Theoretical and X-Ray Evidence of Electrostatic Phosphonium anti and gauche Effects.

Sulphur, not phosphorus, is the only known third-row element capable of experiencing an electrostatic gauche effect with fluorine. Some six-membered rings containing an endocyclic phosphorus atom and a ß-fluorine substituent that can interconvert to axial (gauche relative to phosphorus) and equatorial positions were then analysed. While phosphines do not establish an electrostatic attraction between fluorine and phosphorus, some oxidised forms exhibit surprising stability for the sterically disfavoured axial orientation. Because the nature of this behaviour was not obvious, since an intramolecular hydrogen bond can appear, a phosphonium derivative was further studied and its axial conformation was found to be highly stable. A preference for the gauche arrangement appears even for the acyclic and sterically hindered (2-fluoroethyl)triphenylphosphonium cation. On the other hand, (ethane-1,2-diyl)bis(phosphonium) cations are exclusively in anti conformation due to an (+/+)-electrostatic repulsion between the positively charged phosphonium groups.

Magnetic photocatalysts from δ-FeOOH and TiO2 and application in reactions for degradation of methylene blue and paracetamol with UV-C and sunlight.

Water contamination is a common problem, especially considering dyes and drugs disposal. A possible and effective treatment method to remove these organic pollutants from water is photocatalytic reaction. This study aimed to improve the photocatalytic properties of TiO2 using iron oxides (Ti/Fe composite). Different magnetic photocatalysts based on commercial TiO2 were obtained with 30, 50, and 80% (wt./wt.) of TiO2 supported on maghemite. X-ray diffraction with Rietveld refinement confirms the presence of γ-Fe2O3, α-Fe2O3, anatase, and rutile, as well as the relative percentages of the phases present in each photocatalyst. The magnetic properties were certified by VSM and sedimentation kinetics in the presence of a magnetic field. Besides their magnetic properties, UV-vis DRS shows that the obtained photocatalysts presented lower bandgap values when compared with TiO2. These factors allowed the materials to absorb radiation in the visible-light region and the separation from the reaction medium by the application of magnetic field. It was observed an enhancement of photodegradation reaction of methylene blue (MB) and paracetamol (PC). For example, when the content of TiO2 increased from 30 to 80% (wt./wt.), the efficiency increased from 58 to 99% (for MB) and 39 for 80% (for PC) under UV (λ = 254 nm). The reactions carried out with solar radiation showed 56 to 95% efficiency to discolor MB. In addition, the results of sedimentation kinetics and characterization confirmed the goals of the synthesis.

Purification of arsenic-contaminated water using iron molybdate filters and monitoring of their genotoxic, mutagenic, and cytotoxic effects through bioassays.

Environmental contamination has been a cause of concern worldwide, being aggravated by anthropogenic activities carried out without the correct disposal of toxic products in the various habitats on our planet. In Brazil, mining companies are responsible for the contamination of large river basins with toxic elements from mining activities. Among these elements, arsenic draws attention because it is highly carcinogenic and found in waters in concentrations above those recommended by regulatory agencies. Here, Fe2(MoO4)3 nanoparticles are synthesized and used as a filter medium in water purification systems contaminated with arsenic. The adsorption kinetics of arsenic by Fe2(MoO4)3 nanoparticles is fast, showing pseudo-second-order rate constants of 0.0044, 0.0080, and 0.0106 g mg-1 min-1 for As3+, As5+, and MMA, respectively. The adsorption isotherms are better adjusted with the Langmuir and Redlich-Peterson models, indicating that the arsenic adsorption occurs in monolayers on the Fe2(MoO4)3 surface. The Fe2(MoO4)3 adsorption capacities determined for the As3+, As5+, and MMA species are 16.1, 23.1, and 23.5 mg g-1, respectively. The Fe2(MoO4)3 filter is efficient in purifying arsenic-contaminated water, reducing its initial concentration from 1000 µg L-1 to levels close to zero. Biological tests indicate that Fe2(MoO4)3 nanoparticles and filtered water have no cytotoxic, genotoxic, and mutagenic risks to human life. Those results suggest that the Fe2(MoO4)3 filter can be used as an efficient and safe technology for the purification of water contaminated by arsenic.

New Approach to Dehydration of Xylose to 2-Furfuraldehyde Using a Mesoporous Niobium-Based Catalyst.

