Novel method for synthesis of aryl hydrazones from α-diazo esters: scope and limitations of nucleophiles

Aryl hydrazones, the precursor of Fischer indole synthesis, were easily obtained by nucleophilic addition of aryllithium reagents to diazo esters. The aryl hydrazones were converted into indoles in good yields by heating with thionyl chloride in alcohol. Grignard reagent was also a good nucleophile, whereas organozinc reagent did not react with diazo esters. Aryllithium reagents were prepared by reacting aryl bromides having various substitutions at 2-, 3-, 4-, or multi positions with n-BuLi. The addition of nucleophiles derived from bromopyridines to diazo esters also gave hydrazones.     

Fabrication of nanosized Pt on rutile TiO2 using a standing wave sonochemical reactor (SWSR) – observation of an enhanced catalytic oxidation of CO

Fine particles of rutile TiO₂ supporting nanosized particles of Pt were prepared by a simultaneous in situ sonochemical reduction and deposition method using a standing wave sonochemical reactor (SWSR). The mean diameter of sonochemically obtained Pt particles are of 2 nm. Following this sonochemical technique, rutile TiO₂ was also deposited with different weight percentages of Pt. Catalytic function of the prepared composite catalysts were tested by the oxidation of CO to CO₂. From the catalytic activity results, it has been found out that the catalysts prepared by the sonochemical method exhibited higher catalytic activity for CO oxidation, probably attributed to the higher Pt particle distribution achieved under sonication. Transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and diffuse reflectance spectroscopy (DRS) were employed to characterize the resulting material.     

CPP-GMR heads with a current screen layer for high areal density

We investigated the potential for high-areal-density recording in current-perpendicular-to-plane giant magnetoresistive (CPP-GMR) heads with a current screen layer. The current screen layer is a nano-oxide layer with confined current paths. We fabricated the current screen CPP-GMR heads with a narrow sensor width of 40–50 nm, a high MR ratio of 17%, and low-resistance-area (RA) product of 0.2 Ω μm². The fabricated heads showed a sufficiently high signal-to-noise ratio (SNR) of 30–40 dB. No extra noise, such as spin-torque noise, was observed. Linear density of 1360 kFCI from the head with the magnetic read width of 45 nm was obtained. Distribution of sensor resistance due to nano-hole area distribution in the current screen layer can be reduced with low-RA film. Spin-torque noise can be suppressed by reducing the current-induced field and controlling the shape anisotropy. Accordingly, the current screen CPP-GMR head is a promising candidate that has the potential for high-areal-density recording.     

Generalized Kerr–NUT–de Sitter metrics in all dimensions

We classify all spacetimes with a closed rank-2 conformal Killing–Yano tensor. They give a generalization of Kerr–NUT–de Sitter spacetimes. The Einstein condition is explicitly solved and written as an indefinite integral. It is characterized by a polynomial in the integrand. We briefly discuss the smoothness conditions of the Einstein metrics over compact Riemannian manifolds.     

Potential antidiabetic zinc(II) complexes of novel 5-oxo-2-thioxopyrrolidine derivatives synthesized via an unprecedented reaction

We have developed a synthetic route to novel ethyl 1-arylmethyl-5-oxo-2-thioxopyrrolidine-3-carboxylates (1a–e) via an unprecedented reaction of ethyl 1-arylmethyl-4-acetoxy-5-oxo-2,5-dihydro-1H-pyrrole-3carboxylates with potassium thioacetate. Synthesized products 1a–e were further converted into their zinc(II) complexes (10a–e), having an S₂O₂-type coordination mode, that showed improved insulin-mimetic activities compared to ZnSO₄, a positive standard, and also the previously reported zinc(II) complexes of ethyl 1-benzyl-4-hydroxy-5-oxo-2,5-dihydro-1H-pyrrole-3-carboxylates with O₄-type coordination mode.     

