Enhancing Removal of Pollutants by Combining Photocatalysis and Photo-Fenton Using Co, Fe-Doped Titanate Nanowires.

Aiming to improve their photocatalytic performance, titanate nanowires (TNW) were modified by Fe and Co (co)-doping, FeTNW, CoTNW and CoFeTNW samples, using a hydrothermal methodology. XRD characterization agrees with the existence of Fe and Co in the lattice structure.and the existence of Co2+ together with the presence of Fe2+ and Fe3+ in the structure was confirmed by XPS. The optical characterization of the modified powders shows the impact of the d-d transitions of both metals in the absorption properties of TNW, mainly in the creation of additional 3d energetic levels within the prohibited zone. The effect of the doping metal(s) in the recombination rate of photo-generated charge carriers suggests a higher impact of Fe presence when compared to Co. The photocatalytic characterization of the prepared samples was evaluated via the removal of acetaminophen. Furthermore, a mixture containing both acetaminophen and caffeine, a well-known commercial combination, was also tested. CoFeTNW sample was the best photocatalyst for the degradation of acetaminophen in both situations. A mechanism for the photo-activation of the modified semiconductor is discussed and a model proposed. It was concluded that both Co and Fe are essential, within the TNW structure, for the successful removal of acetaminophen and caffeine.

Impact of Fe, Mn co-doping in titanate nanowires photocatalytic performance for emergent organic pollutants removal.

The unexpected incorporation of ionic Mn and Fe in the crystalline structure of titanate nanowires was accomplished when a contaminated a titanium source was used. The presence of Mn (8.1 mg L-1) and Fe (4.3 mg L-1) result in the production of a novel co-doped (Fe,Mn) titanate nanowires (TNW) material with improved optical and photocatalytic properties. After structural characterization, the results indicate that both Mn and Fe were incorporated in the TNW structure by replacement of Na+ in the interlayers, together with Ti4+ substitution in the TiO6 octahedra. The potential of this new material to be used for pollutants photocatalytic degradation was further investigated. The terephthalic acid was used as probe molecule to first evaluate the catalytic ability of the pristine and FeMnTNW modified powders for the photo-assisted hydroxyl radical formation. Afterwards, the degradation process of a model emergent pollutant, caffeine, was studied. The results showed that FeMnTNW was the best photocatalyst, with the complete caffeine removal (20 mg L-1) within 60 min of radiation (13 mg catalyst/L solution). The action of several oxidant species, including h+, OH• and O2•-, during caffeine removal was carefully analyzed using specific radical scavengers. A mechanism for the charge-transfer in irradiated FeMnTNW particles, including the possibility of a photo-Fenton and photodegradation combination process, is proposed and discussed.

The effect of ionic Co presence on the structural, optical and photocatalytic properties of modified cobalt-titanate nanotubes.

With the aim of producing materials with enhanced optical and photocatalytic properties, titanate nanotubes (TNTs) modified by cobalt doping (Co-TNT) and by Na(+)→ Co ion-exchange (TNT/Co) were successfully prepared by a hydrothermal method. The influence of the doping level and of the cobalt position in the TNT crystalline structure was studied. Although no perceptible influence of the cobalt ion position on the morphology of the prepared titanate nanotubes was observed, the optical behaviour of the cobalt modified samples is clearly dependent on the cobalt ions either substituting the Ti(4+) ions in the TiO6 octahedra building blocks of the TNT structure (doped samples) or replacing the Na(+) ions between the TiO6 interlayers (ion-exchange samples). The catalytic ability of these materials on pollutant photodegradation was investigated. First, the evaluation of hydroxyl radical formation using the terephthalic acid as a probe was performed. Afterwards, phenol, naphthol yellow S and brilliant green were used as model pollutants. Anticipating real world situations, photocatalytic experiments were performed using solutions combining these pollutants. The results show that the Co modified TNT materials (Co-TNT and TNT/Co) are good catalysts, the photocatalytic performance being dependent on the Co/Ti ratio and on the structural metal location. The Co(1%)-TNT doped sample was the best photocatalyst for all the degradation processes studied.

Composição química e toxicidade frente Aedes aegypti L. e Artemia salina Leach do óleo essencial das folhas de Myrcia sylvatica (G. Mey. ) DC. / Chemical composition and toxicity against Aedes aegypti L. and Artemia salina Leach of the essential oil from Myrcia sylvatica (G. Mey. ) DC. leaves.