Furfural chemistry is one of the most promising platforms directly derived from lignocellulose biomass. In this study, a niobium-based catalyst (mNb-bc) was synthesized by a new fast and simple method. This new method uses microemulsion to obtain a catalyst with a high specific surface area (340 m2 g-1), defined mesoporosity, and high acidity (65 µmol g-1). Scanning electron microscopy revealed that mNb-bc has a rough surface. The mNb-bc was used to catalyze the conversion reaction of xylose into 2-furfuraldehyde in a monophasic system using water as a green solvent. This reaction was investigated using a 23 experimental design by varying the temperature, time, and catalyst-to-xylose ratio (CXR). The responses evaluated were xylose conversion (X c), reaction yield (Y), and selectivity to 2-furfuraldehyde (S). The optimized reaction conditions were used to evaluate the reaction kinetics. At milder reaction conditions of 140 °C, 2 h, and a CXR of 10%, mNb-bc led to an X c value of 41.2%, an S value of 77.1%, and a Y value of 31.8%.

Gold-Coated Superparamagnetic Iron Oxide Nanoparticles Attenuate Collagen-Induced Arthritis after Magnetic Targeting.

The aim of the study was to evaluate if gold-coated superparamagnetic iron oxide nanoparticles (AuSPION) magnetic-targeted to the arthritic articulation of collagen induced arthritis (CIA) rats are able to ameliorate rheumatoid arthritis without producing significant biological adverse effects in comparison to colloidal Au nanoparticles (AuC) and metotrexate (MTX). Male Wistar rats were divided into control; arthritic; AuSPION (150 µg kg-1); AuC (150 µg kg-1) and MTX (2.5 µg kg-1). Treatments were administered thrice every other day by the intraperitoneal route 15 min after all groups had a neodymium magnet coupled to the right ankle joint (kept for 1 h). Paw edema and body weight were measured weekly. Joint sections were evaluated by Haematoxylin & Eosin and immunohistochemistry (TNF-α, IL-1ß). Biomarkers of oxidative stress were used to evaluate toxicity. Among the evaluated treatments, AuSPION led to significant clinical improvements (decreased edema and infiltration by leukocytes as well as less positively immunostained cells for both TNF-α and IL-1ß in synovium) accompanied by a lack of toxicity as indicated by redox state and genotoxicity assays. Our results clearly indicate that the magnetic targeting of AuSPION suppresses joint edema and inflammation, cytokine expression as well as the redox imbalance, thereby contributing to an amelioration of arthritis severity in CIA rats. The results demonstrate for the first time the potentiality of AuSPION administration under a magnetic field as an attractive alternative for future treatments of rheumatic diseases.

Simple synthesis and characterization of l-Cystine functionalized δ-FeOOH for highly efficient Hg(II) removal from contamined water and mining waste.

l-Cystine functionalized δ-FeOOH nanoparticles (Cys-δ-FeOOH) were prepared by a cheap and straightforward method for using as an adsorbent of Hg(II) in aqueous solution. X-ray diffraction (XRD), attenuated total reflectance infrared spectroscopy (ATR-IR), and Raman spectroscopy confirmed that Cys-δ-FeOOH was successfully synthesized. Cys-δ-FeOOH with 14 nm crystal size, 34 m2 g-1 surface area, and 9 nm pore size were produced. The functionalization of the δ-FeOOH surface with cysteine decreases the point of zero charge of the iron oxyhydroxide from 8.4 in δ-FeOOH to 5.7 in Cys-δ-FeOOH, which is beneficial for the adsorption of Hg(II) near neutral pH. The maximum Hg(II) adsorption capacity of the δ-FeOOH and Cys-δ-FeOOH at pH 7 were found to be 35 mg g-1 and 217 mg g-1, respectively. The kinetics data were best fitted by a pseudo-second-order model, suggesting chemical adsorption on the surface and pores of Cys-δ-FeOOH nanoparticles. Finally, δ-FeOOH and Cys-δ-FeOOH filters were constructed for purifying mercury-contaminated water. The filters were highly efficient to treat mercury-contaminated water from a Brazilian river, reducing the concentration of mercury in water to values below the allowed limits by the current legislation.

Synthesis of glycerol carbonate over a 2D coordination polymer built with Nd3+ ions and organic ligands.

In this work, a two-dimensional coordination polymer was synthesized and the structure was determined by single-crystal X-ray diffraction. The crystal structure belongs to the space group Pna21 and was characterized by Raman and FT-infrared spectroscopy, powder X-ray diffraction and Brunauer-Emmett-Teller surface area analysis. Catalyst activities were evaluated through the synthesis of glycerol carbonate from glycerol and urea using a batch reactor. After the optimization of both reaction and reaction conditions, the activity results showed that the coordination polymer used as a heterogeneous catalyst has good values of conversions and selectivity for the manufacturing of glycerol carbonate in a fine-chemical process. The analysis of powder X-ray diffraction and spectroscopy for the coordination polymer employed, before and after the reaction, shows that some changes have taken place in the crystal structure during the process, in spite of a recovery at the end of the reaction. The advantages and limitations of the coordination polymer were discussed and compared with those of the previous heterogeneous catalysts in the literature.

