Heterogeneous Fenton-like surface properties of oxygenated graphitic carbon nitride.

The photo-Fenton activity of graphitic carbon nitride (g-C3N4) has been widely studied, nevertheless, its Fenton-like catalytic behavior in the dark has not yet been demonstrated. In the present work, it is shown that oxygenated g-C3N4 obtained at different temperatures (500-600 °C) can degrade indigo carmine with hydrogen peroxide in the dark by a reaction similar to a conventional Fenton's reaction. Based on an extensive characterization of g-C3N4, we conclude that Fenton-like activity is directly related to the oxygenated functional groups on g-C3N4 structure, mainly by -OH functional groups. Oxygenated functional groups (e.g., hydroquinone-like groups) can reduce the H2O2 and generate oxidizing hydroxyl radicals, just like in the Fenton reaction performed by metals. In addition to new information on g-C3N4 surface reactivity revealed by this study, the metal-free oxygenated g-C3N4 catalyst may be an alternative to traditional metal catalysts used in Fenton-like reactions for advanced oxidation.

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.

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.

Validation of a robust LLE-GC-MS method for determination of trihalomethanes in environmental samples.

An analytical liquid-liquid extraction-gas chromatography-mass spectrometry (LLE-GC-MS) method was developed and validated for the determination of trihalomethanes (THMs) in environmental samples. The compounds studied were trichloromethane (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and tribromomethane (TBM). The calibration curves for the THMs showed high linearity in the range of 1-1000 µg L-1. Studies of intra-day and inter-day precision, limit of detection (LOD), limit of quantification (LOQ), accuracy, and recovery were performed with low (10 µg L-1), medium (40 µg L-1), and high (200 µg L-1) concentrations of THMs. The intra-day and inter-day precision RSD varied in the ranges of 0.17-6.95% and 0.26-15.70%, respectively. No statistical differences were observed between the analysis of the concentration of certified reference materials (CRM 4M8140-U) and the values reported by CRM, indicating the good accuracy of the proposed method. The recovery was 88.75-119.21%. The LOD and LOQ were smaller than 0.13 and 0.40 µg L-1. Compared with reported LLE-GC-MS methods, the validated method had similar LOD and enhanced LOQ, precision, accuracy, and recovery. Also, the method is robust, selective to THMs, and the total time for the extraction and GC separation of THMs is about 18 min. The method was useful for detecting and quantifying low concentrations of TCM (40-80 µg L-1) formed by water chlorination in the presence of Microcystis aeruginosa cyanobacteria, thus demonstrating its applicability for monitoring THMs in real samples.

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.

Bismuth Vanadate Photoelectrodes with High Photovoltage as Photoanode and Photocathode in Photoelectrochemical Cells for Water Splitting.

Using dual-photoelectrode photoelectrochemical (PEC) devices based on earth-abundant metal oxides for unbiased water splitting is an attractive means of producing green H2 fuel, but is challenging, owing to low photovoltages generated by PEC cells. This problem can be solved by coupling n-type BiVO4 with n-type Bi4 V2 O11 to create a virtual p/n junction due to the formation of a hole-inversion layer at the semiconductor interface. Thus, photoelectrodes with high photovoltage outputs were synthesized. The photoelectrodes exhibited features of p- and n-type semiconductors when illuminated under an applied bias, suggesting their use as photoanode and photocathode in a dual-photoelectrode PEC cell. This concept was proved by connecting a 1 mol % W-doped BiVO4 /Bi4 V2 O11 photoanode with an undoped BiVO4 /Bi4 V2 O11 photocathode, which produced a high photovoltage of 1.54 V, sufficient to drive stand-alone water splitting with 0.95 % efficiency.

Molecularly imprinted polymers for selective adsorption of quinoline: theoretical and experimental studies.

