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In this work, lovegrass (Cpa), an abundant grass of the Poaceae family, was employed as feedstock for the production of activated carbon in a conventional furnace using ZnCl2 as a chemical activator. The prepared material (Cpa-AC) was characterized by pH of the point of zero charges (pHpzc), Boehm’s titration method, CHN/O elemental analysis, ATR-FTIR, N2 adsorption/desorption curves, and SEM. This carbon material was used for adsorption of acetylsalicylic acid (ASA) and sodium diclofenac (DFC). FTIR analysis identified the presence of O-H, N-H, O-C=O), C-O, and aromatic ring bulk and surface of (Cpa-AC) adsorbent. The quantification of the surface functional groups showed the presence of a large amount of acidic functional groups on the surface of the carbon material. The isotherms of adsorption and desorption of N2 confirm that the Cpa-AC adsorbent is mesopore material with a large surface area of 1040 m2 g−1. SEM results showed that the surface of Cpa-AC is rugous. The kinetic study indicates that the system followed the pseudo-second-order model (pH 4.0). The equilibrium time was achieved at 45 (ASA) and 60 min (DCF). The Liu isotherm model best fitted the experimental data. The maxima sorption capacities (Qmax) for ASA and DFC at 25 °C were 221.7 mg g−1 and 312.4 mg g−1, respectively. The primary mechanism of ASA and DFC adsorption was justified considering electrostatic interactions and π-π interactions between the Cpa-AC and the adsorbate from the solution.

Chitosan nanocapsules containing polyunsaturated fatty acid (PUFA) concentrates from tuna oil, with EPA + DHA contents around 57% (w w−1), were developed by emulsification process, using different chitosan concentration (1.0%, 1.5%, 2.0%, w v−1) and stirring speed (10,000, 15,000, 20,000 rpm). The effects of these parameters on particle size and zeta potential were evaluated. The physical and oxidative stabilities were used to measure the product quality during storage. Chitosan concentration, stirring speed and its interaction significantly affected ( p

Few data are available about the effect of dimethylated forms (DMA) on aquatic organisms. As rarely a contaminant occurs alone, studies evaluating the combined effect of different contaminants in aquatic organisms are needed. In fact, the presence of nanomaterials, such as titanium dioxide nanoparticles (nTiO2), in the aquatic environment is now a reality due to its intensive production and use. So, this study evaluated the toxicological effects of DMA in an acute exposure condition and considered the potential influence of nTiO2 on the effects induced by DMA in the polychaete, Laeonereis culveri. The animals were exposed over 48 h to DMA (50 and 500 μg/l) alone or in combination with nTiO2 (1 mg/l). Biochemical parameters such as concentration of reactive oxygen species (ROS), glutathione-S-transferase (GST) activity, levels of reduced glutathione levels (GSH) and macromolecular (lipid and DNA) damage were evaluated, as well the DNA repair system. In addition, the accumulation of total As and the chemical speciation of the metalloid in the organisms was determined. The results showed that: (1) only the group exposed to 500 μg of DMA/l accumulated As and when co-exposed to nTiO2, this accumulation was not observed. (2) The levels of ROS increased in the group exposed to 50 μg/l of DMA alone and the effect was reversed when this group was co-exposed to nTiO2 (3) None of the treatments showed altered GST activity or GSH levels. (4) All groups that received nTiO2 (alone or in combination with DMA) showed lipid peroxidation. (5) The exposure to DMA (both concentrations) alone or in combination with nTiO2 induced DNA damage in L. culveri. These results showed that DMA exhibits a genotoxic effect and that co-exposure to nTiO2 had an influence on its toxicity. So the occurrence of both contaminants simultaneously can represent a threat to aquatic biota.

Aquatic animals are vulnerable to arsenic (As) toxicity. However, rarely does a contaminant occur alone in the aquatic environment. For this reason, this study was conducted to evaluate whether titanium dioxide nanoparticles (nTiO2) can interfere with the effects induced by As in Litopenaeus vannamei. Arsenic accumulation and metabolic capacity; expression and enzymatic activity of GSTΩ (glutathione-S-transferase omega isoform); antioxidant responses such as GSH, GR, and GST (reduced glutathione levels, glutathione reductase, and glutathione-S-transferase activity, respectively); and lipid peroxidation in the gills and hepatopancreas of shrimp were evaluated. The results are summarized as follows: (1) higher accumulation of As occurred in both tissues after exposure to As alone; (2) co-exposure to nTiO2 affected the capacity to metabolize As; (3) GSTΩ gene expression was not modified, but its activity was decreased by co-exposure to both contaminants; (4) As alone increased the GSH levels in the hepatopancreas, and co-exposure to nTiO2 reduced these levels in both tissues; (5) a decrease in the GST activity in the gills occurred with all treatments; (6) in the gills, GR activity was increased by As, and nTiO2 reversed this increase, whereas in the hepatopancreas co-exposure inhibited enzyme activity; (7) only in the hepatopancreas lipid damage was observed when animals were exposed to As or nTiO2 but not in co-exposure. The results showed that the As induces toxic effects in both tissues of shrimp and that co-exposure to nTiO2 can potentiate these effects and decrease the capacity to metabolize As, favoring the accumulation of more toxic compounds.

