Spectroscopic study of the polymerization of intercalated anilinium ions in different montmorillonite clays

The polymerization of the intercalated aniline ions was studied in three different clays, Swy2-montmorillonite (MMT), synthetic mica-montmorillonite (Synl) and pillarized Swy2-montmorillonite (PILC). PANI is formed between the MMT and Syn1 clay layers, being confirmed by the shift of d(001) peak in the X-ray pattern. X-ray Absorption near to Si K edge (Si K XANES) data show that the structures of clays are preserved after the polymerization process and in addition to the SEM images show that morphologies of the clays are maintained after polymerization, indicating no polymerization in their external surface. UV-vis-NIR and resonance Raman data display that the PANI formed in Syn1 galleries has higher amount of phenazinic rings than observed for PANI intercalated in montmorillonite (MMT) clay. No polymer formation was detected in the PILC. N K XANES and EPR spectroscopies show the presence of azo and radical nitrogen in intercalated PAN! chains. Hence, the results are rationalized considering the structural differences between the clays for understanding the role of the anilinium polymerization within the clays galleries. (C) 2011 Elsevier B.V. All rights reserved.

Influence of neodymium ions on photocatalytic activity of TiO(2) synthesized by sol-gel and precipitation methods

Titanium dioxide with and without the addition of neodymium ions was prepared using sol-gel and precipitation methods. The resulting catalysts were characterized by thermal analysis, X-ray diffraction and BET specific surface area. Neodymium addition exerted a remarkable influence on the phase transition temperature and the surface properties of the TiO(2) matrix. TiO(2) samples synthesized by precipitation exhibit an exothermic event related from the amorphous to anatase phase transition at 510 degrees C, whereas in Nd-doped TiO(2) this transition occurred at 527 degrees C. A similar effect was observed in samples obtained using sol-gel method. The photocatalytic reactivity of the catalysts was evaluated by photodegradation of Remazol Black B (RB) under ultraviolet irradiation. Nd-doped TiO(2) showed enhanced photodegradation ability compared to undoped TiO(2) samples, independent of the method of synthesis. In samples obtained by sol-gel, RB decoloration was enhanced by 16% for TiO(2) doped with 0.5% neodymium ions. (C) 2010 Elsevier B.V. All rights reserved.

The role of solvent on the doping of polyaniline with Fe(III) ions

The products formed from the reaction of emeraldine base polyaniline (EB-PANI) with Fe(III) ions in N-methyl-pyrrolidone (NMP), dimethylacetamide (DMA), dimethylformamide (DMF) and m-cresol media have been investigated using UV-VIS-NIR and resonance Raman (lambda(0) = 632.8 and 1064 nm) spectroscopies. Through these results it was verified that the different PANI forms in solution can be formed by the suitable choice of the solvent. The behavior of Fe(III)/EB-PANI in different solvents was rationalized in terms of the interactions among Fe(III) ions, EB-PANI and solvent. In basic NMP, DMA and DMF media, the reaction of Fe(III) with EB-PANI yields EB-PANI doping giving ES-PANI and/or the EB-PANI oxidation to PB-PANI. The formation of ES-PANI is favored in DMF while PB-PANI is formed in a greater extension in NMP and DMA. In acidic m-cresol, only ES-PANI is produced in Fe(III)/EB-PANI solutions indicating the important role played by the solvent in the nature of the product. (C) 2010 Elsevier B.V. All rights reserved.

Removal of metal ions from aqueous solution by chelating polymeric hydrogel

Polysaccharide natural seed coat from the tree Magonia pubescens, in the form of hydrogel was used to remove metals in aqueous solution. Swelling tests indicate that seed coat presents hydrogel behavior, with maximum water absorption of 292 g water/g. Adsorption experiments performed using Na(+), Mg(2+), K(+), Ca(2+), Cr(3+), Fe(3+) and Zn(2+) demonstrated that the polysaccharide structure has a high capacity to extract these ions from the aqueous solution. Scanning electron microscopy revealed significant morphological changes of the material before and after water contact. Differential scanning calorimetry measurements indicate a signal shift of the water evaporation temperature in the material with adsorbed zinc. X-ray photoelectron spectroscopy analysis combined with theoretical studies by the density functional theory and on Hartree-Fock (HF) level evidence that the metallic ions were adsorbed through coordination with hydroxyl groups of polysaccharide. In the case of Zn(2+) the lowest HF energy was observed for the tetracoordination mode, where Zn(2+) is coordinated by two hydroxyl groups and two water molecules.

