Biomechanical effects of environmental and engineered particles on human airway smooth muscle cells

The past decade has seen significant increases in combustion-generated ambient particles, which contain a nanosized fraction (less than 100 nm), and even greater increases have occurred in engineered nanoparticles (NPs) propelled by the booming nanotechnology industry. Although inhalation of these particulates has become a public health concern, human health effects and mechanisms of action for NPs are not well understood. Focusing on the human airway smooth muscle cell, here we show that the cellular mechanical function is altered by particulate exposure in a manner that is dependent upon particle material, size and dose. We used Alamar Blue assay to measure cell viability and optical magnetic twisting cytometry to measure cell stiffness and agonist-induced contractility. The eight particle species fell into four categories, based on their respective effect on cell viability and on mechanical function. Cell viability was impaired and cell contractility was decreased by (i) zinc oxide (40-100 nm and less than 44 mu m) and copper(II) oxide (less than 50 nm); cell contractility was decreased by (ii) fluorescent polystyrene spheres (40 nm), increased by (iii) welding fumes and unchanged by (iv) diesel exhaust particles, titanium dioxide (25 nm) and copper(II) oxide (less than 5 mu m), although in none of these cases was cell viability impaired. Treatment with hydrogen peroxide up to 500 mu M did not alter viability or cell mechanics, suggesting that the particle effects are unlikely to be mediated by particle-generated reactive oxygen species. Our results highlight the susceptibility of cellular mechanical function to particulate exposures and suggest that direct exposure of the airway smooth muscle cells to particulates may initiate or aggravate respiratory diseases.

Vanadium complexes with thiosemicarbazones: Synthesis, characterization, crystal structures and anti-Mycobacterium tuberculosis activity

The development of more efficient anti-tuberculosis drugs is of interest. Three oxovanadium(IV) and three cis-dioxovanadium(V) complexes with thiosemicarbazone derivatives bearing moieties with different lipophilicity have been prepared and had their inhibitory activity against Mycobacterium tuberculosis H(37)Rv ATCC 27294 evaluated. The analytical methods used by the complexes` characterization included IR, EPR, (1)H, (13)C and (51)V NMR spectroscopies, elemental analysis, cyclic voltammetry, magnetic susceptibility measurement and single crystal X-ray diffractometry. [VO(acac)(aptsc)], [VO(acac)(apmtsc)] and [VO(acac)(apptsc)] (acac = acetylacetonate; Haptsc = 2-acetylpyridinethiosemicarbazone; Hapmtsc = 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc = 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone) are paramagnetic and their EPR spectra are consistent with the monoanionic N,N,S-tridentate coordination of the thiosemicarbazone ligands, resulting in octahedral structures of rhombic symmetry and with the oxidation state +IV for the vanadium atom. As result of oxidation of the vanadium(IV) complexes above, the diamagnetic cis-dioxovanadium(V) complexes [VO(2)(aptsc)[, [VO(2)(apmtsc)[ and [VO(2)(apptsc)] are formed. Their (1)H, (13)C and (51)V NMR spectra were acquired and support a distorted square pyramidal geometry for them, in accord with the solid state X-ray structures determined for [VO(2)(aptsc)] and [VO(2)(apmtsc)]. In general, the vanadium compounds show comparable or larger anti-M. tuberculosis activities than the free thiosemicarbazone ligands, with MIC values within 62.5-1.56 (mu g/mL). (C) 2008 Elsevier Ltd. All rights reserved.