In recent times, however, due to the emergence of bacterial strains with resistance to conventional antibiotics, silver has again gained attention as an alternative for developing new efficient bactericides, including the use of silver nanoparticles (AgNPs). However, the improper disposal of these items after use may cause toxicological effects on organisms in the environment. To evaluate the potential environmental hazard of nanosilver-coated dressings, the nematode Caenorhabditis elegans was chosen as a test organism. The assays were conducted in 24-well plates that contain four different sizes of coated dressing to obtain different concentrations. L1 and L4 C. elegans larval stages were exposed to these nanosilver concentrations. Dressing cutouts were arranged between two layers of agar for 3 days and Escherichia coli (OP 50 strain) was added as food source for the worms. After the exposure period, growth, reproduction, fertility, silver concentration in the medium and the concentration of reactive oxygen species (ROS) in the worms were evaluated. Scanning and transmission electron microscopy analyses were performed on the coated dressings, as well as analyses of zeta potential, ionic release and antibacterial power in two bacterial strains (Pseudomonas aeruginosa and Staphylococcus aureus). It was verified the antibacterial power of the coated dressing, in both bacteria strains tested. Characterization of the coated dressing indicated heterogeneous nanoparticles, as well as distinct zeta potentials for the medium in water and saline medium (0.9% NaCl). L1 larval worms exposed to nanosilver-coated dressing showed a high ROS concentration and reductions in growth, fertility and reproduction. Worms exposed to the coated dressing during the L4 stage showed almost no response. Overall, the obtained results indicate the potential environmental hazard of nanosilver-coated dressings. Fil: Ayech, Alinne. Universidade Federal do Rio Grande; Brasil Fil: Josende, M. E.. Universidade Federal do Rio Grande; Brasil Fil: Ventura Lima, J.. Universidade Federal do Rio Grande; Brasil Fil: Ruas, Caroline Pires. Universidade Federal do Rio Grande; Brasil Fil: Gelesky, M. A.. Universidade Federal do Rio Grande; Brasil Fil: Ale, Analía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina Fil: Cazenave, Jimena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina Fil: Galdopórpora, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquimica. Instituto de Química y Metabolismo del Fármaco; Argentina Fil: Desimone, Martín Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquimica. Instituto de Química y Metabolismo del Fármaco; Argentina Fil: Duarte, Miriam. Universidade Federal do Rio Grande; Brasil Fil: Halicki, Priscila Cristina Bartolomeu. Universidade Federal do Rio Grande; Brasil Fil: Ramos, Daniela Fernandes. Universidade Federal do Rio Grande; Brasil Fil: Carvalho, L. M.. Universidade Federal de Santa Maria; Brasil Fil: Leal, Gabriela Camera. Universidade Federal de Santa Maria; Brasil Fil: Monserrat, José María. Universidade Federal do Rio Grande; Brasil

This work reports, for the first time, the synthesis of new fatty N-acylamino hydrazides and demonstrates the activity of these compounds as low-molecular-weight organic gelators and templates for preparation of gold nanoparticles (AuNPs). Initially, we evaluated the gelation properties of fatty N-acylamino hydrazides in various nonpolar and polar solvents (n-hexane, toluene, benzene, cyclohexane, and ethanol). Fatty N-acylamino hydrazide derived of the glycine and stearic acid (C18:0) did not form gels in any of the tested solvents. All other hydrazides did form gels in at least two of the organic solvents tested. The morphology of each gel was observed via scanning electron microscopy. The organogels derived from alanine, valine, and phenylalanine had translucid properties, while the serine organogels were opaque. Afterwards, the synthesis of AuNPs in the presence of the organogelator using microwave irradiation was realized. Organogelator agents reduced HAuCl4 showing plasmon band peaks between 530 and 543 nm. In addition, the method does not require a reducing agent, which is typically a potential source of contamination and toxicity. Therefore, this work confirms the importance of the hydrazide group of the new fatty N-acylamino hydrazides in gel formation and as organogelator agents for preparation of AuNPs.

