Monitorization of alveolar deposited surface area of nanoparticles and ultrafine particles in different environments

Nanotechnology is an important emerging industry with a projected annual market of around one trillion dollars by 2015. It involves the control of atoms and molecules to create new materials with a variety of useful functions. Although there are advantages on the utilization of these nano-scale materials, questions related with its impact over the environment and human health must be addressed too, so that potential risks can be limited at early stages of development. At this time, occupational health risks associated with manufacturing and use of nanoparticles are not yet clearly understood. However, workers may be exposed to nanoparticles through inhalation at levels that can greatly exceed ambient concentrations. Current workplace exposure limits are based on particle mass, but this criteria could not be adequate in this case as nanoparticles are characterized by very large surface area, which has been pointed out as the distinctive characteristic that could even turn out an inert substance into another substance exhibiting very different interactions with biological fluids and cells. Therefore, it seems that, when assessing human exposure based on the mass concentration of particles, which is widely adopted for particles over 1 μm, would not work in this particular case. In fact, nanoparticles have far more surface area for the equivalent mass of larger particles, which increases the chance they may react with body tissues. Thus, it has been claimed that surface area should be used for nanoparticle exposure and dosing. As a result, assessing exposure based on the measurement of particle surface area is of increasing interest. It is well known that lung deposition is the most efficient way for airborne particles to enter the body and cause adverse health effects. If nanoparticles can deposit in the lung and remain there, have an active surface chemistry and interact with the body, then, there is potential for exposure. It was showed that surface area plays an important role in the toxicity of nanoparticles and this is the metric that best correlates with particle-induced adverse health effects. The potential for adverse health effects seems to be directly proportional to particle surface area. The objective of the study is to identify and validate methods and tools for measuring nanoparticles during production, manipulation and use of nanomaterials.

Study of Annealed Indium Tin Oxide-Films prepared by RF Reactive Magnetron Sputtering

Tin doped indium oxide (ITO) films were deposited on glass substrates by rf reactive magnetron sputtering using a metallic alloy target (In-Sn, 90-10). The post-deposition annealing has been done for ITO films in air and the effect of annealing temperature on the electrical, optical and structural properties of ITO films was studied. It has been found that the increase of the annealing temperature will improve the film electrical properties. The resistivity of as deposited film is about 1.3 x 10(-1) Omega*cm and decreases down to 6.9 x 10(-3) Omega*cm as the annealing temperature is increased up to 500 degrees C. In addition, the annealing will also increase the film surface roughness which can improve the efficiency of amorphous silicon solar cells by increasing the amount of light trapping.

Determination of airborne nanoparticles in elderly care centres

According to numerous studies, airborne nanoparticles have a potential to produce serious adverse human health effects when deposited into the respiratory tract. The most important parts of the lung are the alveolar regions with their enormous surface areas and potential to transfer nanoparticles into the blood stream. These effects may be potentiated in case of the elderly, since this population is more susceptible to air pollutants in general and more to nanoparticles than larger particles. The main goal of this investigation was to determine the exposure of institutionalized elders to nanoparticles using Nanoparticle Surface Area Monitor (NSAM) equipment to calculate the deposited surface area (DSA) of nanoparticles into elderly lungs. In total, 193 institutionalized individuals over 65 yr of age were examined in four elderly care centers (ECC). The occupancy daily pattern was achieved by applying a questionnaire, and it was concluded that these subjects spent most of their time indoors, including the bedroom and living room, the indoor microenvironments with higher prevalence of elderly occupancy. The deposited surface area ranged from 10 to 46 μm2/cm3. The living rooms presented significantly higher levels compared with bedrooms. Comparing PM10 concentrations with nanoparticles deposited surface area in elderly lungs, it is conceivable that living rooms presented the highest concentration of PM10 and were similar to the highest average DSA. The temporal distribution of DSA was also assessed. While data showed a quantitative fluctuation in values in bedrooms, high peaks were detected in living rooms.

Synthesis and characterization of rabies virus glycoprotein-tagged amphiphilic cyclodextrins for siRNA delivery in human glioblastoma cells: in vitro analysis

In man brain cancer is an aggressive, malignant form of tumour, it is highly infiltrative in nature, is associated with cellular heterogeneity and affects cerebral hemispheres of the brain. Current drug therapies are inadequate and an unmet clinical need exists to develop new improved therapeutics. The ability to silence genes associated with disease progression by using short interfering RNA (siRNA) presents the potential to develop safe and effective therapies. In this work, in order to protect the siRNA from degradation, promote cell specific uptake and enhance gene silencing efficiency, a PEGylated cyclodextrin (CD)-based nanoparticle, tagged with a CNS-targeting peptide derived from the rabies virus glycoprotein (RVG) was formulated and characterized. The modified cyclodextrin derivatives were synthesized and co-formulated to form nanoparticles containing siRNA which were analysed for size, surface charge, stability, cellular uptake and gene-knockdown in brain cancer cells. The results identified an optimised co-formulation prototype at a molar ratio of 1:1.5:0.5 (cationic cyclodextrin:PEGylated cyclodextrin:RVG-tagged PEGylated cyclodextrin) with a size of 281±39.72nm, a surface charge of 26.73±3mV, with efficient cellular uptake and a 27% gene-knockdown ability. This CD-based formulation represents a potential nanocomplex for systemic delivery of siRNA targeting brain cancer.

