Influence of sugar cane burning on aerosol soluble ion composition in Southeastern Brazil

Seasonal variability in the major soluble ion composition of atmospheric particulate matter in the principal sugar cane growing region of central São Paulo State indicates that pre-harvest burning of sugar cane plants is an important influence on the regional scale aerosol chemistry. Samples of particulate matter were collected between April 1999 and February 2001 in coarse (> 3.5 mum) and fine (< 3.5 mum) fractions, and analysed for HCOO-, CH3COO-, C2C42-, SO42- . Results indicated that the principal sources of the aerosols investigated NO3-, Cl-, Na+, K+, NH4+, Mg2+ and Ca2+ were local or regional in nature (scale of tens to a few hundreds of km), and that differences between air masses of varying origins were small. Fine particles were typically acidic, containing secondary nitrates, sulphates and organic species. Coarse fraction concentrations were mainly influenced by physical parameters (wind speed, movement of vehicles and surface condition) affecting rates of re-suspension, although secondary nitrate and sulphate were also present in the larger particles.Concentrations of all measured species except sodium and chloride were higher during the burning season. Although concentrations were lower than often found in polluted urban environments, the massive increases during much of the year, due to a single anthropogenic activity (sugar cane burning) are indicative of a very large perturbation of the lower troposphere in the region relative to the natural condition. These aerosols are suspected of promoting respiratory disease. They also represent an important mechanism for the tropospheric transport of species relevant to surface acidification (sulphates, nitrates, ammonium and organic acids) and soil nutrient status (potassium, nitrogen, ammonium, calcium), so their impact on fragile natural ecosystems (following deposition) needs to be considered. (C) 2004 Elsevier Ltd. All rights reserved.

Thermodynamic aspects of ion intercalation in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: Application to the Everit's salt/Prussian Blue transition

The K+ reversible processes for ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K+ ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.

Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion

The low-weight Pd(II) coordination polymers [(N(3))(HL)Pd {Pd(3)(mu-N(3))(mu-L)(5)}10(mu-L)(2)Pd(L)(HL)]{L = Pz(-) (1); mPz(-) (2), IPz(-)(3)} and [(N(3))(HPz)Pd{Pd(6)(mu-N(3))(2)(mu-PZ)(5)(mu-L)(5)}(10)(mu-L)(2)Pd(Pz)(HPz)] {L = mPz(-) (4), dmPz(-) (5); IPz(-) (6)} {L = pyrazolate (Pz(-)), 4-methylpyrazolate(mPz(-)), 4-iodopyrazo late (IPz(-)), 3,5-dimethylpyrazolate (dmPz(-))} have been prepared in this work. IR spectra clearly indicated the exobidentate nature of pyrazolato ligands as well the end-on coordination mode of the azido group. The molecular weight determinations by osmometry indicated that the species have a low degree of polymerization (n = 10). NMR experiments showed two pyrazolate environments in a 2:1 ratio, being assigned to the six-membered ring Pd(mu-L)(2)Pd and the Pd(mu-N(3))(mu-L)Pd metallocycle, respectively. UV-visible spectroscopy gave further evidences for the oligomeric structures of 1-6. Some alternative structures for the isostructural polymers have been suggested. (c) 2005 Elsevier Ltd. All rights reserved.

Hexagonal-shaped tin glycolate particles: A preliminary study of their suitability as li-ion insertion electrodes

Tin glycolate particles were prepared by a simple, one-step, polyol-mediated synthesis in air in which tin oxalate precursor was added to ethylene glycol and heated at reflux. Hexagonal-shaped, micron-sized tin glycolate particles were formed when the solution had cooled. A series of tin oxides was produced by calcination of the synthesized tin glycolate at 600-800 degrees C. It was revealed that the micron-sized, hexagonal-shaped tin glycolate now consisted of nanosized tin-based particles (80-120 nm), encapsulated within a tin glycolate shell. XRD, TGA, and FT-IR measurements were conducted to account for the three-dimensional growth of the tin glycolate particles. When applied as an anode material for Li-ion batteries, the synthesized tin glycolate particles showed good electro-chemical reactivity in Li-ion insertion/ deinsertion, retaining a specific capacity of 416mAhg(-1) beyond 50cycles. Ibis performance was significantly better than those of all the other tin oxides nanoparticles (< 160mAhg(-1)) obtained after heat treatment in air. We strongly believe that the buffering of the volume expansion by the glycolate upon Li-Sn alloying is the main factor for the improved cycling of the electrode.