Although some studies have showed the effects of different crystalline structures of nTiO2 (anatase and rutile) and their applicability in several fields, few studies has analyzed the effect of coexposure with other environmental contaminants such as copper. Thus, the objective of this study was to evaluate if the coexposure to nTiO2 (nominal concentration of 1 mg/L; anatase or rutile) can increase the incorporation and toxic effect induced by Cu (nominal concentration of 56 μg/L) in different tissues of Linmoperna fortunei after 120 h of exposure. Our results showed that the coexposure increased the accumulation of Cu in the gills and adductor muscle independently of the crystalline form and can positively or negatively modulate the antioxidant system, depending on the tissue analyzed. However, exposure only to rutile nTiO2 induced damage in the adductor muscle evidenced by the infiltration of hemocytes in this tissue. Additionally, histomorphometric changes based on fractal dimension analysis showed that coexposure to both forms of nTiO2 induced damage in the same tissue. These results suggest that both crystalline forms exhibited toxicity depending on the analyzed tissue and that coexposure of nTiO2 with Cu may be harmful in L. fortunei, indicating that increased attention to the use and release of nTiO2 in the environment is needed to avoid deleterious effects in aquatic biota.

This study aimed at evaluating an alternative catalyst based on CeO2/Al2O3 in methylene blue photodegradation. Samples with 6, 12 and 24 wt% ceria on alumina were synthesized and characterized by BET surface area, XRD, FTIR spectroscopy, SEM, EDS, TEM and point of zero charge. Photocatalyst tests were performed under UV radiation from a mercury lamp and monitored by UV–VIS spectrophotometry. Different pH conditions were evaluated. A first order kinetic model was used for fitting and analyzing experimental data. The sample with the highest CeO2 loading had the highest activity at neutral pH in the methylene blue photodegradation process and reached 93% degradation. Electrons photogenerated in CeO2 and the resulting holes interacted with medium molecules to form radicals that started dye degradation.

In the present study, different in vitro and electrochemical protocols were employed to determine the mitoprotective properties of carbon nanotubes family (pristine-CNT, oxidized-CNT) based on free radical scavenging ability against the most aggressive reactive oxygen species (ROS) as hydroxyl radical (·OH) formed by Fenton-Haber-Weiss reaction, which was experimentally induced on isolated rat-liver mitochondria through Fe 2+ ions overload. The results suggest that the mitochondrial Fenton-inhibition response involves a significant reduction of (·OH) concentration linked to iron-complexing ability of CNT-family, following the order: carboxylated-CNT > pristine-CNT ∼ hydroxylated-CNT, without affecting the electrochemical mitochondrial membrane potential in Fe 2+ -overloaded mitochondria. Besides, a new in silico dose-response QSPR-model was applied suggesting reliability for the CNT-dose-effect series predictions towards the mitochondrial Fenton ROS-inhibition with excellent linear behavior on the training set ( R 2 = 0.901; R 2 ( adj .) = 0.901; Q 2 ( LOO-CV ) = 0.901) and test set ( Q 2 F1 = 0.9008; Q 2 F2 = 0.9008; Q 2 F3 = 0.9009; MAE = 21.213) for internal and external validation respectively, with p 70,000 data points. Lastly, these experimental and theoretical evidences open a gate to the rational design of novel carbon nanomaterials toward mitochondrial nanomedicine based redox-targeting as an alternative of treatment of several chronic diseases where pathological Fenton-reaction mechanisms have been directly involved.

Arsenic (As) is a ubiquitous contaminant in the environment and it is known to induce oxidative stress in aquatic organisms. In an attempt to remove As from water, some studies have suggested the titanium dioxide nanomaterial (nTiO