Development of Fe/Nb-based solar photocatalysts for water treatment: impact of different synthesis routes on materials properties.

Semiconductors based on Fe/Nb oxides can present both solar sensitivity and high catalytic activity. However, there is still a lack regarding the comparison between different routes to produce Fe/Nb-based solar photocatalysts and the evaluation of the impact of the synthesis operating conditions on the material properties. In this work, Fe/Nb2O5 ratio, type of precipitating agent, presence/absence of washing stage, and temperature of calcination were verified to be the most relevant parameters in the synthesis by the co-precipitation method. These factors led to remarkable differences in the properties and performance of the photocatalysts produced by each distinct synthesis route. Composition, iron species present in the materials, crystallinity characteristics, and pH of the catalysts were affected, leading to different photocatalytic activities under UV-Vis light. Due to their characteristics, the synthesized materials are potential photocatalysts for application in solar processes. Graphical abstract ᅟ.

Purification of arsenic-contaminated water with K-jarosite filters.

The high toxicity and potential arsenic accumulation in several environments have encouraged the development of technologies for its removal from contaminated waters. However, the arsenic released into aquatic environment comes mainly from extremely acidic mining effluents, making harder to find stable adsorbents to be used in these conditions. In this work, K-jarosite particles were synthesized as a stable adsorbent in acidic medium for eliminating arsenic from contaminated water. The adsorption capacities of K-jarosite for As3+, As5+, and monomethylarsonic acid were 9.45, 12.36, and 8.21 mg g-1, respectively. Most arsenic in water was adsorbed within the first 10 min, suggesting the fast arsenic adsorption kinetics of K-jarosite particles. Because of that, a K-jarosite filter was constructed for purifying water at a constant flow. The K-jarosite filter was highly efficient to treat arsenic-contaminated water from a Brazilian river, reducing the concentration of arsenic in water to near zero. These data suggest the K-jarosite filter can be used as a low-cost technology for purifying arsenic-contaminated water in acidic medium.

Peroxoniobium inhibits leukemia cell growth.

A new class of polyoxoniobate complex has been synthesized and characterized as a novel anticancer agent for photodynamic therapy. The complex inhibits the growth of chronic myelogenous leukemia cells with an IC50 value of 30 µM, in the dark. However, upon exposure to light (365 nm) there is a fivefold increase in the cytotoxic activity. Light radiation activate the complex with the formation of radical species capable of interacting with DNA according to our experimental and theoretical data.

PET-modified red mud as catalysts for oxidative desulfurization reactions.

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS).

Magnetic iron species highly dispersed over silica: use as catalysts for removal of pollutants in water.

Fe2O3-SiO2 composites were prepared by impregnation (sample FeIMP) or doping (sample FeDOP) in the structure of porous silica. The dye removal capacity of the materials was investigated through adsorption and oxidation studies of methylene blue and rhodamine B. N2 adsorption/desorption measurements on FeIMP and FeDOP resulted in specific areas of 27 and 235 m2 g-1, respectively. Mössbauer spectroscopy and XRD data detected hematite and maghemite as the iron phases in the samples FeIMP and FeDOP, respectively. Adsorption isotherms and kinetic studies of the dyes were better fitted in DKR model for FeDOP, where the process follows a pseudo-second order with the interparticle diffusion step being the rate-limiting step. On the other hand, FeIMP has better fit in the Langmuir model. Photocatalytic activity was observed in FeDOP under UV irradiation by the presence of reaction-hydroxylated intermediates for MB (m/z = 301) and RhB (m/z = 459). However, the photocatalytic activity was strongly influenced by the adsorption affinity between dye/catalyst. Photogenerated holes are the species responsible for the dye degradation when the adsorption is too strong, while hydroxyl radical action will be favored when the adsorption is not vigorous as detected by ESI-MS. Graphical Abstract Action of photogenerated holes and free electrons into the photocatalytically mechanism of methylene blue degradation over a semiconductor.

Adsorption of arsenic from water and its recovery as a highly active photocatalyst.