Size, electrophoretic mobility, and ion dissociation of vesicles prepared with synthetic amphiphiles

Vesicles prepared with synthetic amphiphiles (dioctadecyldimethylammonium bromide and chloride, dihexadecyl phosphate and its sodium salt) were obtained by sonication, ethanol injections, and chloroform injections. The hydrodynamic diameter of vesicles (Dh), estimated from the diffusivity measured by quasielastic light scattering, ranged from 230 to 3000 Å. The electrophoretic mobility (Um) was measured by free-flow electrophoresis. The zeta potential (ζ) and the degree of counterion dissociation (α) of the vesicles were calculated from Um and conductivity data, α decreased with increasing Dh of the vesicles, probably due to the decreasing headgroup area and the increasing counterion association needed to relax the surface electrostatic potential. The electrophoretic mobility was also calculated (Uc) according to an impenetrable, nonconducting sphere model with a spherically symmetric charge distribution approximation. Within the limits of the experimental error(s) of the (different) methods employed and the assumptions made in the calculations, the fact that the Um/Uc ratio ranged from 1.3 to 7.5 was considered to be a good agreement between the calculated and the experimental values. © 1990 American Chemical Society.

Calcium hydroxide root canal sealers: Evaluation of pH, calcium ion concentration and conductivity

The calcium hydroxide ionization of four root canal sealers (Sealapex, CRCS, Sealer 26, and Apexit) was studied by measuring conductivity and pH and by conducting atomic absorption spectrophotometry. Samples 6 mm in diameter and 15 mm long were prepared from these sealers. After setting and 48 h storage in a desiccator, five samples of each material were placed in 50 mL distilled water and analysed after 0,1,2,4, 6 and 24 h and 5, 15 and 30 days. The results showed that Sealapex was the root canal sealer showing the highest pH, ionic calcium and total calcium values (P<0.05) throughout the experimental period, followed by CRCS, Apexit and Sealer 26.

Interfacial concentrations of chloride and bromide and selectivity for ion exchange in vesicles prepared with dioctadecyldimethylammonium halides, lipids, and their mixtures

The local concentrations of chloride, Cl b, and bromide, Br b, in the interface of vesicles prepared with dioctadecyldimethylammonium chloride, DODAC, or bromide, DODAB, dipalmitoylphosphatidylcholine, DPPC, dimyristoylphosphatidylcholine, DMPC, and mixtures of DMPC, DPPC, and DODAC were determined by chemical trapping by analyzing product yields from spontaneous dediazoniation of vesicle-bound 2,6-dimethyl-4-hexadecylbenzenediazonium ion. The values of Cl b and Br b in DODAC and DODAB vesicles increase with vesicle size, in agreement with previous data showing that counterion dissociation decreases with vesicle size. Addition of tetramethylammonium chloride displaces bromide from the DODAB vesicular interface. The value for the selectivity constant for Br/Cl exchange at the DODAB vesicular interface obtained by chemical trapping was ∼2.0, well within values obtained for comparable amphiphiles. In vesicles of DPPC the values of Cl b were very sensitive to the nature of the cation and decreased in the order Ca 2+ > Mg 2+ > Li + > Na + > K + = Cs + = Rb + ≥ +. The effect of the cation becomes more important as temperature increases above the phase transition temperature, T m, of the lipid. The values of Cl b increased sigmoidally with the mol % of DODAC in vesicles prepared with DODAC/lipid mixtures. In sonicated vesicles prepared with DODAC and DMPC (or DPPC), the values of Cl b reach local concentrations measured for the pure amphiphile at 80 mol % DODAC. These results represent the first extensive study of local concentration of ions determined directly by chemical trapping in vesicles prepared with lipids, synthetic ampliiphiles, and their mixtures.

Characterization of proanthocyanidins from Parkia biglobosa (Jacq.) G. Don. (Fabaceae) by flow injection analysis - Electrospray ionization ion trap tandem mass spectrometry and liquid chromatography/electrospray ionization mass spectrometry

The present study investigates the chemical composition of the African plant Parkia biglobosa (Fabaceae) roots and barks by Liquid Chromatography - Electrospray Ionization and Direct Injection Tandem Mass Spectrometry analysis. Mass spectral data indicated that B-type oligomers are present, namely procyanidins and prodelphinidins, with their gallate and glucuronide derivatives, some of them in different isomeric forms. The analysis evidenced the presence of up to 40 proanthocyanidins, some of which are reported for the first time. In this study, the antiradical activity of extracts of roots and barks from Parkia biglobosa was evaluated using DPPH method and they showed satisfactory activities.