The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

Metal ions and carcinogenesis

Metals are essential for the normal functioning of living organisms. Their uses in biological systems are varied, but are frequently associated with sites of critical protein function, such as zinc finger motifs and electron or oxygen carriers. These functions only require essential metals in minute amounts, hence they are termed trace metals. Other metals are, however, less beneficial, owing to their ability to promote a wide variety of eleterious health effects, including cancer. Metals such as arsenic, for example, an produce a variety of diseases ranging from keratosis of the palms and feet to cancers in multiple target organs. The nature and type of metal-induced pathologies appear to be dependent on the concentration, speciation, and length of exposure. Unfortunately, human contact with metals is an inescapable consequence of human life, with exposures occurring from both occupational and environmental sources. A uniform mechanism of action for all harmful metals is unlikely, if not implausible, given the diverse chemical properties of each metal. In this chapter we will review the mechanisms of carcinogenesis of arsenic, cadmium, chromium, and nickel, the four known carcinogenic metals that are best understood. The key areas of speciation, bioavailability, and mechanisms of action are discussed with particular reference to the role of metals in alteration of gene expression and maintenance of genomic integrity.

α,ω-Bis(trichlorostannyl)alkanes as Bis(monodentate) lewis acids toward halide ions

The reactions between X₃Sn(CH₂)_nSnX₃ (X = Cl, Br; _n = 1, 3, 4, 8) and halide in solution are described. ¹¹⁹Sn NMR spectroscopy (CD₂Cl₂) indicates formation of five-coordinate dinuclear 1:2 adducts, [X₄Sn(CH₂)_nSnX₄]^2-, with chloride and bromide. A trigonal-bipyramidal geometry has been confirmed in the solid state for the compound having X = Cl and _n = 4. In contrast, fluoride reacts with X₃Sn(CH₂)_nSnX₃ to give six-coordinate tin species, [F₅Sn(CH₂)_nSnF₅].^4- There was no evidence indicating that the tin atoms could act as a bidentate acid.

Contribution of fungi to primary biogenic aerosols in the atmosphere: wet and dry discharged spores, carbohydrates, and inorganic ions

Biogenic aerosols play important roles in atmospheric chemistry physics, the biosphere, climate, and public health. Here, we show that fungi which actively discharge their spores with liquids into the air, in particular actively wet spore discharging Ascomycota (AAM) and actively wet spore discharging Basidiomycota (ABM), are a major source of primary biogenic aerosol particles and components. We present the first estimates for the global average emission rates of fungal spores.

Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the spores of AAM and ABM may account for a large proportion of coarse particulate matter in tropical rainforest regions during the wet season (0.7–2.3 μg m⁻³). For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively wet discharged basidiospores (ABS). ABM emissions seem to account for most of the atmospheric abundance of mannitol (10–68 ng m⁻³), and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter (7–49 ng m⁻³), but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season (17–43 ng m⁻³), and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations.

Based on the average abundance of mannitol reported for extratropical continental boundary layer air (~25 ng m⁻³), we have also calculated a value of ~17 Tg yr⁻¹ as a first estimate for the global average emission rate of ABS over land surfaces, which is consistent with the typically observed concentrations of ABS (~10³–10⁴ m⁻³; ~0.1^–1 μg m⁻³). The global average atmospheric abundance and emission rate of total fungal spores, including wet and dry discharged species, are estimated to be higher by a factor of about three, i.e. 1 μg m⁻³ and ~50 Tg yr⁻¹. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr⁻¹ of anthropogenic primary organic aerosol; 12–70 Tg yr⁻¹ of secondary organic aerosol) indicate that emissions from fungi should be taken into account as a significant global source of organic aerosol. The effects of fungal spores and related chemical components might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