Pt(II) and Ag(I) complexes with acesulfame: Crystal structure and a study of their antitumoral, antimicrobial and antiviral activities

Two new complexes of platinum(II) and silver(I) with acesulfame were synthesized. Acesulfame is in the anionic form acesulfamate (ace). The structures of both complexes were determined by X-ray crystallography. For K(2)[PtCl(2)(ace)(2)] the platinum atom is coordinated to two Cl(-) and two N-acesulfamate atoms forming a trans-square planar geometry. Each K(+) ion interacts with two oxygen atoms of the S(=O)(2) group of each acesulfamate. For the polymeric complex [Ag(ace)](n) the water molecule bridges between two crystallographic equivalent Agl atoms which are related each other by a twofold symmetry axis. Two Agl atoms, related to each other by a symmetry centre, make bond contact with two equivalent oxygen atoms. These bonds give rise to infinite chains along the unit cell diagonal in the ac plane. The in vitro cytotoxic analyses for the platinum complex using HeLa (human cervix cancer) cells show its low activity when compared to the vehicle-treated cells. The Ag(I) complex submitted to in vitro antimycobacterial tests, using the Microplate Alamar Blue (MABA) method, showed a good activity against Mycobacterium tuberculosis, responsible for tuberculosis, with a minimal inhibitory concentration (MIC) value of 11.6 mu M. The Ag(I) complex also presented a promising activity against Gram negative (Escherichia colt and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis) microorganisms. The complex K(2)[PtCl(2)(ace)(2)] was also evaluated for antiviral properties against dengue virus type 2 (New Guinea C strain) in Vero cells and showed a good inhibition of dengue virus type 2 (New Guinea G strain) replication at 200 mu M, when compared to vehicle-treated cells. (C) 2010 Elsevier Inc. All rights reserved.

Ruthenium (II) phosphine/picolinate complexes as antimycobacterial agents

The synthesis, characterization and the anti-Mycobacterium tuberculosis (MTB) activities of three ruthenium complexes containing the 2-pyridinecarboxylic acid anion (picolinate), with formulae cis-[Ru(pic)(dppm)(2)]PF(6) (1), Cis- [Ru(pic)(dppe)(2)]PF(6) (2) and [Ru(pic)(2)(PPh(3))(2)] (3) [pic = 2-pyridinecarboxylate; dppm = bis(diphenylphosphino)methane: dppe = 1,2-bis(diphenylphosphino)ethane; PPh(3) = triphenylphosphine] are reported in this article. The complexes were characterized by elemental analysis, spectroscopic and electrochemical techniques. Their in vitro anti mycobacterial activity was determinated as the Minimum Inhibitory Concentration (MIC) for MTB cell growth, measured by the REMA method. The best MICs were found for complexes (1) and (2), with values of 0.78 and 0.26 mu g/mL, respectively. The results are comparable to or better than ""first line"" or ""second line"" drugs commonly used in the treatment of TB. (C) 2009 Elsevier Masson SAS. All rights reserved.

ON THE NATURE OF THE PROTOTYPE LUMINOUS BLUE VARIABLE AG CARINAE. II. WITNESSING A MASSIVE STAR EVOLVING CLOSE TO THE EDDINGTON AND BISTABILITY LIMITS

We show that the significantly different effective temperatures (T(eff)) achieved by the luminous blue variable AG Carinae during the consecutive visual minima of 1985-1990 (T(eff) similar or equal to 22,800 K) and 2000-2001 (T(eff) similar or equal to 17,000 K) place the star on different sides of the bistability limit, which occurs in line-driven stellar winds around T(eff) similar to 21,000 K. Decisive evidence is provided by huge changes in the optical depth of the Lyman continuum in the inner wind as T(eff) changes during the S Dor cycle. These changes cause different Fe ionization structures in the inner wind. The bistability mechanism is also related to the different wind parameters during visual minima: the wind terminal velocity was 2-3 times higher and the mass-loss rate roughly two times smaller in 1985-1990 than in 2000-2003. We obtain a projected rotational velocity of 220 +/- 50 km s(-1) during 1985-1990 which, combined with the high luminosity (L(star) = 1.5 x 10(6) L(circle dot)), puts AG Car extremely close to the Eddington limit modified by rotation (Omega Gamma limit): for an inclination angle of 90 degrees, Gamma(Omega) greater than or similar to 1.0 for M(circle dot) less than or similar to 60. Based on evolutionary models and mass budget, we obtain an initial mass of similar to 100 M(circle dot) and a current mass of similar to 60-70 M(circle dot) for AG Car. Therefore, AG Car is close to, if not at, the Omega Gamma limit during visual minimum. Assuming M = 70 M(circle dot), we find that Gamma(Omega) decreases from 0.93 to 0.72 as AG Car expands toward visual maximum, suggesting that the star is not above the Eddington limit during maximum phases.