Genotoxic Responses of Mitochondrial Oxygen Consumption Rate and Mitochondrial Semiquinone Radicals in Tumor Cells

Our recent report demonstrated that genotoxic stimuli enhance mitochondrial energy metabolism in various tumor cell lines. However, the mitochondrial response against genotoxic stimuli has not been fully elucidated. In this study, to investigate mitochondrial functions in X-irradiated cells, the oxygen consumption rate (OCR) in human cervical adenocarcinoma HeLa cells was examined by electron spin resonance (ESR) spectroscopy with lithium 5,9,14,18,23,27,32,36-octa-n-butoxy-2,3-naphthalocyanine. ESR oximetry demonstrated that basal respiration, ATP-linked respiration, proton leak, maximal respiration, and reserve capacity increased in HeLa cells 24 h after X-irradiation. However, a flow cytometric analysis using MitoTracker Green showed that mitochondrial mass also increased following X-irradiation. When the OCR was standardized to the mitochondria membrane mass, the radiation-induced increases in the respiratory parameters disappeared. This finding indicated that the radiation-induced increase in cellular OCR was explained by an increase in mitochondrial mass but not by the activation of mitochondrial respiratory-related enzymes. In addition, mitochondrial semiquinone radicals at g?=?2.004 were detected by low-temperature (110 K) ESR spectroscopy. The ESR signal intensity of semiquinone radicals was enhanced by X-irradiation, suggesting an increase in the electron flow in the electron transport chain. These data will be important to understand the mechanism of radio-sensitization by mitochondria-targeting reagents in tumor cells.     

Ultrasound-induced cytolysis of cancer cells is enhanced in the presence of micron-sized alumina particles

Micron-sized alumina particles have been shown to enhance sonochemical free radical formation in aqueous solutions and simultaneously increase the solution temperature and acoustic (white) noise, effects attributable to enhanced inertial cavitation [T. Tuziuti, J. Phys. Chem. A 109 (2005) 4869–4872]. In the current study, the same ultrasound exposure system was applied to in vitro cancer cells as a model system to determine the effect of alumina particles on the long-term survival of cells and on the major pathways of cell death, i.e., either apoptosis or necrosis. Following 6 h of incubation after ultrasound treatment, it was found that the cells died mainly through necrosis, irrespective of whether the exposure was conducted in the presence of alumina particles or not. Alumina particles were non-toxic to cells alone, but were found to decrease the long-term survivability of cells that survived the initial exposure. This effect depended on the size and concentration of particles. These results correlated well with the effect of alumina particles on the sonochemical oxidation of KI under the same exposure conditions. Spin-trapping with 5,5-dimethyl-pyroline N-oxide (DMPO) and electron spin resonance spectroscopy indicated that the sonochemical formation of OH radicals increased in the presence of alumina particles. The current study is consistent with the well known observation that micron-sized particles enhance the acoustic cavitation process.     

Segregation of vapor and gas in a sonoluminescing bubble

Computer simulations of bubble oscillations in water are performed for various noble gases taking into account the segregation of water vapor and noble gas inside a collapsing bubble, which was predicted by Storey and Szeri [J. Fluid Mech. 396 (1999) 203]. It is clarified that the number of water vapor molecules dissociated inside a collapsing bubble is larger for heavier noble gases because of the lower thermal conductivity and the segregation of vapor and noble gas. It is also clarified that the temperature inside a helium bubble at the collapse increases considerably by the mixture segregation because a lesser amount of vapor is trapped inside a collapsing bubble. It is also clarified that multibubble sonoluminescence (MBSL) from heavier noble gases is brighter because of the lower ionization potential which results in the higher electron density and stronger plasma emissions.     

Influence of dissolved oxygen content on multibubble sonoluminescence with ambient-pressure reduction

The efficiency of chemical reactions in the presence of ultrasound at reduced pressures has been monitored using the influence of dissolved oxygen (DO) content on a luminol solution undergoing multibubble sonoluminescence. From these measurements under the condition of constant ultrasonic frequency and constant amplitude of sound pressure, it is shown that the intensity of sonoluminescence is higher at subatmospheric ambient pressure than at atmospheric pressure under the same degree of saturation. Also, it is found that there is an appropriate content of DO to produce the highest intensity of the luminescence and its value varies with ambient pressure.