Métodos "verdes" de produção de nanomateriais que promovem nanotecnologias sustentáveis

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química

Morphology and structure of particles produced by femtosecond laser ablation of fused silica

The aim of the present work was to study the morphology and structure of the nanoparticles produced by femtosecond laser ablation of fused silica. Ultrashort laser pulses of 1030 nm wavelength and 550 fs duration were tightly focused by a high numerical aperture microscope objective at the surface of fused silica samples while scanning the sample in relation to the stationary laser beam. Laser tracks were created with pulse energies in the range 5-100 mu J, resulting in ablation debris of different morphologies. The debris were examined by scanning and transmission electron microscopy for their morphology and crystal structure in relation to the incident laser pulse energy. Ejected particles with sizes ranging from a few nanometers to a few microns were found. Their morphologies can be broadly classified into three categories: very fine round nanoparticles with diameters lower than 20 nm, nanoparticles with intermediate sizes between 50 and 200 nm, and big irregular particles with typical size between 0.5 and 1.5 mu m. The fine nanoparticles of the first category are predominantly observed at higher pulse energies and tend to aggregate to form web-like and arborescent-like structures. The nanoparticles with intermediate sizes are observed for all pulse energies used and may appear isolated or aggregated in clusters. Finally, the larger irregular particles of the third category are observed for all energies and appear normally isolated.

A new chemical route to synthesise TM-doped (TM = Co, Fe) TiO2 nanoparticles

Since the discovery of ferromagnetism well above room temperature in the Co-doped TiO2 system, diluted magnetic semiconductors based on TiO2 doped with transition metals have generated great interest because of their potential use in the development of spintronic devices. The purpose of this paper is to report on a new and swift chemical route to synthesise highly stable anatase single-phase Co- and Fe-doped TiO2 nanoparticles, with dopant concentrations of up to 10 at.-% and grain sizes that range between 20 and 30 nm. Complementary structural, microstructural and chemical analyses of the different nanopowders synthesised strongly support the hypothesis that a homogeneous distribution of the dopant element in the substitutional sites of the anatase structure has been achieved. Moreover, UV/Vis diffuse reflectance spectra of powder samples show redshifts to lower energies and decreasing bandgap energies with increasing Co or Fe concentration, which is consistent with n-type doping of the TiO2 anatase matrix. Films of Co-doped TiO2 were successfully deposited onto Si (100) substrates by the dip-coating method, with suspensions of Ti1-xCOxO2 nanoparticles in ethylene glycol. ((C)Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Determination 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.

Homogeneous and heterogenised new gold C-scorpionate complexes as catalysts for cyclohexane oxidation

Gold(III) complexes of type [AuCl2{eta(2)-RC(R'pz)(3)}]Cl [R = R' = H (1), R = CH2OH, R' = H (2) and R = H, R' = 3,5-Me-2(3), pz = pyrazol-1-yl] were supported on carbon materials (activated carbon, carbon xerogel and carbon nanotubes) and used for the oxidation of cyclohexane to cyclohexanol and cyclohexanone, with aqueous H2O2, under mild conditions.

Notice on a methodology for characterizing emissions of ultrafine particles/nanoparticles in microenvironments

Bearing in mind the potential adverse health effects of ultrafine particles, it is of paramount importance to perform effective monitoring of nanosized particles in several microenvironments, which may include ambient air, indoor air, and also occupational environments. In fact, effective and accurate monitoring is the first step to obtaining a set of data that could be used further on to perform subsequent evaluations such as risk assessment and epidemiologic studies, thus proposing good working practices such as containment measures in order to reduce occupational exposure. This paper presents a useful methodology for monitoring ultrafine particles/nanoparticles in several microenvironments, using online analyzers and also sampling systems that allow further characterization on collected nanoparticles. This methodology was validated in three case studies presented in the paper, which assess monitoring of nanosized particles in the outdoor atmosphere, during cooking operations, and in a welding workshop.

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.

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.

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.