Comparison between blue and green stimulated luminescence of Al(2)O(3):C

This paper presents a systematic comparison of OSL signals from Al(2)O(3):C when stimulated with blue and green light. Al(2)O(3):C detectors were irradiated with various doses and submitted to various bleaching regimes using yellow, green and blue light. Most of the investigations were carried out using Luxel (TM)-type detectors used in the commercial Luxet (TM) and InLight (TM) dosimetry systems (Landauer Inc.). Al(2)O(3):C single crystals and Al(2)O(3):C powder were also used to complement the investigations. The results show that, although blue stimulation provides faster readout times (OSL curves that decayed faster) and higher initial OSL intensity than green stimulation, blue stimulation introduced complicating factors. These include incomplete bleaching of the dosimetric trap when the Al(2)O(3):C detectors are bleached with yellow or green light and the OSL is recorded with blue light stimulation, and an increased residual level due to stimulation of charge carriers from deep traps. The results warrant caution when using blue stimulation to measure the OSL signal from Al(2)O(3):C detectors, particularly if the doses involved are low and the detectors have been previously exposed to high doses. (C) 2010 Elsevier Ltd. All rights reserved.

Thermal and structural properties of commercial dental resins light-cured with blue emitting diodes (LEDs)

We have investigated the thermal and structural properties of different commercial dental resins: Filtek(TM) Z-350, Grandio(A (R)), Tetric Ceram(A (R)), and TPH Spectrum(A (R)). The purpose of the present study was to evaluate quantitatively the photo-polymerization behavior and the effect of filler contents on the kinetic cures of the dental resins by using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. We have successfully obtained the low and high glass transition T (g) values of the dental composite resins from DSC curves. It was also observed a good agreement between the both T (g) values, activation energies from thermal degradation, and the degree of conversion obtained for all samples. The results have shown that Tetric Ceram(A (R)) dental resin presented the higher T (g) values, activation energy of 215 +/- A 6 KJ mol(-1), and the higher degree of conversion (63%) when compared to the other resins studied herein.

Changes on degree of conversion of dual-cure luting light-cured with blue LED

The indirect adhesive procedures constitute recently a substantial portion of contemporary esthetic restorative treatments. The resin cements have been used to bond tooth substrate and restorative materials. Due to recently introduction of the self-bonding resin luting cement based on a new monomer, filler and initiation technology has become important to study the degree of conversion of these new materials. In the present work the polymerization reaction and the filler content of dual-cured dental resin cements were studied by means of infra-red spectroscopy (FT-IR) and thermogravimetry (TG). Twenty specimens were made in a metallic mold (8 mm diameter x 1 mm thick) from each of 2 cements, PanaviaA (R) F2.0 (Kuraray) and RelyX (TM) Unicem Applicap (3M/ESPE). Each specimen was cured with blue LED with power density of 500 mW/cm(2) for 30 s. Immediately after curing, 24 and 48 h, and 7 days DC was determined. For each time interval 5 specimens were pulverized, pressed with KBr and analyzed with FT-IR. The TG measurements were performed in Netzsch TG 209 under oxygen atmosphere and heating rate of 10A degrees C/min from 25 to 700A degrees C. A two-way ANOVA showed DC (%) mean values statistically significance differences between two cements (p < 0.05). The Tukey`s test showed no significant difference only for the 24 and 48 h after light irradiation for both resin cements (p > 0.05). The Relx-Y (TM) Unicem mean values were significantly higher than PanaviaA (R) F 2.0. The degree of conversion means values increasing with the storage time and the filler content showed similar for both resin cements.

