The effect of ionic strength on the structural organization of dioctadecyldimethylammonium bromide in aqueous solution

High-curvature and stabilized vesicles of dioctadecyldimethylammonium bromide (DODABr) can be formed spontaneously in aqueous electrolytic solution. It is shown by cryo-transmission electron microscopy that 5.0 mM DODABr molecules associate in water at a temperature above its gel-to-liquid-crystalline phase transition temperature (T(m)approximate to45 degreesC) in a variety of complex bilayer structures. However, in the presence of NaCl the preferred structures formed are unilamellar and bilamellar vesicles with high curvature and the dispersion is polydisperse in size and geometry, but the main vesicle population contains spherical, flattened and smoothed structures. It is, however, less polydisperse than the corresponding salt-free dispersion, and the size polydispersity and the vesicle curvature radius tend to decrease with NaCl concentration. Long cylindrical bilamellar vesicles, with a very thin water layer separating the bilayers are also formed in the presence of 10 mM NaCl. The effect of the ionic strength on T-m, obtained by differential scanning calorimetry, is shown to depend on the nature of the counterion: Br- decreases, whereas Cl- increases Tm of DODABr, indicating different affinity of these counterions for the vesicle surfaces.

Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

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

A general treatment for the conductivity of electrolytes in the whole concentration range in aqueous and nonaqueous solutions

Despite the great importance of ion transport, most of the widely accepted models and theories are valid only in the not very practical limit of low concentrations. Aiming to extend the range of applicability to moderate concentrations, a number of modified models and equations (some approximate, some fundamented on different assumptions, and some just empirical) have been reported. In this work, a general treatment for the electrical conductivity of ionic solutions has been developed, considering the electrical conductivity as a transport phenomenon governed by dissipation and feedback. A general expression for the dependence of the specific conductivity on the solution viscosity (and indirectly on concentration), from which the whole conductivity curve can be obtained, has been derived. The validity of this general approach is demonstrated with experimental results taken from the literature for aqueous and nonaqueous solutions of electrolytes.

Interactions between the non-ionic surfactant C(12)E(5) and poly(ethylene oxide) studied using dynamic light scattering and fluorescence quenching

Dynamic light scattering measurements have been made to elucidate changes in the coil conformation of a high molecular weight poly(ethylene oxide) (PEG) fraction when the non-ionic surfactant C(12)E(5) is present in dilute solutions. The measurements were made at 20 degrees C as functions of(a) the C(12)E(5) concentration at constant PEO concentration, (b) the PEO concentration at constant C(12)E(5) concentration, and (c) the C(12)E(5)/PEO concentration ratio. The influence of temperature on the interactions in terms of the relaxation time distributions was also examined up to the cloud point. It was found that when the C(12)E(5)/PEO weight ratio was >2 and when the temperature was >14 degrees C, the correlation functions became bimodal with well-separated components. The fast mode derives fi om individual surfactant micelles which are present in the solution at high number density. The appearance of the slow mode, which dominates the scattering, is interpreted as resulting from the formation of micellar clusters due to an excluded-volume effect when the high molar mass (M = 6 x 10(5)) PEO is added to the surfactant solution. It is shown that the micellar clusters form within the PEO coils and lead to a progressive swelling of the latter for steric reasons. The dimensions of the PEO/C(12)E(5) complex increase with increasing surfactant concentration to a value of R(H) approximate to 94 nm (R(g) approximate to 208 nm) at C-C12E5 = 3.5%. Fluorescence quenching measurements show that the average aggregation number of C(12)E(5) increases significantly on addition of the high molar mass PEG. With increasing temperature toward the cloud point the clusters increase in number density and/or become larger. The cloud point is substantially lower than that for C12E5 in water solution and is strongly dependent on the PEO concentration.

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.

Correlation between local structure and ionic conductivity of potassium-doped siloxane poly(propyleneoxyde) ormolytes

The local order around K for K(CF3SO3) doped Siloxane-Poly(propyleneoxide) hybrids at different doping concentration was investigated by x-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge. The results indicate that the use of HCl as hydrolytic catalyst for gelation induces the precipitation of KCl. The ionic conductivity is strongly related to the presence of oxygen atoms as first neighbours around potassium and to the amount of KCl precipitate. © Physica Scripta 2005.

Characterization of a tannase from Emericela nidulans immobilized on ionic and covalent supports for propyl gallate synthesis

The extracellular tannase from Emericela nidulans was immobilized on different ionic and covalent supports. The derivatives obtained using DEAE-Sepharose and Q-Sepharose were thermally stable from 60 to 75 °C, with a half life (t50) >24 h at 80 °C at pH 5. 0. The glyoxyl-agarose and amino-glyoxyl derivatives showed a thermal stability which was lower than that observed for ionic supports. However, when the stability to pH was considered, the derivatives obtained from covalent supports were more stable than those obtained from ionic supports. DEAE-Sepharose and Q-Sepharose derivatives as well as the free enzyme were stable in 30 and 50 % (v/v) 1-propanol. The CNBr-agarose derivative catalyzed complete tannic acid hydrolysis, whereas the Q-Sepharose derivative catalyzed the transesterification reaction to produce propyl gallate (88 % recovery), which is an important antioxidant. © 2012 Springer Science+Business Media Dordrecht.