Resumo Estudos têm contribuído para a definição de importantes diretrizes acerca da conservação de documentos de arquivo e, em especial, a conservação preventiva, fomentando a discussão e a consolidação de políticas que busquem auxiliar na preservação dos acervos. Nessa perspectiva, a presente pesquisa, realizada em parceria entre o Instituto de Ciências Humanas e da Informação - curso de Arquivologia -, e a Escola de Química e Alimentos da Universidade Federal do Rio Grande, tem como objetivo avaliar possíveis ações de danos provocados pelo uso das folhas autoadesivas nos documentos textuais em suporte papel, visando contribuir com as discussões e estudos sobre a temática de conservação e preservação dos acervos. A metodologia para o desenvolvimento deste trabalho foi dividida em etapas que consistiram em: seleção da amostragem e pesquisa sobre o surgimento dos blocos autoadesivos, revisão do referencial teórico, análise dos dados coletados través da técnica de microscopia eletrônica de varredura e posterior divulgação dos resultados da pesquisa. Abstract Studies have contributed to the definition of important guidelines on the file record keeping and in particular preventive conservation fostering discussion and the consolidation of policies that seek to assist in the preservation of collections. In this perspective the present research, which is a work in partnership between the Institute of Humanities and information - Archivology course, and the School of Chemistry and Food, Universidade Federal do Rio Grande, aims to evaluate possible actions deterioration caused by the use of self-adhesive sheets in textual paper documents, to contribute to discussions and studies on the theme of conservation and preservation of collections. The methodology for the development of this work has been divided into steps that were: the sample selection and research on the emergence of adhesive plates, review the theoretical framework, analysis of data collected slant electron microscopy technique and subsequent dissemination of research results.

Saxitoxins (STXs) are potent neurotoxins that also induce cytotoxicity through the generation of reactive oxygen species. Carbon nanotubes (CNTs) are nanomaterials that can promote a Trojan horse effect, facilitating the entry of toxic molecules to cells when adsorbed to nanomaterials. The interaction of pristine single-walled (SW)CNTs and carboxylated (SWCNT-COOH) nanotubes with STX was evaluated by ab initio simulation and bioassays using the cell line HT-22. Cells (5 × 104 cells/mL) were exposed to SWCNT and SWCNT-COOH (5 μg mL−1), STX (200 μg L−1), SWCNT+STX, and SWCNT-COOH+STX for 30 min or 24 h. Results of ab initio simulation showed that the interaction between SWCNT and SWCNT-COOH with STX occurs in a physisorption. The interaction of SWCNT+STX induced a decrease in cell viability. Cell proliferation was not affected in any treatment after 30 min or 24 h of exposure (p > 0.05). Treatment with SWCNT-COOH induced high reactive oxygen species levels, an effect attenuated in SWCNT-COOH+STX treatment. In terms of cellular oxygen consumption, both CNTs when coexposed with STX antagonize the toxin effect. Based on these results, it can be concluded that the results obtained in vitro corroborate the semiempirical evidence found using density functional theory ab initio simulation. Environ Toxicol Chem 2017;36:1728–1737. © 2016 SETAC

Eragrostis plana Nees leaves, abundant lignocellulosic biomass, was used as carbon source for preparation of activated carbon, by using microwave-assisted pyrolysis and chemical activation. The novel activated carbon (MWEPN) was characterised by FTIR, CHN elemental analysis, Boehm’s titration method, TGA, SEM, N2 adsorption/desorption curves and pH of the point of zero charge (pHpzc). Afterwards, the adsorbent was successfully employed for adsorption of the two emerging contaminants (caffeine and 2-nitrophenol). The results indicated that MWEPN had a predominantly mesoporous structure with a high surface area of 1250 m2 g−1. FTIR analysis indicated the presence of carbonyl, hydroxyl and carboxylic groups on the surface of MWEPN. The Boehm analysis showed the existence of the high amount of acid moieties on the surface of activated carbon. Adsorption kinetic indicated that the system followed the Avrami fractional order at the optimal pH of 7. The equilibrium time was attained at 30 min. The Liu isotherm model better described the isothermal data. Based on the Liu isotherm, the maximum sorption capacities (Qmax) of caffeine and 2-nitrophenol adsorbed onto activated carbon at 25 °C were 235.5 and 255.8 mg g−1, respectively.

Interactions between the single walled carbon nanotube (SWCNT) family and a mitochondrial ADP/ATP carrier (ANT-1) were evaluated using constitutional (functional groups, number of carbon atoms, etc.) and electronic nanodescriptors defined by (n, m)-Hamada indexes (armchair, zig-zag and chiral). The Free Energy of Binding (FEB) was determined by molecular docking simulation and the results showed that FEB was statistically more negative (p SWCNT-OH > SWCNT, suggesting that polar groups favor the anchorage to ANT-1. In this regard, it was showed that key ANT-1 amino acids (Arg 79, Asn 87, Lys 91, Arg 187, Arg 234 and Arg 279) responsible for ADP-transport were conserved in ANT-1 from different species examined to predict SWCNT interactions, including shrimp Litopenaeus vannamei and fish Danio rerio commonly employed in ecotoxicology. The SWCNT-ANT-1 inter-atomic distances for the key ANT-1 amino acids were similar to that with carboxyatractyloside, a classical inhibitor of ANT-1. Significant linear relationships between FEB and n-Hamada index were found for zig-zag SWCNT and SWCNT-COOH (R2 = 0.95 in both cases). A Perturbation Theory-Nano-Quantitative Structure-Binding Relationship (PT-NQSBR) model was fitted that was able to distinguish between strong (FEB < −14.7 kcal mol−1) and weak (FEB ≥ −14.7 kcal mol−1) SWCNT–ANT-1 interactions. A simple ANT-1-inhibition respiratory assay employing mitochondria suspension from L. vannamei, showed good accordance with the predicted model. These results indicate that this methodology can be employed in massive virtual screenings and used for making regulatory decisions in nanotoxicology.