RESUMO A dengue está entre as doenças virais de propagação vetorial mais importante no mundo, causando sérios impactos de morbidade e mortalidade. Desta forma, o presente trabalho teve como objetivo analisar a composição química e a toxicidade do óleo essencial de Myrcia sylvatica (G. Mey) D.C. frente Aedes aegypti e Artemia salina. Folhas de M. sylvatica foram coletadas no Parque Nacional da Chapada das Mesas, no município de Carolina (MA) no mês de fevereiro de 2012. O óleo foi obtido por hidrodestilação e sua composição química foi determinada por cromatografia gasosa acoplada à espectrometria de massa (CG/EM). O bioensaio frente Artemia salina e às larvas de 3° estádio de Aedes aegypti foram realizados em diferentes concentrações. Os dados de mortalidade foram avaliados por regressão linear para determinar os valores de CL50. Obteve-se 0,5% de rendimento, sendo o (E)-cariofileno o constituinte majoritário. O óleo essencial apresentou uma CL50 = 79,44 µg/mL frente A. salina, sendo considerado altamente tóxico. No entanto, este óleo não demonstrou efeito sobre as larvas de A. aegypti. Considerando que o teste de Artemia salina tem correlação com atividades biológicas de grande interesse terapêutico como antitumoral, o óleo essencial das folhas de M. sylvatica demonstrou potencial para desenvolvimento de produtos farmacêuticos.

ABSTRACT Dengue is among the most important viral diseases of vector spread in the world, causing serious impacts of morbidity and mortality. Thus, this study aimed to analyze the chemical composition and toxicity of the Myrcia sylvatica (G. Mey.) DC essential oil against Aedes aegypti and Artemia salina Leach. Leaves of M. sylvatica. were collected in the Tables Chapada National Park, in the municipality of Carolina (MA) in february 2012. The oil was obtained by hydrodistillation and their chemical composition was determined by GC / MS. The bioassay front and Artemia salina larvae of the 3° stage of Aedes aegypti were performed at different concentrations. Mortality data were evaluated by linear regression to determine the LC50. Was obtained 0.5% yield values, and (E) -caryophyllene the major constituent. The essential oil showed a LC50 = 79.44 mg / mL front A. saline and is considered highly toxic. However, this oil showed no effect on larvae of A. aegypti. Whereas the brine shrimp test has regard to several biological activities, as antitumoral property, the essential oil from the leaves of M. sylvatica demonstrated potential for development of medicines.

Green synthesis of covellite nanocrystals using biologically generated sulfide: potential for bioremediation systems.

This work describes the synthesis of CuS powders in high yield and via an environmentally friendly and straightforward process, under ambient conditions (temperature and pressure), by adding to aqueous copper (II) a nutrient solution containing biologically generated sulfide from sulfate-reducing bacteria (SRB). The powders obtained were composed of CuS (covellite) nanoparticles (NPs) exhibiting a spheroid morphology (<5 nm). The relevance of this method to obtain CuS supported solid substrates has been demonstrated by performing the synthesis in the presence of TiO2 and SiO2 submicron particles. We further extended the work carried out, which substantiates the potential of using biogenic sulfide for the production of covellite nanocrystals and composites, using the effluent of a bioremediation column. Hence, such process results in the synthesis of added value products obtained from metal rich effluents, such as metallurgical and industrial ones, or Acid Mine Drainage (AMD), when associated with bioremediation processes.

Ferromagnetic order in aged Co-doped TiO2 anatase nanopowders.

This paper reports on the ferromagnetic properties of aged Ti(1-x)CoxO(2-delta) anatase nanopowders with different Co contents (0.03 < or = x < or = 0.10). It is shown for the first time that aged Co:TiO2 anatase samples retain rather high values of magnetization (M), remanence (Mr) and coercivity (Hc) which provide strong evidence for a preserved long-range ferromagnetic order. Room temperature M, Mr and Hc values were measured in the ranges of [0.05, 0.79] microB/Co, [0.044, 0.096] microB/Co and [366.7,494.8]Oe, respectively, which are in the same range as in general reported either for newly prepared thin films or nanoparticles.

Photocatalytic decolorization of methylene blue in the presence of TiO2/ZnS nanocomposites.

The synthesis of distinct nanocrystalline TiO2 capped ZnS samples was carried out using a chemical deposition method. The materials characterization showed that the presence of ZnS onto TiO2 surface results in a red shift of the material band edge when compared with the initial semiconductor. The photocatalytic activity of the prepared nanocomposites was tested on the decolorization of methylene blue (MB) aqueous solutions. The dye photodecolorization process was studied considering the influence of experimental parameters such as catalyst concentration, TiO2/ZnS ratio, pH and methylene blue adsorption rate. The material with the best catalytic activity towards the methylene blue photodecolorization was the TiO2 doped with 0.2% of ZnS. The complete photodecolorization of a 20ppm methylene blue solution, at natural pH was achieved in less than 20min, nearly 70min faster than the TiO2 photoassisted process.