The effects of solvent on the synthesis of molecularly imprinted polymers (MIPs) for the selective adsorption of quinoline were evaluated in this work. The MIPs were synthesized by the "bulk" method using the quinoline molecule (IQ) as a template in different solvents, such as toluene (MIPT) and chloroform (MIPC). The adsorbents were characterized by thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), and N2 adsorption/desorption measurements. The influences of time, adsorbate concentration, and temperature on the adsorption of quinoline by MIPT and MIPC were evaluated. Maximum adsorption capacities (q e) of 35.23 and 24.10 mg g-1 were obtained for MIPT and MIPC, respectively. Thermodynamic studies indicate that occur physisorption and a spontaneous process (Δads G° < 0) entropically directed. Finally, the highest selectivity and reusability of MIPC for quinoline adsorption was ascribed to the better interaction between the chloroform and monomer, which favors the formation of porous adsorbents with higher numbers of adsorption sites.

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%.

Current Status of Magnetite-Based Core@Shell Structures for Diagnosis and Therapy in Oncology Short running title: Biomedical Applications of Magnetite@Shell Structures.

Superparamagnetic iron oxides, as magnetite (Fe3O4) or maghemite (γ-Fe2O3), are primary materials with intrinsic properties that enable them, as single components or as special composites, to base advanced techniques in medical clinical practices, as a contrast agent in magnetic resonance imaging (MRI), as magnetically-induced hyperthermic heat generator, and as a magnetic guide to locally deliver drugs to specific sites in the human body. An interesting approach to developing nanoplatforms for those applications consists in manufacturing core@shell nanostructures, in which the precursor magnetic iron oxide (usually, magnetite) acts as a core, and an organic, or inorganic compound is used as a shell in a multifunctional composite. In this review, we report the current advances in the use of magnetite-based core@shell nanostructures, including Fe3O4@SiO2 and Fe3O4@polymers, in MRI, magnetic hyperthermia and drug delivery systems for diagnosis and therapy of tumor cells. The development of nanoplatforms for combined therapy and diagnostic (theranostic) is also addressed.

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%).

Use of activated carbon as a reactive support to produce highly active-regenerable Fe-based reduction system for environmental remediation.

Composites based on iron supported on high surface area activated carbon were prepared and characterized with (57)Fe Mössbauer spectroscopy, X-ray diffraction, saturation magnetization measurements and temperature-programmed reduction. Upon thermal treatment, the supported iron oxides react with carbon to yield reduced chemical species, i.e. Fe(3)O(4) and Fe(0). This so produced composite was found to be highly efficient in two environmental applications: (i) degradation of textile dye and (ii) reduction of Cr(VI) in aqueous medium. Sequential reuses evidenced a progressive chemical deactivation of the composites due to a corresponding oxidation of the reactive species. Even after being virtually deactivated, the initial chemical reducing ability of the composites can be regenerated by heating at 800 degrees C under N(2) atmosphere, and then reused for several consecutive times.

Magnetic properties of nanoparticles obtained by different chemical routes.

It is well known that nano-sized materials often present chemical, electronic, magnetic, and mechanical properties that are potentially interesting for many technological applications comparatively to their corresponding bulk properties. This paper describes the main differences in magnetic properties among nanomagnetite powders prepared by three methods: (I) reduction-precipitation of ferric chloride by reaction with Na2SO3; (II) reduction of hematite with coal, and (III) reduction of hematite with hydrogen gas. The obtained materials were characterized by powder X-ray diffraction (XRD), saturation magnetization measurements, and Mössbauer spectroscopy. Saturation magnetization values varied from 60 to 86 J T(-1)kg(-1). XRD and Mössbauer spectroscopy results at 298 K showed the clear effect of the preparation routes on the crystallographic structure and crystallite size of the magnetic species. Magnetite was formed in varying proportions in all samples, with crystallite sizes estimated by Scherrer formula of about 10, 26, and 33 nm for samples prepared by methods (I), (II), and (III), respectively. The Mössbauer spectrum of the sample prepared by method (I) consisted of broad lines and hyperfine field for magnetite lower than that typically reported for the bulk material.