Despite arsenic being one of the most widely distributed toxicants over the world, its reported occurrence in Latin America is relatively low when compared to North America, Europe, and Asia. Regardless, it still requires proper assessment; especially considering its potential interaction with other new contaminants, such as nanomaterials. In the present study, a brief introduction to arsenic contamination in Latin America is made, its main methods of intake by humans are described, and concerns regarding its interaction with other contaminants, especially nanomaterials, are presented. A multigenerational approach through five generations of Caenorhabditis elegans was performed to assess, at ecotoxicological relevant concentrations, the toxic effects of arsenic/nanomaterial interaction through the measurement of biochemical and physiological parameters. The reactive oxygen species (ROS) and lipid peroxidation levels were assessed, levels of reduced glutathione (GSH) determined, and the enzyme activities of glutamate cysteine ligase (GCL), glutathione-S-transferase (GST), and catalase (CAT) were measured. Fertility, reproduction, and growth parameters were also assessed and compared. A nanomaterial modulatory effect was found to accentuate the toxicity of arsenic on some of the most important enzymes in the antioxidant defense system; deleterious effects were also found in the development and reproduction of the animals throughout the generations. This work shows that multigenerational approaches can unveil toxic effects that would remain cryptic when evaluated in only one generation.

Rhodium and platinum nanoparticles were supported in polymeric membranes with 10, 20 and 40 µm thickness. The polymeric membranes were prepared combining cellulose acetate and the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI.(NTf)2. The presence of metal nanoparticles induced an increase in the polymeric membrane surface areas. The increase of the IL content resulted in an improvement of elasticity and decrease in tenacity and toughness, whereas the stress at break was not affected. The presence of IL probably causes an increase in the separation between the cellulose molecules that result in a higher flexibility and processability of the polymeric membrane. The CA/IL/M(0) combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The CA/IL/M(0) polymeric membrane displays higher catalytic activity (up to 7.353 h-1) for the 20 mm of CA/IL/Pt(0) and stability than the nanoparticles dispersed only in the IL.

Transition metal-containing membrane films of 10, 20, and 40 μm thickness were obtained by the combination of irregularly shaped nanoparticles with monomodal size distributions of 4.8 ± 1.1 nm (Rh(0)) and 3.0 ± 0.4 nm (Pt(0)) dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI·(NTf)(2)) with a syrup of cellulose acetate (CA) in acetone. The Rh(0) and Pt(0) metal concentration increased proportionally with increases in film thickness up to 20 μm, and then the material became metal saturated. The presence of small and stable Rh(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The augmentation of the IL content resulted in an increase of elasticity and decrease in tenacity and toughness, whereas the stress at break was not influenced. The introduction of IL probably causes an increase in the separation between the cellulose macromolecules that results in a higher flexibility, lower viscosity, and better formability of the cellulose material. The nanoparticle/IL/CA combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The nanoparticle/IL/cellulose acetate film membranes display higher catalytic activity (up to 7353 h(-1) for the 20 μm film of CA/IL/Pt(0)) and stability than the nanoparticles dispersed only in the IL.

The surface-enhanced Raman scattering (SERS) spectra obtained using Ag nanoparticles (NPs) dispersed in 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4) ionic liquid and from an Ag island film spin coated with BMIBF4 are reported. The SERS spectra of the Ag NPs/BMIBF4 interface do not show enhancement of the BF4− symmetric stretching signal at 765 cm−1; however, this vibrational mode is enhanced in the SERS spectra of BMIBF4 recorded using Ag island films. The results are discussed in terms of the role of water molecules in the structure of the BMIBF4 adsorbed on the different Ag substrates. Further evidence for the function of water in the structure of the investigated interfaces was obtained by surface-enhanced infrared absorption (SEIRA) spectroscopy. The results support the conclusion that the presence of water in the Ag NPs/BMIBF4 dispersion promotes the aggregation of the Ag NPs.