Silver ion release from electrodes of nanotubes of TiO2 impregnated with Ag nanoparticles applied in photoelectrocatalytic disinfection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Hydroxythiazole-Based Fluorescent Probes for Fluoride Ion Detection

This work describes the synthesis of five O-silyloxy-1,3-thiazoles and their use as fast-response turn-on probes for fluoride ion detection in polar aprotic solvents and in aqueous cetyltrimethylammonium bromide micellar medium. The fluoride-triggered deprotection of these silyl ethers results in ca. 180-nm shifts in the fluorescence emission wavelengths. All compounds are suitable for the detection of fluoride ions with a detection limit in DMSO of 107 mol?L1; derivatives containing a 2-pyridyl moiety in the thiazole system are more efficient than those with a 3- or 4-pyridyl moiety. Typical anionic interferents, such as acetate or chloride, are not detected by O-silyloxy-1,3-thiazoles, making these compounds very specific for fluoride.

Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry

The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (Rp-p). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N-2 and CO2 were tested as the drift gas, and similar a but considerably better values of R-p and Rp-p were always observed for CO2. Copyright (C) 2012 John Wiley & Sons, Ltd.

Tailored SERS substrates obtained with cathodic arc plasma ion implantation of gold nanoparticles into a polymer matrix

This manuscript reports on the fabrication of plasmonic substrates using cathodic arc plasma ion implantation, in addition to their performance as SERS substrates. The technique allows for the incorporation of a wide layer of metallic nanoparticles into a polymer matrix, such as PMMA. The ability to pattern different structures using the PMMA matrix is one of the main advantages of the fabrication method. This opens up new possibilities for obtaining tailored substrates with enhanced performance for SERS and other surface-enhanced spectroscopies, as well as for exploring the basic physics of patterned metal nanostructures. The architecture of the SERS-active substrate was varied using three adsorption strategies for incorporating a laser dye (rhodamine): alongside the nanoparticles into the polymer matrix, during the polymer cure and within nanoholes lithographed on the polymer. As a proof-of-concept, we obtained the SERS spectra of rhodamine for the three types of substrates. The hypothesis of incorporation of rhodamine molecules into the polymer matrix during the cathodic arc plasma ion implantation was supported by FDTD (Finite-Difference Time-Domain) simulations. In the case of arrays of nanoholes, rhodamine molecules could be adsorbed directly on the gold surface, then yielding a well-resolved SERS spectrum for a small amount of analyte owing to the short-range interactions and the large longitudinal field component inside the nanoholes. The results shown here demonstrate that the approach based on ion implantation can be adapted to produce reproducible tailored substrates for SERS and other surface-enhanced spectroscopies.

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers.

Counter-ion effect on surfactant-DNA gel particles as controlled DNA delivery systems

The ability to entrap drugs within vehicles and subsequently release them has led to new treatments for a number of diseases. Based on an associative phase separation and interfacial diffusion approach, we developed a way to prepare DNA gel particles without adding any kind of cross-linker or organic solvent. Among the various agents studied, cationic surfactants offered particularly efficient control for encapsulation and DNA release from these DNA gel particles. The driving force for this strong association is the electrostatic interaction between the two components, as induced by the entropic increase due to the release of the respective counter-ions. However, little is known about the influence of the respective counter-ions on this surfactant-DNA interaction. Here we examined the effect of different counter-ions on the formation and properties of the DNA gel particles by mixing DNA (either single-(ssDNA) or double-stranded (dsDNA)) with the single chain surfactant dodecyltrimethylammonium (DTA). In particular, we used as counter-ions of this surfactant the hydrogen sulfate and trifluoromethane sulfonate anions and the two halides, chloride and bromide. Effects on the morphology of the particles obtained, the encapsulation of DNA and its release, as well as the haemocompatibility of these particles are presented, using counter-ion structure and DNA conformation as controlling parameters. Analysis of the data indicates that the degree of counter-ion dissociation from the surfactant micelles and the polar/hydrophobic character of the counter-ion are important parameters in the final properties of the particles. The stronger interaction with amphiphiles for ssDNA than for dsDNA suggests the important role of hydrophobic interactions in DNA.

Protomers: formation, separation and characterization via travelling wave ion mobility mass spectrometry

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH3, whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO2 loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups. Copyright (C) 2012 John Wiley & Sons, Ltd.