Morphology and Blue Photoluminescence Emission of PbMoO(4) Processed in Conventional Hydrothermal

PbMoO(4) micro-octahedrons were prepared by the coprecipitation method at room temperature without the presence of surfactants and processed in a conventional hydrothermal at different temperatures (from 60 to 120 degrees C) for 10 min. These micro-octahedrons were structurally characterized by X-ray diffraction (XRD) and micro-Raman (MR) spectroscopy, and its morphology was investigated by field-emission gun scanning electron microscopy (FEG-SEM). The optical properties were analyzed by ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns and MR spectra confirmed that the PbMoO(4) micro-octahedrons are characterized by a scheelite-type tetragonal structure. FEG-SEM micrographs points, out that these structures present a polydisperse particle size distribution in consequence of a predominant growth mechanism via aggregation of particles. In addition, it was observed that the hydrothermal conditions favored a spontaneous formation of micro-octahedrons interconnected along a common crystallographic orientation (oriented-attachment), resulting in self-organized structures. An intense blue PL emission at room temperature was observed in these micro-octahedrons when they were excited with a 350 nm wavelength. The origin of the PL emissions as well as its intensity variations are explained by means of a model based on both distorted [MoO(4)] and [PbO(8)] clusters into the lattice.

Degree of Conversion and Temperature Increase of a Composite Resin Light Cured with an Argon Laser and Blue LED

Different light sources and power densities used on the photoactivation process may provide changes in the degree of conversion (DC%) and temperature ( T) of the composite resins. Thus, the purpose of this study was to evaluate the DC (%) and T (degrees C) of the microhybrid composite resin (Filtek (TM) Z-250, 3M/ESPE) photoactivated with one argon laser and one LED (light-emitting diode) with different power densities. For the KBr pellet technique, the composite resin was placed into a metallic mould (2-mm thickness, 4-mm diameter) and photoactivated as follows: a continuous argon laser (CW) and LED LCUs with power density values of 100, 400, 700, and 1000 mW/cm(2) for 20 s. The measurements for DC (%) were made in a FTIR spectrometer Bomen ( model MB 102, Quebec, Canada). Spectroscopy ( FTIR) spectra for both uncured and cured samples were analyzed using an accessory of the reflectance diffusion. The measurements were recorded in absorbance operating under the following conditions: 32 scans, 4 cm(-1) resolution, 300 to 4000-cm(-1) wavelength. The percentage of unreacted carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1638 cm(-1)) against an internal standard before and after the curing of the specimen: aromatic C-C (peak at 1608 cm(-1)). For T (degrees C), the samples were created in a metallic mould (2-mm thickness, 4-mm diameter) and photoactivated for 20 s. The thermocouple was attached to the multimeter allowing temperature readings. The DC (%) and T (degrees C) were submitted to ANOVA and Tukey`s test (p < 0.05). The degree of conversion values varied from 35.0 to 50.0% ( 100 to 1000 mW/cm(2)) for an argon laser and from 41.0 to 49% (100 to 1000 mW/cm(2)) for an LED. The temperature change values varied from 1.1 to 13.1 degrees C (100 to 1000 mW/cm(2)) for an argon laser and from 1.9 to 15.0 degrees C (100 to 1000 mW/cm(2)) for an LED. The power densities showed a significant effect on the degree of conversion and changes the temperature for both light-curing units.

Intense violet-blue photoluminescence in BaZrO3 powders: A theoretical and experimental investigation of structural order-disorder

Intense violet-blue photoluminescence (PL) emission at room temperature was verified in BaZrO3 (BZO) powders with structural order-disorder. Ab-initio calculations, ultraviolet-visible absorption spectroscopy and PL were performed. Theoretical results showed that the local disorder in the network-formed Zr clusters present an important role in the formation of hole-electron pair. The experimental data and theoretical results are in agreement, indicating that the PL emission in BZO powders can be related to the structural order-disorder degree in the lattice. (C) 2008 Elsevier B.V. All rights reserved.