This article describes the preparation of silica xerogels by the sol–gel technique, using tetraethoxysilane as precursor and hydrofluoric acid as catalyst, in the presence of imidazolium ionic liquids (ILs). The applied ILs 1–3 contained the 1-monoethylene glycol monomethyl ether-3-methylimidazolium cation in combination with the methanesulfonate (1), tetrafluoroborate (2) and hexafluorophosphate (3) anions, respectively. Characterization of these materials was performed by photography, scanning electron microscopy, atomic force microscopy, X-ray diffraction, thermogravimetric analysis and nitrogen adsorption-desorption isotherms. The IL anion was identified as a powerful morphology controller. The methanesulfonate anion of IL 1 induced the formation of a compact lamellar monolith with an interlamellar distance of 1.5 nm and a flat surface. A free flowing powder of aggregated spherical particles was obtained in the presence of tetrafluoroborate IL 2, and the hexafluorophosphate anion of IL 3 induced the formation of porcelain like aggregates with honeycomb shapes.

A surface-enhanced Raman spectroscopy (SERS) study of imidazolium ionic liquid stabilized gold(0) nanoparticles (GNPs) furnished previously unknown knowledge about the coordination and stabilization mode of the imidazolium cation. GNPs were prepared by hydrazine reduction of a chloroauric acid solution in 1-triethylene glycol monomethyl ether-3-methylimidazolium methanesulfonate 2 as ether-functionalized room-temperature ionic liquid (RTIL). UV–vis spectroscopy showed the presence of GNP aggregates as absorptions extended to the NIR region. A parallel coordination mode for the imidazolium cation of RTIL 2 on the GNP surface was observed by SERS, which occurred without the simultaneous coordination of the 1-triethylene glycol monomethyl ether-functionality. Instead of this, the ether-functionality was directed away from the GNP surface and acted as steric barrier between the GNPs/GNP aggregates, thus preventing further aggregation. These new insights suggest that the imidazolium cation is responsible for electrosteric stabilization.

The production and use of nanoparticles, as titanium dioxide (nanoTiO2) is growing exponentially in the last years and their release into aquatic environment seem be inevitable. Once into environment, this nanomaterial can interact with other contaminant, as arsenic, and to exert toxic effect in living organisms. So, the objective of present study was to evaluate if the co-exposure to nanoTiO2 (1 mg/L) can alter the As effect (nominal concentration of 50 μg/L) in the estuarine polychaeta Laeonereis acuta after 48 h of exposure. Were performed biochemical analyses such ROS production, enzymatic activities (GST, GR and GSTΩ), total antioxidant capacity against peroxyl radicals and damage to macromolecules (lipid and DNA), besides also were determined the accumulation of total arsenic and arsenic speciation in the worms. The results showed that co-exposure induced an increase in the ROS levels, decrease in total antioxidant capacity, increase in GR activity, and damage in lipid and DNA. Also, the co-exposure showed to affect the metabolization capacity of arsenic characterized by increase in dimethylated arsenic forms, a compound moderately toxic. So, these results suggest that the co-exposure to both contaminants is harmful to this species and the use of nanoTiO2 to treatment of contaminated water by arsenic should be considered of a toxicological point of view.

The acute toxicity of titanium dioxide nanoparticles (nTiO2) that occur concomitantly in the aquatic environment with other contaminants such as arsenic (As) is little known in crustaceans. The objective of the present study is to evaluate whether coexposure to nTiO2 can influence the accumulation, metabolism, and oxidative stress parameters induced by arsenic exposure in the gills and hepatopancreas of the shrimp Litopenaeus vannamei. Organisms were exposed by dissolving chemicals in seawater (salinity = 30) at nominal concentrations of 10 μg/L nTiO2 or As(III), dosed alone and in combination. Results showed that there was not a significant accumulation of As in either tissue type, but the coexposure altered the pattern of the metabolism. In the hepatopancreas, no changes were observed in the biochemical response, while in the gills, an increase in the glutamate-cysteine-ligase (GCL) activity was observed upon exposure to As or nTiO2 alone, an increase in the reduced glutathione (GSH) levels was observed upon exposure to As alone, and an increase in the total antioxidant capacity was observed upon exposure to nTiO2 or nTiO2 + As. However, these modulations were not sufficient enough to prevent the lipid damage induced by nTiO2 exposure. Our results suggest that coexposure to nTiO2 and As does not alter the toxicity of this metalloid in the gills and hepatopancreas of L. vannamei but does alter its metabolism, favoring its accumulation of organic As species considered moderately toxic.