Synthesis of Sub-5 NM Co-Doped SnO2 nanoparticles and their structural microstructural, optical and photocatalytic properties

A swift chemical route to synthesize Co-doped SnO2 nanopowders is described. Pure and highly stable Sn1-xCoxO2-delta (0 <= x <= 0.15) crystalline nanoparticles were synthesized, with mean grain sizes <5 nm and the dopant element homogeneously distributed in the SnO2 matrix. The UV-visible diffuse reflectance spectra of the Sn1-xCoxO2-delta samples reveal red shifts, the optical bandgap energies decreasing with increasing Co concentration. The samples' Urbach energies were calculated and correlated with their bandgap energies. The photocatalytic activity of the Sn1-xCoxO2-delta samples was investigated for the 4-hydroxylbenzoic acid (4-HBA) degradation process. A complete photodegradation of a 10 ppm 4-HBA solution was achieved using 0.02% (w/w) of Sn0.95Co0.05O2-delta nanoparticles in 60 min of irradiation. (C) 2014 Elsevier B.V. All rights reserved.

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.

Is it possible to remove polymeric nanoparticles from aqueous paints during the activated sludge treatment?

The market for emulsion polymers (latexes) is large and growing at the expense of other manufacturing processes that emit higher amounts of volatile organic solvents. The paint industry is not an exception and solvent-borne paints have been gradually substituted by aqueous paints. In their life-cycle, much of the aqueous paint used for architectural or decorative purposes will eventually be discharged into wastewater treatment facilities, where its polymeric nanoparticles (mainly acrylic and styrene-acrylic) can work as xenobiotics to the microbial communities present in activated sludge. It is well established that these materials are biocompatible at macroscopic scale. But is their behaviour the same at nanoscale? What happens to the polymeric nanoparticles during the activated sludge process? Do nanoparticles agregate and are discharged together with the sludge or remain in emulsion? How do microorganisms interact with these nanoparticles? Are nanoparticles degradated by them? Are they adsorbed? Are these nanoparticles toxic to the microbial community? To study the influence of these xenobiotics in the activated sludge process, an emulsion of cross-linked poly(butyl methacrylate) nanoparticles of ca. 50 nm diameter was produced and used as model compound. Activated sludge from a wastewater treatment plant was tested by the OCDE’s respiration inhibition test using several concentrations of PBMA nanoparticles. Particle aggregation was followed by Dynamic Light Scattering and microorganism surfaces were observed by Atomic Force Microscopy. Using sequential batch reactors (SBRs) and continuous reactors, both inoculated with activated sludge, the consumption of carbon, ammonia, nitrite and nitrate was monitored and compared, in the presence and absence of nanoparticles. No particles were detected in all treated waters by Dynamic Light Scattering. This can either mean that microorganisms can efficiently remove all polymer nanoparticles or that nanoparticles tend to aggregate and be naturally removed by precipitation. Nevertheless respiration inhibition tests demonstrated that microorganisms consume more oxygen in the presence of nanoparticles, which suggests a stress situation. It was also observed a slight decrease in the efficiency of nitrification in the presence of nanoparticles. AFM images showed that while the morphology of some organisms remained the same both in the presence and absence of nanoparticles, others assumed a rough surface with hilly like shapes of ca. 50 nm when exposed to nanoparticles. Nanoparticles are thus likely to be either incorporated or adsorbed at the surface of some organisms, increasing the overall respiration rate and decreasing nitrification efficiency. Thus, despite its biocompatibility at macroscopic scale, PBMA is likely to be no longer innocuous at nanoscale.

Approaches to tuberculosis mucosal vaccine development using nanoparticles and microparticles: a review

Next-generation vaccines for tuberculosis should be designed to prevent the infection and to achieve sterile eradication of Mycobacterium tuberculosis. Mucosal vaccination is a needle-free vaccine strategy that provides protective immunity against pathogenic bacteria and viruses in both mucosal and systemic compartments, being a promising alternative to current tuberculosis vaccines. Micro and nanoparticles have shown great potential as delivery systems for mucosal vaccines. In this review, the immunological principles underlying mucosal vaccine development will be discussed, and the application of mucosal adjuvants and delivery systems to the enhancement of protective immune responses at mucosal surfaces will be reviewed, in particular those envisioned for oral and nasal routes of administration. An overview of the essential vaccine candidates for tuberculosis in clinical trials will be provided, with special emphasis on the potential different antigens and immunization regimens.