Evaluation of ionic degradation and slot corrosion of metallic brackets by the action of different dentifrices

OBJETIVO: avaliar in vitro a degradação iônica e corrosão do fundo do slot de braquetes metálicos submetidos à escovação com dentifrícios, realizando análises da composição química por Espectroscopia de Energia Dispersiva (EDS) e qualitativa por Microscopia Eletrônica de Varredura (MEV). MÉTODOS: foram selecionados 38 braquetes divididos aleatoriamente em quatro grupos experimentais (n = 7). Dois grupos (n = 5) funcionaram como controles positivo e negativo. Aparelhos ortodônticos simulados foram confeccionados com fios de aço inoxidável 0,019" x 0,025" e anéis elastoméricos. Os grupos foram divididos de acordo com o tratamento de superfície: G1 (Máxima Proteção Anticáries®); G2 (Total 12®); G3 (Sensitive®); G4 (Branqueador®); Controle Positivo (saliva artificial) e Controle Negativo (sem tratamento). Foram realizados 28 ciclos de escovação e avaliações antes (T0) e após (T1) o experimento. RESULTADOS: o teste de Wilcoxon indicou não existir diferença nas concentrações iônicas de titânio (Ti), cromo (Cr), ferro (Fe) e níquel (Ni) entre os grupos. O grupo G2 apresentou redução significativa (p < 0,05) na concentração do íon alumínio (Al) e os grupos G3 e G4 apresentaram aumento significativo (p < 0,05) nas concentrações do íon alumínio. A análise em MEV mostrou aumento nas características indicativas de corrosão dos grupos G2, G3 e G4. CONCLUSÃO: a análise por EDS revelou que os grupos controle e G1 não sofreram alterações na composição química. O grupo G2 apresentou degradação na quantidade de íons Al, e G3 e G4 sofreram aumento na concentração de Al. A imersão em saliva artificial e o dentifrício Máxima Proteção Anticáries® não alteraram o polimento de superfície. Os dentifrícios Total 12®, Sensitive® e Branqueador® alteraram o polimento de superfície.

Using ionic liquid combined with HPLC-DAD to analyze semi-permanent hair dyes in commercial formulations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

Ionic Transport and Water Vapor Uptake of Ammonium Exchanged Perfluorosulfonic Acid Membranes

Nafion membranes series N117 doped with ammonium, at different cation fractions (H+/NH4+), were investigated for ionic transport and water vapor uptake, for several water activities and temperatures. Ammonium cations change both properties of the polymer in a similar manner. Membrane ionic conductivity and water vapor uptake (lambda) decrease as the ammonium concentration increases in the polymer. Ionic transport activation energies are calculated and the transport mechanism of ammonium ions in Nafion is discussed. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.040203jes] All rights reserved.

Structure and Ionic Conductivity in the Mixed-Network Former Chalcogenide Glass System [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3)

Glasses in the system [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3) (0.0 <= x <= 1.0) were prepared by the melt quenching technique, and their properties were characterized by thermal analysis and impedance spectroscopy. Their atomic-level structures were comprehensively characterized by Raman spectroscopy and B-11, P-31, and Na-23 high resolution solid state magic-angle spinning (MAS) NMR techniques. P-31 MAS NMR peak assignments were made by the presence or absence of homonuclear indirect P-31-P-31 spin-spin interactions as detected using homonuclear J-resolved and refocused INADEQUATE techniques. The extent of B-S-P connectivity in the glassy network was quantified by P-31{B-11} and B-11{P-31} rotational echo double resonance spectroscopy. The results clearly illustrate that the network modifier alkali sulfide, Na2S, is not proportionally shared between the two network former components, B and P. Rather, the thiophosphate (P) component tends to attract a larger concentration of network modifier species than predicted by the bulk composition, and this results in the conversion of P2S74-, pyrothiophosphate, Na/P = 2:1, units into PS43-, orthothiophosphate, Na/P = 3:1, groups. Charge balance is maintained by increasing the net degree of polymerization of the thioborate (B) units through the formation of covalent bridging sulfur (BS) units, B S B. Detailed inspection of the B-11 MAS NMR spectra reveals that multiple thioborate units are formed, ranging from neutral BS3/2 groups all the way to the fully depolymerized orthothioborate (BS33-) species. On the basis of these results, a comprehensive and quantitative structural model is developed for these glasses, on the basis of which the compositional trends in the glass transition temperatures (T-g) and ionic conductivities can be rationalized. Up to x = 0.4, the dominant process can be described in a simplified way by the net reaction equation P-1 + B-1 reversible arrow P-0 + B-4, where the superscripts denote the number of BS atoms for the respective network former species. Above x = 0.4, all of the thiophosphate units are of the P-0 type and both pyro-(B-1) and orthothioborate (B-0) species make increasing contributions to the network structure with increasing x. In sharp contrast to the situation in sodium borophosphate glasses, four-coordinated thioborate species are generally less abundant and heteroatomic B-S-P linkages appear to not exist. On the basis of this structural information, compositional trends in the ionic conductivities are discussed in relation to the nature of the charge-compensating anionic species and the spatial distribution of the charge carriers.