The hydroformylation of 1-alkenes can be performed in solventless conditions using ligand-modified or unmodified Rh(0) nanoparticles prepared in imidazolium ionic liquids as catalyst precursors. There is a strong influence of the nanoparticle size on the hydroformylation reaction. Aldehydes are generated when 5.0 nm Rh(0) nanoparticles are used in the hydroformylation of 1-alkenes and l/b selectivities up to 25 can be achieved by addition of Xantphos (9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene). Although small nanoparticles also generate catalytically active species the chemoselectivity decreases (around 11–17% of olefin isomerization) compared to those performed with the 5.0 nm nanoparticles. In contrast, the large sized nanoparticles (15 nm) produce only small amounts of aldehydes similar to that observed with a classical heterogeneous Rh/C catalyst precursor. TEM, XRD, IR and NMR experiments indicated that these Rh(0) nanoparticles are probably degraded under the reaction conditions into soluble mononuclear Rh-carbonyl catalytically active species.

The influence of substituents on rate constants of the hydrogenation of monoalkylbenzenes by transition metal nanoparticles or by classical heterogeneous catalysts can be rationalized in terms of the Taft rule. A series of the initial reaction rate constants obtained from various competitive toluene/benzene and toluene/monoalkylbenzene hydrogenation experiments catalyzed by transition-metal nanoparticles prepared in the presence of imidazolium ionic liquids or surfactants [Ir(0), Rh(0) and Ru(0)] or by classical heterogeneous catalysts (PtO 2 , Rh/C, Rh/Al 2 O 3 , Ru/ C, Ru/Al 2 O 3 and Pd/C) have been correlated with the Taft equation (logk B K B k A K A = ρE s ). Satisfactory correlation coefficients (r) (between 0.96 and 0.99) and positive slopes (p) between 0.38 and 0.83 have been obtained. The results clearly show that the reaction constants for the alkyl-substituents can be expressed by steric factors and are independent of any other non-steric factors. It is suggested that bulky alkylbenzene substituents, for both transition metal nanoparticles and classical heterogeneous hydrogenation reactions, lower the overall hydrogenation rate, implying a more disturbed transition state compared to the initial state of the hydrogenation (in terms of the HoriutiPolanyi mechanism). This competitive method is suitable for the estimation of the constant selectivity for couples of alkylbenzenes in which the difference in hydrogenation rates are very high and experimentally difficult to measure and also useful for the design of more selective "nano" and classical catalysts for hydrogenation reactions.

PdCl2 immobilized in polyacrylamide (PAM), named Pd/PAM, produced at an extremely low cost, was found to be an efficient catalyst for Suzuki-Miyaura cross-coupling reactions. Iodo- and bromoarenes may couple with phenylboronic acid under eco-friendly conditions (i.e., phosphine-free and with ethanol as the solvent) to give excellent product yields. Aryl chlorides, in contrast, were found to be unsuitable reagents in this context, yielding modest results. The recyclability of Pd/PAM is limited because of PdII leaching, which leaves only the base polymer on the surface after six runs. The Pd/PAM catalyst was initially prepared via the formation of a PAM hydrogel using an aqueous PdCl2 solution. After drying, the solid Pd/PAM was characterized by scanning electron microscopy (SEM), electron-dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), and inductively coupled plasma optical emission spectrometry (ICP OES).

Hydrogen reduction of cationic or neutral Ir(i) compounds, namely [Ir(COD)(2)]BF(4) and [Ir(COD)Cl](2)respectively. in the ionic liquid (IL) 1-alkyl-3-methylimidazolium tetrafluoroborate affords either irregularly sized spherical (from 1.9 +/- 0.4 to 3.6 +/- 0.9 nm) or worm-like metal nanoparticles, depending on the nature of the imidazolium alkyl group and the type of iridium precursor. The ionic Ir(i) precursor tends to be dissolved and concentrated on the IL polar domains (populated by the imidazolium nucleus and tetrafluoroborate anions) while the neutral precursor dissolves preferentially in the non-polar region of the IL (populated mainly by N-alkyl side chains). The size, or volume, of the nano-region where the Ir(i) precursor is dissolved and reduced, determines the size and, probably, the shape of the formed nanoparticles. The HR-TEM image shows that the Ir(0) with worm-like shape are polycrystalline and formed from aggregation individual "spherical" nanoparticles of around 1.9 nm. The catalytic activity of Ir(0) NPs on the hydrogenation of cyclohexene (0.01 mol L(-1) of Ir atoms in IL, 75 degrees C, 8 bar of H(2), 500 rpm stirring, 1/1000 Ir(0)/cyclohexene ratio) is always greater in C(1)C(10)I.BF(4) than C(1)C(4)I.BF(4), regardless of the nature of Ir(i) precursor. Moreover, the cyclohexene hydrogenations performed with Ir(0) nanocatalysts made from ionic Ir(i) precursor are approximately twice faster than those NPs obtained from the neutral Ir(i) precursor, in the same IL.