Photodynamic therapy associating Photogem (R) and blue LED on L929 and MDPC-23 cell culture

To evaluate the cytotoxicity of PDT (photodynamic therapy) with Photogem (R) associated to blue LED (light-emitting diode) on L929 and MDPC-23 cell cultures, 30000 cells/cm(2) were seeded in 24-well plates for 48 h, incubated with Photogem (R) (10, 25 or 50 mg/l) and irradiated with an LED source (460 +/- 3 nm; 22 mW/cm(2)) at two energy densities (25.5 or 37.5 J/cm(2)). Cell metabolism was evaluated by the MTT (methyltetrazolium) assay (Dunnet`s post hoc tests) and cell morphology by SEM (scanning electron microscopy). Flow cytometry analysed the type of PDT-induced cell death as well and estimated intracellular production of ROS (reactive oxygen species). There was a statistically significant decrease of mitochondrial activity (90% to 97%) for all Photogem (R) concentrations associated to blue LED, regardless of irradiation time. It was also demonstrated that the mitochondrial activity was not recovered after 12 or 24 h, characterizing irreversible cell damage. PDT-treated cells presented an altered morphology with ill-defined limits. In both cell lines, there was a predominance of necrotic cell death and the presence of Photogem (R) or irradiation increased the intracellular levels of ROS. PDT caused severe toxic effects in normal cell culture, characterized by the reduction of the mitochondrial activity, morphological alterations and induction of necrotic cell death.

Photodynamic therapy for American cutaneous leishmaniasis: The efficacy of methylene blue in hamsters experimentally infected with Leishmania (Leishmania) amazonensis

The aim of this study was to investigate the effectiveness of Photodynamic Therapy (PDT) using Methylene Blue (MB) as the photosensitizing compound and a Light-Emitting Diode (LED) in American cutaneous leishmaniasis (ACL). Hamsters were experimentally infected with Leishmania (Leishmania) amazonensis. After the development of the lesions in the footpad, the animals were treated with MB three times a week for 3 months. Ten minutes after each application of MB, the lesions were irradiated with LED for 1 h. The lesions were evaluated weekly by the measurement of the hamster footpad thickness. At the end of the treatment the parasitic load was quantified in the regional lymph node of the hamsters. The treatment promoted a decrease in the thickness of infected footpad (P = 0.0001) and reduction in the parasitic load in the regional lymph node (P = 0.0007) of the animals from group treated with MB + LED. PDT using MB + LED in ACL caused by L. amazonensis shows a strong photodynamic effect. This therapy is very promising, once it is an inexpensive system and the own patient can apply it in their wound and in their house without the need of technical assistance. (C) 2011 Elsevier Inc. All rights reserved.

Structure effects of self-assembled Prussian blue confined in highly organized mesoporous TiO(2) on the electrocatalytic properties towards H(2)O(2) detection

Here we report the derivatization of mesoporous TiO(2) thin films for the preparation of H(2)O(2) amperometric sensors. The coordination of the bifunctional ligand 1,10 phenantroline, 5,6 dione on the surface Ti(IV) ions provides open coordination sites for Fe(II) cations which are the starting point for the growth of a layer of Prussian blue polymer. The porous structure of the mesoporous TiO(2) allows the growth, ion by ion of the coordination polymer. Up to four layer of Prussian blue can be deposit without losing the porous structure of the film, which results in an enhanced response of these materials as H(2)O(2) sensors. These porous confined PB modified electrodes are robust sensors that exhibit good reproducibility, environmental stability and high sensitivity towards H(2)O(2) detection. (C) 2010 Elsevier B.V. All rights reserved.

On the pH dependence of electroactivity of poly(methylene blue) films

The electrochemical behavior of poly(methylene blue) on different electrodes has been investigated by electrochemical quartz crystal microbalance and in situ spectrophotometric measurements coupled to cyclic voltammetry. Polymeric films were obtained potentiodynamically and the charge transport mechanism was analyzed. The electrochemical results show that polymer electroactivity depends not only on pH but also on the substrate. Charge compensation changes with both pH and the size of the anions showing a transition in the pH range of polymer pKa. It was demonstrated by spectroelectrochemical experiments that the electroactivity of the film depends on the radical/radical cation equilibrium. The potentials where the most electroactive species are formed have been determined. (C) 2009 Elsevier Ltd. All rights reserved.