Determination of airborne nanoparticles in elderly care centres

According to numerous studies, airborne nanoparticles have a potential to produce serious adverse human health effects when deposited into the respiratory tract. The most important parts of the lung are the alveolar regions with their enormous surface areas and potential to transfer nanoparticles into the blood stream. These effects may be potentiated in case of the elderly, since this population is more susceptible to air pollutants in general and more to nanoparticles than larger particles. The main goal of this investigation was to determine the exposure of institutionalized elders to nanoparticles using Nanoparticle Surface Area Monitor (NSAM) equipment to calculate the deposited surface area (DSA) of nanoparticles into elderly lungs. In total, 193 institutionalized individuals over 65 yr of age were examined in four elderly care centers (ECC). The occupancy daily pattern was achieved by applying a questionnaire, and it was concluded that these subjects spent most of their time indoors, including the bedroom and living room, the indoor microenvironments with higher prevalence of elderly occupancy. The deposited surface area ranged from 10 to 46 mu m(2)/cm(3). The living rooms presented significantly higher levels compared with bedrooms. Comparing PM10 concentrations with nanoparticles deposited surface area in elderly lungs, it is conceivable that living rooms presented the highest concentration of PM10 and were similar to the highest average DSA. The temporal distribution of DSA was also assessed. While data showed a quantitative fluctuation in values in bedrooms, high peaks were detected in living rooms.

Emissions of nanoparticles during friction stir welding (FSW) of aluminium alloys

Friction stir welding (FSW) is now well established as a welding process capable of joining some different types of metallic materials, as it was (1) found to be a reliable and economical way of producing high quality welds, and (2) considered a "clean" welding process that does not involve fusion of metal, as is the case with other traditional welding processes. The aim of this study was to determine whether the emission of particles during FSW in the nanorange of the most commonly used aluminum (Al) alloys, AA 5083 and AA 6082, originated from the Al alloy itself due to friction of the welding tool against the item that was being welded. Another goal was to measure Al alloys in the alveolar deposited surface area during FSW. Nanoparticles dimensions were predominantly in the 40- and 70-nm range. This study demonstrated that microparticles were also emitted during FSW but due to tool wear. However, the biological relevance and toxic manifestations of these microparticles remain to be determined.

Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes

fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.

Surface morphology and phase transformations of femtosecond laser-processed saphire

The morphological and structural modifications induced in sapphire by surface treatment with femtosecond laser radiation were studied. Single-crystal sapphire wafers cut parallel to the (0 1 2) planes were treated with 560 fs, 1030 nm wavelength laser radiation using wide ranges of pulse energy and repetition rate. Self-ordered periodic structures with an average spatial periodicity of similar to 300 nm were observed for fluences slightly higher than the ablation threshold. For higher fluences the interaction was more disruptive and extensive fracture, exfoliation, and ejection of ablation debris occurred. Four types of particles were found in the ablation debris: (a) spherical nanoparticles about 50 nm in diameter; (b) composite particles between 150 and 400 nm in size; (c) rounded resolidified particles about 100-500 nm in size; and (d) angular particles presenting a lamellar structure and deformation twins. The study of those particles by selected area electron diffraction showed that the spherical nanoparticles and the composite particles are amorphous, while the resolidified droplets and the angular particles, present a crystalline a-alumina structure, the same of the original material. Taking into consideration the existing ablation theories, it is proposed that the spherical nanoparticles are directly emitted from the surface in the ablation plume, while resolidified droplets are emitted as a result of the ablation process, in the liquid phase, in the low intensity regime, and by exfoliation, in the high intensity regime. Nanoparticle clusters are formed by nanoparticle coalescence in the cooling ablation plume. (C) 2013 Elsevier B.V. All rights reserved.

Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

Mechanical properties of stent-graft materials

An aneurysm is a localized blood-filled dilatation of an artery whose consequences can be deadly. One of its current treatments is endovascular aneurysm repair, a minimally invasive procedure in which an endoprosthesis, called a stent-graft, is placed transluminally to prevent wall rupture. Early stent-grafts were custom designed for the patient through the assembling of off-the-shelf components by the operating surgeon. However, nowadays, stent-grafts have become a commercial product. The existing endoprostheses differ in several aspects, such as shape design and materials, but they have in common a metallic scaffold with a polymeric covering membrane. This article aims to gather relevant information for those who wish to understand the principles of stent-grafts and even to develop new devices. Hence, a stent-graft classification based on different characteristics is presented and the desired features for an ideal device are pointed out. Additionally, the materials currently in use to fabricate this type of endoprosthesis are reviewed and new materials are suggested.