We report the use of myristic acid as a tuning agent for the surface plasmon resonance of highly stable colloids containing gold nanoparticles. The large nonlinear optical response of these systems was also investigated.

Uma série de líquidos iônicos 1-alquil éter (e 1-alquil)-3-metilimidazólio 2-4 ([CxOyMIm]+[Ânion]??��� ou [CxMIm]+[Ânion]??���, onde MIm = 3-metilimidazólio; CxOy = 1-alquil éter, C7O3 =-(CH2)2O(CH2)2O(CH2)2OCH3 (A), C3O1 = -(CH2)2OCH3 (B); Cx = 1-alquil, C10 = C10H21 (C), C4 = C4H9 (D); e [Ânion]??��� = H3CSO3 ??��� (2), BF4 ??��� (3) ou PF6 (4)) foram preparados e caracterizados. A força da ligação de hidrogênio entre o cátion e o ânion dos líquidos iônicos 2-4 depende principalmente do ânion e diminui na ordem H3CSO3 ??��� > BF4 ??��� > PF6 ??���. Todos os líquidos iônicos metanosulfonatos 2 possuem uma forte desblindagem para o próton H2 do ciclo imidazólio. Os líquidos iônicos funcionalizados com um grupo 1-alquil éter mostram densidades mais altas em comparação com seus equivalentes do grupo 1-alquil. Os sais 2a-b, 3a-d e 4a-b são líquidos iônicos à temperatura ambiente. E, todos os líquidos iônicos 1-alquil éter funcionalizados (exceto 4b) são completamente amorfos. As maiores faixas líquidas foram obtidas com os líquidos iônicos tetrafluoroborato devido as suas solidificações a temperaturas baixas e excelente estabilidade térmica. Estes dados fornecem informações importantes para o entendimento sobre possíveis aplicações e a preparação de líquidos iônicos com tarefas específicas. A set of 1-alkyl ether (and 1-alkyl)-3-methylimidazolium ionic liquids 2-4 ([CxOyMIm]+[Anion]??�or [CxMIm]+[Anion]??�, where MIm = 3-methylimidazolium; CxOy = 1-alkyl ether, C7O3 =-(CH2)2O(CH2)2O(CH2)2OCH3 (A), C3O1 = -(CH2)2OCH3 (B); Cx = 1-alkyl, C10 = C10H21 (C), C4 =C4H9 (D); and [Anion]??� = H3CSO3??� (2), BF4??� (3) or PF6??� (4)) was prepared and characterized. The cation-anion hydrogen bonding strength showed to be mainly anion dependent and decreased in the order H3CSO3 ??� > BF4 ??� > PF6 ??�. All methanesulfonate ionic liquids 2 possessed a strongly deshielded H2 imidazolium ring proton. 1-Alkyl ether functionalized ionic liquids showed higher densities in comparison to their 1-alkyl equivalents. The salts 2a-b, 3a-d and 4a-b are room-temperature ionic liquids. All 1-alkyl ether functionalized ionic liquids (except 4b) are completely amorphous. The widest liquid ranges were obtained with the tetrafluoroborate ionic liquids due to their late solidification and excellent thermal stability. These data provide important information for the understanding of their application scope and the preparation of task-specific ionic liquids.

Rh(0) nanoparticles (ca. 4 nm) dispersed in an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate) were immobilized within a silica network, prepared by the sol-gel method. The effect of the sol-gel catalyst (acid or base) on the encapsulated ionic liquid and Rh(0) content, on the silica morphology and texture, and on the catalyst alkene hydrogenation activity was investigated. The Rh(0) content in the resulting xerogels (ca. 0.1 wt% Rh/SiO(2)) was shown to be independent of the sol-gel process. However, acidic conditions afforded higher contents of encapsulated ionic liquid and xerogels with larger pore diameters, which in turn might be responsible for the higher catalyst activity in hydrogenation of the alkenes.

Stable Pd(0) and Rh(0) nanoparticles with small and narrow size distribution can be prepared from relative large and agglomerated transition-metal particles dispersed in 1-n-butyl-3methylimidazolium hexafluorophosphate ionic liquid by simple laser irradiation. The laser irradiation is a complementary method for the generation of stable metal colloids in ionic liquids and also for the regeneration of small-size nanoparticles that may result from their agglomeration after different applications.