The contamination of water with arsenic has aroused concern around the world due to its toxic effects. Thus, the development of low-cost technologies for treating water contaminated with toxic metals is highly advisable. Adsorption is an attractive technology for purification of contaminated water, but it only transfers the contaminant from water to the solid adsorbent, which provokes another problem related to solid residue disposal. In this work, we developed a sustainable method for purifying water contaminated with arsenic by using δ-FeOOH nanoparticles. The adsorption capacities of nanomaterial for As3+ and As5+ species were 40 and 41 mg g-1, respectively, and were highly efficient to purify arsenic-contaminated water from a Brazilian river. The concentration of arsenic in water was close to zero after the water treatment by δ-FeOOH. Once the arsenic is adsorbed, it can be recovered by treatment with NaOH solutions. Approximately 85 % of the total adsorbed arsenic could be recovered and used as a precursor to produce useful material (Ag3AsO4) with excellent photocatalytic activity. It was active under visible light and had a high recyclability for oxidation of rhodamine B. Finally, the simple method described is promising to design sustainable process of environmental remediation with minimum residue generation.

A hole inversion layer at the BiVO4/Bi4V2O11 interface produces a high tunable photovoltage for water splitting.

The conversion of solar energy into hydrogen fuel by splitting water into photoelectrochemical cells (PEC) is an appealing strategy to store energy and minimize the extensive use of fossil fuels. The key requirement for efficient water splitting is producing a large band bending (photovoltage) at the semiconductor to improve the separation of the photogenerated charge carriers. Therefore, an attractive method consists in creating internal electrical fields inside the PEC to render more favorable band bending for water splitting. Coupling ferroelectric materials exhibiting spontaneous polarization with visible light photoactive semiconductors can be a likely approach to getting higher photovoltage outputs. The spontaneous electric polarization tends to promote the desirable separation of photogenerated electron- hole pairs and can produce photovoltages higher than that obtained from a conventional p-n heterojunction. Herein, we demonstrate that a hole inversion layer induced by a ferroelectric Bi4V2O11 perovskite at the n-type BiVO4 interface creates a virtual p-n junction with high photovoltage, which is suitable for water splitting. The photovoltage output can be boosted by changing the polarization by doping the ferroelectric material with tungsten in order to produce the relatively large photovoltage of 1.39 V, decreasing the surface recombination and enhancing the photocurrent as much as 180%.

Composites based on PET and red mud residues as catalyst for organic removal from water.

In this study, we obtained a composite based on carbon/iron oxide from red mud and PET (poly(ethylene terephthalate)) wastes by mechanical mixture (10, 15 and 20wt.% of PET powder/red mud) followed by a controlled thermal treatment at 400°C under air. XRD analyses revealed that the α-Fe2O3 is the main phase formed from red mud. TPR analyses showed that the iron oxide present in the composites undergoes reduction at lower temperature to form Fe(2+) species present in Fe3O4, indicating that the iron oxide in the composite can exhibit greater reactivity in the catalytic processes compared to the original red mud. In fact, catalytic tests showed that the composites presented higher capacity to remove methylene blue dye (MB), presenting about 90% of removal after 24h of reaction. The MB removal was also monitored by mass spectrometer with ionization via electrospray (ESI-MS), which demonstrated the occurrence of the oxidation process, showing the formation of MB oxidation products. The stability of the composites was confirmed after four reuse cycles. The results seem to indicate that PET carbon deposited over the iron oxide from red mud promotes adsorption of the contaminant allowing its contact with the iron atoms and their consequent reaction.

Capacidade funcional e qualidade de vida entre sujeitos saudáveis e pacientes com apneia obstrutiva do sono / Functional capacity and quality of life between healthy subjects and patients with obstructive sleep apnea

Caso-controle. Objetivos do estudo: Comparar a capacidade funcional, parâmetros respiratórios e qualidade de vida entre sujeitos saudáveis e pacientes com apneia obstrutiva do sono. Metodologia: Em 19 pacientes com apneia obstrutiva do sono e 19 sujeitos saudáveis foram avaliadas a qualidade de vida (The Medical Study 36-item Short-Form Health Survey), capacidade funcional (teste de caminhada de seis minutos), função pulmonar (espirometria) e força muscular respiratória(manovacuometria). Resultados: Os pacientes apresentaram declínio na qualidade de vida pelos domínios capacidade funcional, estado geral de saúde e saúde mental. A distância percorrida no teste de caminhada de seis minutos foi menor nos pacientes com apneia obstrutiva do sono. Os parâmetros respiratórios não diferiram entre os grupos. Conclusão: Pacientes com apneia obstrutiva do sono apresentam comprometimento da qualidade de vida e da capacidade funcional...