The Role of Water Chemistry in the Concentration of Hematite Ore

Selective flocculation and dispersion processes rely on differences in the surface chemistry of fine mineral particles (<25 >ìm) to allow for the concentration of specific minerals from an ore body. The effectiveness of selective flocculation and dispersion processes for the concentration of hematite (Fe2O3) ore are strongly dependent on the ionic content of the process water. The goal of this research was to analyze the ionic content of an operating selective flocculation and dispersion type hematite ore concentrator and determine how carbon dioxide affects the filtration of the final product. A detailed water chemistry analysis of the entire process was determined to show concentration profiles throughout the process. This information was used to explain process phenomena and promote future research into this subject. A subsequent laboratory study was conducted to show how carbon dioxide affects filtration rate and relate this effect to the zeta potential of the constituents of the concentrated hematite ore.

Mean snow accumulation rate, and mean methane sulfonate, chloride and nitrate concentration in snow pits and firn cores of Dronning Maud Land

We quantified postdepositional losses of methane sulfonate (MSA-), nitrate, and chloride at the European Project for Ice Coring in Antarctica (EPICA) drilling site in Dronning Maud Land (DML) (75°S, 0°E). Analyses of four intermediate deep firn cores and 13 snow pits were considered. We found that about 26 ± 13% of the once deposited nitrate and typically 51 ± 20% of MSA- were lost, while for chloride, no significant depletion could be observed in firn older than one year. Assuming a first order exponential decay rate, the characteristic e-folding time for MSA- is 6.4 ± 3 years and 19 ± 6 years for nitrate. It turns out that for nitrate and MSA- the typical mean concentrations representative for the last 100 years were reached after 5.4 and 6.5 years, respectively, indicating that beneath a depth of around 1.2-1.4 m postdepositional losses can be neglected. In the area of investigation, only MSA- concentrations and postdepositional losses showed a distinct dependence on snow accumulation rate. Consequently, MSA- concentrations archived at this site should be significantly dependent on the variability of annual snow accumulation, and we recommend a corresponding correction. With a simple approach, we estimated the partial pressure of the free acids MSA, HNO3, and HCl on the basis of Henry's law assuming that ionic impurities of the bulk ice matrix are localized in a quasi-brine layer (QBL). In contrast to measurements, this approach predicts a nearly complete loss of MSA-, NO3 - , and Cl-.

Haemolymph inorganic ion composition, physiology and behaviour dependent on temperature and ambient magnesium concentration in early life history stages of Paralomis granulosa (Decapoda, Anomura, Lithodidae)

Marine brachyuran and anomuran crustaceans are completely absent from the extremely cold (-1.8 °C) Antarctic continental shelf, but caridean shrimps are abundant. This has at least partly been attributed to low capacities for magnesium excretion in brachyuran and anomuran lithodid crabs ([Mg2+]HL = 20-50 mmol/L) compared to caridean shrimp species ([Mg2+]HL = 5-12 mmol/L). Magnesium has an anaesthetizing effect and reduces cold tolerance and activity of adult brachyuran crabs. We investigated whether the capacity for magnesium regulation is a factor that influences temperature-dependent activity of early ontogenetic stages of the Sub-Antarctic lithodid crab Paralomis granulosa. Ion composition (Na+, Mg2+, Ca2+, Cl-, [SO4]2-) was measured in haemolymph withdrawn from larval stages, the first and second juvenile instars (crabs I and II) and adult males and females. Magnesium excretion improved during ontogeny, but haemolymph sulphate concentration was lowest in the zoeal stages. Neither haemolymph magnesium concentrations nor Ca2+:Mg2+ ratios paralleled activity levels of the life stages. Long-term (3 week) cold exposure of crab I to 1 °C caused a significant rise of haemolymph sulphate concentration and a decrease in magnesium and calcium concentrations compared to control temperature (9 °C). Spontaneous swimming activity of the zoeal stages was determined at 1, 4 and 9 °C in natural sea water (NSW, [Mg2+] = 51 mmol/L) and in sea water enriched with magnesium (NSW + Mg2+, [Mg2+] = 97 mmol/L). It declined significantly with temperature but only insignificantly with increased magnesium concentration. Spontaneous velocities were low, reflecting the demersal life style of the zoeae. Heart rate, scaphognathite beat rate and forced swimming activity (maxilliped beat rate, zoea I) or antennule beat rate (crab I) were investigated in response to acute temperature change (9, 6, 3, 1, -1 °C) in NSW or NSW + Mg2+. High magnesium concentration reduced heart rates in both stages. The temperature-frequency curve of the maxilliped beat (maximum: 9.6 beats/s at 6.6 °C in NSW) of zoea I was depressed and shifted towards warmer temperatures by 2 °C in NSW + Mg2+, but antennule beat rate of crab I was not affected. Magnesium may therefore influence cold tolerance of highly active larvae, but it remains questionable whether the slow-moving lithodid crabs with demersal larvae would benefit from an enhanced magnesium excretion in nature.