Relationship between Cu and Zn extractable foliar contents and BCR sequential extraction in soil treated with organic amendments.

The application of organic wastes to soils, such as municipal solid waste compost (MSWC) or treated urban sewage sludge (USS) is a current practice for maintaining soil organic matter, reclaiming degraded soils and supplying plant nutrients. Since USS and MSWC may contain organic contaminants, heavy metals or pathogens, this practice represents a potential problem to the environment. In the case of heavy metals both bioavailability and toxicity seems to be critically dependent on the chemical form of the element. In this work, a pot experiment was carried out with different levels of MSWC and USS, as well as an inorganic solution of Cu and Zn. The aim was to obtain information about their bioavailability, mobility and toxicity and correlation among the different soil extracted fractions (F1--Exchangeable metal associated with carbonated phases, F2--Reducible metal or associated with Fe and Mn oxides, F3--Oxidizable metal bound to organic matter) with the Cu and Zn foliar (Cu(F) and Zn(F)) and pseudo totals contents (Cu(Ptotal) and Zn(Ptotal)), using the BCR sequential and aqua regia extraction procedure. Both of these methods were adequate to predict the Cu and Zn available to the plant, as high values on the Cu(F)-Cu(sigma123), Cu(F)-Cu(Ptotal), Zn(F)-Zn(sigma123) and Zn(F)-Zn(Ptotal) correlations were verified. Copper bounded mainly to F3, while Zn bounded to F1, F2 and F3 fractions and the regression analysis revelled that Cu and Zn ryegrass absorption were made mainly on F1 and F3 for Cu and F1 for Zn.

Bonding in liquid carbon studied by time-resolved x-ray absorption spectroscopy.

Even the most basic properties of liquid carbon have long been debated due to the challenge of studying the material at the required high temperature and pressure. Liquid carbon is volatile and thus inherently transient in an unconstrained environment. In this paper we use a new technique of picosecond time-resolved x-ray absorption spectroscopy to study the bonding of liquid carbon at densities near that of the solid. As the density of the liquid increases, we see a change from predominantly sp-bonded atomic sites to a mixture of sp, sp2, and sp3 sites and compare these observations with molecular dynamics simulations.

Vagotomy reduces obesity in MSG-treated rats.

In order to study the role of vagus nerve activity at the onset of obesity induced by monosodium glutamate (MSG), 30-day-old MSG-rats were vagotomized or sham operated. Body weight and food intake were recorded until animals were 90 days old and then sacrificed. Naso-anal length was recorded for all animals. Periepididymal and retroperitoneal fat pads were isolated and weighed. Reduction of body weight and naso-anal length were registered in 30-day-old MSG-rats. Obesity could also be observed, as increase of Lee index indicated. Results were most evident in 90-day-old MSG-rats. In both groups neither body weight gain nor food intake was changed by vagotomy. However, fat accumulation on tissues was reduced by vagotomy in MSG-rats. The results showed that MSG-obesity is not related to an increment in food intake behavior. Vagotonia might play a role at the onset of MSG-obesity.

Some studies of crosslinking chitosan-glutaraldehyde interaction in a homogeneous system.

Chitosan dissolved in acetic acid reacted with glutaraldehyde solution, ranging in concentration from 0.10 to 25.0 x 10(-2) mol dm3. The modified polymers were characterized by means of carbon, hydrogen and nitrogen elemental analysis, scanning electron microscopy, X-ray diffractometry, 13C nuclear magnetic resonance (NMR), infrared and Raman spectroscopies. The uptake of metallic cations in aqueous medium was checked through copper. The obtained data from 13C NMR, infrared and Raman spectroscopies evidenced the formation of an ethylenic double bond in the chitosan glutaraldehyde interaction. These data suggest that free pendant amine groups of chitosan polymer interact with the aldehydic group of the glutaraldehyde to form stable imine bonds, due to the resonance established with adjacent double ethylenic bonds. The crosslinking is formed by the nonuniform length of chains and by terminal unities. The crosslinking formation can involve two chitosan unities belonging, or not, to the same polymeric chain. The sequence of reactions was established for a chitosan:glutaraldehyde molar proportion of 1:20. The degree of crystallinity and particle size decreased as the amount of glutaraldehyde was increased in the polymer. Physical and chemical properties are not just affected for the chitosan glutaraldehyde reaction, but are also affected strongly by the dissolution of the natural chitosan.

Silicon nitride coating on titanium to enable titanium-ceramic bonding.