The influence of geometry and wall character of pores on the permeation of ions and water through desalination membranes

The transport of water and ions across mimicked nanotube membranes with pseudo atoms is studied using molecular dynamics simulations under equilibrium conditions and hydrostatic pressure. Different pore surface properties are constructed by assigning partial charges on the sites of specified atoms to explore the influence of charges and polarity. The energetics of water and ion transports through the nanopores was calculated to evaluate their filterability to water. The simulation results show that the free energy barriers to water and ion conductions much depend on the charges at the pore entrance and the dipole within the pore. The membranes with hydrophobic pores and negatively charged entrances would be very efficient in the water transport and ion rejection. The charges and dipoles of the pore wall and the aligned dipoles of water molecules in the pore can create a significant force on ions.

Improved extraction of heavy metal ions using membrane technology

Investigates tha application of polymer membranes in industrial wastewater treatment. Several novel membrane systems have been developed. The new systems overcome the problems of low extractant capacity and slow rate of extraction of the traditional membrane system. These new systems offer significant scope for the treatment of industrial wastewater containing heavy metal ions.

Using polyatomic primary ions to probe an amino acid and a nucleic base in water ice

In this study on pure water ice, we show that protonated water species [H₂O]_nH⁺ are more prevalent than (H₂O)_n⁺ ions after bombardment by Au+ monoatomic and Au₃⁺ and C₆₀⁺ polyatomic projectiles. This data also reveals significant differences in water cluster yields under bombardment by these three projectiles. The amino acid alanine and the nucleic base adenine in solution have been studied and have been shown to have an effect on the water cluster ion yields observed using an Au₃⁺ ion beam.

Wool powders used as sorbents to remove Co2+ ions from aqueous solution

The Co2+ sorption of two wool powders was investigated using its radioisotope 57Co (T1/2=271.8 days and γ=122.1 and 136.5 keV) as a tracer. The effects of the type of buffer, the pH value, the contact time and the initial concentration of Co2+ on the sorption behaviour of wool powders were studied. The Co2+ releasing ability of wool powders and the re-use of wool powders to sorb Co2+ were also examined. The optimum sorption of Co2+ by the powders occurred at pH 8 in phosphate buffer and pH 10 in ammonium sulphate buffer. Fourier-transform infrared spectroscopy (FTIR) was used to study the changes in chemical structure of the wool after exposure to both buffer solutions. Compared to the untreated wool fibre, the fine wool powders showed rapid sorption rates and high sorption capacities for Co2+. Co2+ ions were recovered after exposing the Co2+ loaded wool to HCl (0.1 M) and buffer at pH 3 (glycine/sodium chloride). After releasing Co2+ ions from wool powders, the efficiency of wool powders re-used to sorb Co2+ was 80% of that of the fresh wool powders. It is concluded from this study that wool powder can be used as an efficient sorbent to remove and release Co2+ from solution.

Sub-ppt detection limits for copper ions with Gly-Gly-His modified electrodes

An electrochemical metal ion sensor has been developed with a detection limit of less than 0.2 ppt by the covalent attachment of the tripeptide Gly-Gly-His as a recognition element to a 3-mercaptopropionic acid modified gold electrode.

Fast colorimetric detection of copper ions using L-Cysteine functionalized gold nanoparticles

This communication reports an efficient visual detection method of Cu²⁺ by L-cysteine functionalized gold nanoparticles in aqueous solution. Upon exposure to Cu²⁺, the gold nanoparticle solution changed from red to blue, in response to surface plasmon absorption of dispersed and aggregated nanoparticles. This colorimetric sensor allows a rapid quantitative assay of Cu²⁺ down to the concentration range of 10⁻⁵ M. Recognition of Cu²⁺ and formation of the aggregates are proposed to occur via a 2 : 1 sandwich complex between L-cysteine and Cu²⁺.