (decreasing excitation wavelength), and thus no evidence of Landau damping in our crystals. In addition, the correlation between the intensity of the chain-related Raman feature at ≈232 cm⁻¹ and the temperature dependence of the B_1g-like phonon at 340 cm⁻¹ has been investigated. In all three crystals, we find a net sharpening of the 340 cm⁻¹ phonon below T_c and essentially no intensity for the ≈232 cm⁻¹ mode under resonance conditions.     

On the luminescence of LiBaF3:Eu

From the temperature dependence of the line—band luminescence intensity ratio of LiBaF₃:Eu²⁺ a 4f−5d activation energy (Δ) of 800 cm⁻¹ is derived, being much higher than the value reported in the literature (100 cm⁻¹). The temperature dependence of the luminescence decay can be well described with Δ = 800 cm⁻¹ and with 4f−4f and 5d−4f radiative probabilities of 4×10²s⁻¹ and 6×10⁵s⁻¹, respectively.     

Measurement of the absolute oscillator strengths of gadolinium using an atomic vapor produced by electron beam heating

The absolute values of the oscillator strength ƒ were measured for the six spectral lines of Gd by means of laser absorption spectroscopy with the atomic vapor produced by electron beam heating. The ƒ values obtained for the transition are 0–17381 cm⁻¹, 215–17750 cm⁻¹, 533–17795 cm⁻¹, 999–18070 cm⁻¹, 999–17931 cm⁻¹, 1719–18070 cm⁻¹ were obtained to be 0.0036, 0.012, 0.014, 0.019, 0.0075 and 0.039, respectively. The error of ƒ values was 24% due to uncertainty of metastable states' density.     

Vibrational spectroscopy of ordered oxygen adiayers on Ni/Cu(001) and Co/Cu(001) thin film systems

We report surface vibrations in c(2 × 2) oxygen adlayers on Ni and Co thin films on a Cu(001) substrate measured at gG by high resolution EELS. For the Ni thin film surface, one phonon peak is measured for varying film thicknesses from 1.3 ML (monolayer) to 6 ML with a constant energy of 221 cm⁻¹. For the Co thin film surface, three loss peaks are found, whose relative intensities change as the film thicknesses are varied. One loss peak at ˜520 cm⁻¹ is tentatively assigned to the Fuchs-Kliewer mode of cobalt oxide (CoO). The other two peaks at 317 and 376 cm⁻¹ are likely related to different bonding sites. Surface phonons on the p(2 × 2) Co thin film (389 cm⁻¹) and a bulk resonance mode (115 cm⁻¹) are also reported.     

Chemically deposited copper oxide thin films: structural, optical and electrical characteristics

Thin films of copper oxide with thickness ranging from 0.05–0.45 μm were deposited on microscope glass slides by successively dipping them for 20 s each in a solution of 1 M NaOH and then in a solution of copper complex. Temperature of the NaOH solution was varied from 50–90°C, while that of the copper solution was maintained at room temperature. X-ray diffraction patterns showed that the films, as prepared, are of cuprite structure with composition Cu₂O. Annealing the films in air at 350°C converts these films to CuO. This conversion is accompanied by a shift in the optical band gap from 2.1 eV (direct) to 1.75 eV (direct). The films show p-type conductivity, 5×10⁻⁴ Ω⁻¹ cm⁻¹ for a film of thickness 0.15 μm. Electrical conductivity of this film increases by a factor of 3 when illuminated with 1 kW m⁻² tungsten halogen radiation. Annealing in a nitrogen atmosphere at temperatures up to 400°C does not change the composition of the films. However, the conductivity in the dark as well as the photoconductivity of the film increases by an order of magnitude. The electrical conductivity of the CuO thin films produced by air annealing at 400°C, is high, 7×10⁻³ Ω⁻¹ cm⁻¹. These films are also photoconductive.     

Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Proton conductive amorphous thin films of tungsten oxide clusters with acidic ligands

Three kinds of peroxo-polytungstic acid (PPTA, C-PPTA and N-PPTA) were obtained by reacting hydrogen peroxide with metallic tungsten, tungsten carbide or tungsten nitride, respectively. Polytungstates, C-PPTA and N-PPTA, were found to contain oxalate and nitrate ligands. Their proton conductivities were compared using thin film specimens spin-coated from their water solution. Conductivity of each as-coated film was in the range from 10⁻³ to 10⁻⁴ S cm⁻¹ under the relative humidity of 40% (25 °C). A sharp decrease in conductivity (to less than 10⁻⁷ S cm⁻¹ at 25 °C) was observed for PPTA without acidic ligands after thermal treatment at 80 °C. However, the effect of thermal treatment on C-PPTA or N-PPTA was much milder. A 80 °C-treated C-PPTA film showed the conductivity of 1.0 × 10⁻⁵ S cm⁻¹ (25 °C) with a very weak dependency on ambient humidity.     

Ultrasonically induced contractions in mouse uterine smooth muscle in vivo

The uteri of live mice were exposed and placed in the path of an ultrasonic field of frequency 3 MHz and peak intensity 2 W cm⁻². It was found that contractions could be induced within the uterus under these conditions. Uterine activity reverted to its normal level when the ultrasonic field was switched off.     

Far-infrared and millimeter wave spectroscopy of superionic copper conductors

Far-infrared and millimeter wave spectra of copper ion conducting crystal RbCu₄Cl_3+xI_2−x, which has the same structure as the room temperature silver ion conductor RbAg₄I₅, were investigated. Broad absorption peaks observed around 40, 80, and 110–200 cm⁻¹ at room temperature show doublet structures at low temperature; this may be attributed to the difference of local structure by chlorine and iodine ion. The 110–200 cm⁻¹ bands seem to be symmetric breathing modes of CuX₄ (X = Cl or I) tetrahedron and the frequency shift coincides with the square root of the mass ratio of conduction ions. The 80 cm⁻¹ band seems to be Rb-X vibration in RbX₆ octahedron. The 40 cm⁻¹ band seems to be the attempt mode which is an outward motion of the mobile ion in halogen cage. The increase of the absorption intensity at the low energy side with temperature corresponds to an increase of the DC conductivity. Plasmon fitting in energy loss function spectra was attempted.