To compare the functional capacity, respiratory parameters and quality of life between healthy subjects and patients with obstructive sleep apnea. Methodology: 19 patients with obstructive sleep apnea and 19 healthy subjects were evaluated regarding their quality of life (The Medical Study 36-Item Short-Form Health Survey), their functional capacity (six-minute walk test), pulmonary function (spirometry) and their strength respiratory muscle(manovacuometer). Results: Patients showed a decline in the quality of life concerning functional capacity domains, general state of health and mental health. The distance walked in the six-minute walktest was shorter for patients with obstructive sleep apnea. Respiratory parameters did not differ between groups. Conclusion: Patients with obstructive sleep apnea present impairment regarding their quality of life and functional capacity...

A fast and environment-friendly method for determination of chemical oxygen demand by using the heterogeneous Fenton-like process (H2O2/Fe(3-x)Co(x)O4 nanoparticles) as an oxidant.

An easy, fast and environment-friendly method for COD determination in water is proposed. The procedure is based on the oxidation of organic matter by the H2O2/Fe(3-x)Co(x)O4 system. The Fe(3-x)Co(x)O4 nanoparticles activate the H2O2 molecule to produce hydroxyl radicals, which are highly reactive for oxidizing organic matter in an aqueous medium. After the oxidation step, the organic matter amounts can be quantified by comparing the quantity of H2O2 consumed. Moreover, the proposed COD method has several distinct advantages, since it does not use toxic reagents and the oxidation reaction of organic matter is conducted at room temperature and atmospheric pressure. Method detection limit is 2.0 mg L(-1) with intra- and inter-day precision lower than 1% (n=5). The calibration graph is linear in the range of 2.0-50 mg L(-1) with a sample throughput of 25 samples h(-1). Data are validated based on the analysis of six contaminated river water samples by the proposed method and by using a comparative method validated and marketed by Merck, with good agreement between the results (t test, 95%).

Magnetic composites based on metallic nickel and molybdenum carbide: a potential material for pollutants removal.

New magnetic composites based on metallic nickel and molybdenum carbide, Ni/Mo(2)C, have been produced via catalytic chemical vapor deposition from ethanol. Scanning electron microscopy, thermal analysis, Raman spectroscopy and X-ray diffraction studies suggest that the CVD process occurs in a single step. This process involves the reduction of NiMo oxides at different temperatures (700, 800 and 900°C) with catalytic deposition of carbon from ethanol producing molybdenum carbide on Ni surface. In the absence of molybdenum the formation of Ni/C was observed. The magnetic molybdenum carbide was successfully used as pollutants removal by adsorption of sulfur and nitrogen compounds from liquid fuels and model dyes such as methylene blue and indigo carmine. The dibenzothiofene adsorption process over Ni/Mo(2)C reached approximately 20 mg g(-1), notably higher than other materials described in the literature and also removed almost all methylene blue dye. The great advantage of these carbide composites is that they may be easily recovered magnetically and reused.

Removal of organic dyes using Cr-containing activated carbon prepared from leather waste.

In this work, hydrogen peroxide decomposition and oxidation of organics in aqueous medium were studied in the presence of activated carbon prepared from wet blue leather waste. The wet blue leather waste, after controlled pyrolysis under CO(2) flow, was transformed into chromium-containing activated carbons. The carbon with Cr showed high microporous surface area (up to 889 m(2)g(-1)). Moreover, the obtained carbon was impregnated with nanoparticles of chromium oxide from the wet blue leather. The chromium oxide was nanodispersed on the activated carbon, and the particle size increased with the activation time. It is proposed that these chromium species on the carbon can activate H(2)O(2) to generate HO radicals, which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water. In fact, in this work we observed that activated carbon obtained from leather waste presented high removal of methylene blue dye combining the adsorption and oxidation processes.

Recycling of solid waste rich in organic nitrogen from leather industry: mineral nutrition of rice plants.

The leather industry produces a large quantity of solid waste (wet blue leather), which contains a high amount of chromium. After its removal from wet blue leather, a solid collagenic material is recovered, containing high nitrogen levels, which can be used as a nitrogen source in agriculture. In order to take more advantage of the collagen, it was enriched with mineral P and K in order to produce NPK formulations. The objective was also to evaluate the efficiency of such formulations as a nutrient supply for rice plants in an Oxisoil, under greenhouse conditions. The application of PK enriched-collagen formulations resulted in N contents in the vegetative parts and grains of rice plants which were equivalent or superior to those obtained with urea and commercial NPK formulations.