Failures that occur in titanium-ceramic restorations are of concern to clinicians. The formation of poorly adhering oxide on titanium at dental porcelain sintering temperatures causes adherence problems between titanium and porcelain, which is the main limiting factor in the fabrication of titanium-ceramic restorations. To overcome this problem a 1-microm thick Si3N4 coating was applied to a titanium surface using a plasma-immersion implantation and deposition method. Such a coating serves as an oxygen diffusion barrier on titanium during the porcelain firings. The protective coating was characterized in the as-deposited condition and after thermal cycling. Cross sections of Ti/Si3N4-porcelain interface regions were examined by various electron microscopy methods and by energy dispersive analysis of X-rays to study the Si3N4 film's effectiveness in preventing titanium oxidation and in forming a bond with porcelain. The experiments have shown that this Si3N4 coating enables significant improvement in Ti-ceramic bonding.

Bioactive surface coatings for nanoscale instruments: effects on CNS neurons.

A method is described for depositing onto medical instruments highly biocompatible and bioactive surface coatings that can promote and stabilize cell attachment. The coatings were made by first depositing thin films of materials, such as diamond-like carbon, or metals, including tantalum, tungsten, platinum, gold, iridium, palladium, and brass. These surfaces were further altered to either promote or inhibit cell growth and spreading by an additional overcoat of biological materials, including the extracellular matrix proteins, laminin, fibronectin, and collagen IV. The deposition technique used a metal or carbon plasma, and the important properties of film adhesion, hardness, density, and smoothness are tailored by control of the ion bombardment energy. The films are translucent enough to permit high resolution light microscopy for rapid and detailed examination of tissue response. These bioactive substrates have been tested on primary central nervous system neurons, and the growth response is excellent. Equally successful have been our attempts to anchor neurons, without associated proliferation of non-neuronal cells, using coatings of poly-d-lysine. The method and the materials could have important ramifications in a number of areas of research and biotechnology, for example for chronic implantation of microelectrode arrays in the cerebral cortex for neuroprosthetic and neural monitoring application and for research on the human central nervous system. Possible application in nonneuronal fields, such as for coronary artery stents and pacemaker electrodes, also are discussed.

Measles control in Maputo, Mozambique, using a single dose of Schwarz vaccine at age 9 months.

In Maputo city, immunization is available at government health facilities, all contacts being used to vaccinate children. Door-to-door mobilization is conducted to identify eligible children and refer them for immunization. Card-documented measles vaccine coverage, estimated by community surveys, rose from 48% in 1982 to 86% in 1986 and 92% in 1992. The median age at measles vaccination was 10.2 months in 1986 and 9.2 months in 1992. The reported measles incidence rates per 100,000 population fell by 92% from 569 in 1977-78 (pre-vaccination) to 44 in 1990-92, and the reported inpatient measles mortality fell from 19.8 to 0.7 per 100,000. Among children whose age at measles onset was known, the proportion of reported measles cases in children under 9 months of age fell from 2162 (20.3% of 10,636 cases) in 1982-85 to 1695 (17.8% of 9501 cases) in 1986-92. The proportion of cases in children aged > or = 5 years increased from 15.2% to 32.8% in the corresponding periods. The global goals for measles control can be achieved by a single dose of Schwarz vaccine at 9 months of age.

PIP: In the attempt to reduce measles mortality by 95% and morbidity by 90% from pre-vaccination levels by 1995, the World Health Organization recommends district-level immunization coverage of greater than 90% and that emphasis be given to measles control in urban areas. This article describes the use of a single dose of Schwarz vaccine administered at nine months of age to control measles in Maputo, Mozambique. Measles vaccine was introduced to the city in early 1979 during a nationwide campaign reaching an estimated 95% of children aged nine months to five years. The national Expanded Program on Immunization was launched in 1981, with vaccination since then delivered daily at well-baby clinics in 18 government health facilities, and since 1991 at another health center once per week. A team of 18 municipal workers also have gone door-to-door since 1983 to identify eligible children and refer them for immunization. Community survey data indicate that card-documented measles vaccine coverage increased from an estimated 48% in 1982 to 86% in 1986 to 92% in 1992. The median age at measles vaccination of 10.2 months in 1986 had declined to 9.2 months by 1992. Moreover, the reported rates of measles incidence per 100,000 population fell from 569 in 1977-78 to 44 in 1990-92, while reported inpatient measles mortality fell from 19.8 to 0.7 per 100,000. Among children whose age at measles onset was known, the proportion of reported measles cases in children under 9 months old fell from 20.3% in 1982-85 to 17.8% in 1986-92, while the proportion of cases among children five years old and older increased from 15.2% to 32.8% in the corresponding periods. These surveillance findings point to the potential for the administration of a single dose of Schwarz vaccine at nine months of age to realize the global goals for measles control.