Assessment of exposure to airborne ultrafine particles in the urban environment of Lisbon, Porugal

The aim of this study was the assessment of exposure to ultrafine in the urban environment of Lisbon, Portugal, due to automobile traffic, and consisted of the determination of deposited alveolar surface area in an avenue leading to the town center during late spring. This study revealed differentiated patterns for weekdays and weekends, which could be related with the fluxes of automobile traffic. During a typical week, ultrafine particles alveolar deposited surface area varied between 35.0 and 89.2 mu m(2)/cm(3), which is comparable with levels reported for other towns such in Germany and the United States. These measurements were also complemented by measuring the electrical mobility diameter (varying from 18.3 to 128.3 nm) and number of particles that showed higher values than those previously reported for Madrid and Brisbane. Also, electron microscopy showed that the collected particles were composed of carbonaceous agglomerates, typical of particles emitted by the exhaustion of diesel vehicles. Implications: The approach of this study considers the measurement of surface deposited alveolar area of particles in the outdoor urban environment of Lisbon, Portugal. This type of measurements has not been done so far. Only particulate matter with aerodynamic diameters <2.5 (PM2.5) and >10 (PM10) mu m have been measured in outdoor environments and the levels found cannot be found responsible for all the observed health effects. Therefore, the exposure to nano- and ultrafine particles has not been assessed systematically, and several authors consider this as a real knowledge gap and claim for data such as these that will allow for deriving better and more comprehensive epidemiologic studies. Nanoparticle surface area monitor (NSAM) equipments are recent ones and their use has been limited to indoor atmospheres. However, as this study shows, NSAM is a very powerful tool for outdoor environments also. As most lung diseases are, in fact, related to deposition of the alveolar region of the lung, the metric used in this study is the ideal one.

Comparison of deposited surface area of airbone ultrafine particles generated from two welding processes

This article describes work performed on the assessment of the levels of airborne ultrafine particles emitted in two welding processes metal-active gas (MAG) of carbon steel and friction-stir welding (FSW) of aluminium in terms of deposited area in alveolar tract of the lung using a nanoparticle surface area monitor analyser. The obtained results showed the dependence from process parameters on emitted ultrafine particles and clearly demonstrated the presence of ultrafine particles, when compared with background levels. The obtained results showed that the process that results on the lower levels of alveolar-deposited surface area is FSW, unlike MAG. Nevertheless, all the tested processes resulted in important doses of ultrafine particles that are to be deposited in the human lung of exposed workers.

Determiation of airborne nanoparticles from welding operations

The aim of this study is to assess the levels of airborne ultrafine particles emitted in welding processes (tungsten inert gas [TIG], metal active gas [MAG] of carbon steel, and friction stir welding [FSW] of aluminum) in terms of deposited area in pulmonary alveolar tract using a nanoparticle surface area monitor (NSAM) analyzer. The obtained results showed the dependence of process parameters on emitted ultrafine particles and demonstrated the presence of ultrafine particles compared to background levels. Data indicated that the process that resulted in the lowest levels of alveolar deposited surface area (ADSA) was FSW, followed by TIG and MAG. However, all tested processes resulted in significant concentrations of ultrafine particles being deposited in humans lungs of exposed workers.

Molybdenum – and tungsten(II) monometallic 3-(2-pyridyl)pyrazole and bimetallic 3-(2-pyridyl)pyrazolate complexes

Molybdenum and tungsten complexes containing the pypzH (3-(2-pyridyl)pyrazole) ligand as a chelating bidentate are prepared: [Mo(CO)(4)(pypzH)], cis-[MoBr(eta(3)-allyl)(CO)(2)(pypzH)], cis-[MoCl(eta(3)-methallyl)(CO)(2)(pypzH)], [MI2(CO)(3)(pypzH)] (M = Mo, W) from [Mo(CO)(4)(NBD)] or the adequate bis(acetonitrile) complexes. The deprotonation of the molybdenum allyl or methallyl complexes affords the bimetallic complexes [cis-{Mo(eta(3)-allyl)(CO)(2)(mu(2)-pypz)}](2) or [cis-{Mo(eta(3)-methallyl)(CO)(2)(mu(2)-pypz)}](2) (mu(2)-pypz = mu(2)-3-(2-pyridyl-kappa N-1) pyrazolate-2 kappa N-1). The allyl complex was subjected to an electrochemical study, which shows a marked connection between both metallic centres through the bridging pyridylpyrazolates.

Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerization

The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.