Mössbauer studies of the corrosion products of iron formed in aqueous ammonium nitrate solution

The products of corrosion reaction of electrolytic iron in 45% ammonium nitrate solution formed under various conditions of time, temperature and pH have been analysed mainly by Mössbauer spectroscopy, in combination with X-ray diffraction, infrared absorption and electron microscopy techniques. γ-Fe00H is found to be the major product of hydrolytic precipitation at pH > 5.6 while only α-FeOOH is formed at pH < 3.0. In the pH range 3.0 < pH < 5.0, α-Fe00H and ferrihydrite are both formed. However, once the nuclei of α-Fe00H are formed under low pH conditions, their growth is favoured even in the otherwise unfavourable slightly acidic medium, resulting in a hydrous α-Fe00H which has two distinct hyperfine fields at the 57Fe nucleus. Magnetite is always formed in the vicinity of the metal and its rate of formation on the surface increases with temperature. α-Fe203 is the major product of hydrolytic precipitation at temperatures >80C. The possible mechanisms for the formation of each of the corrosion products are discussed.

Photodimerization of coumarin in aqueous and micellar media

The photochemical and photophysical processes of many organic compounds are a function of the environment in which they are present. In this connection we have chosen to investigate the environmental perturbations on the photodimerization of coumarin,l and the results of our study in aqueous and micellar media are presented in this paper. Coumarin has historically been the subject of intense photochemical and spectroscopic interest, mainly as a consequence of its importance in biological systems. Coumarin has been chosen for our investigation as its fascinating photochemical behavior has been fairly well explored,2 and therefore the environmental influence, which is the subject of our concern, would be easily understandable.

Thermodynamics of cobalt-manganese alloys using fluoride and oxide electrolytes

Abstract is not available.

Solubility of ibuprofen in aqueous ethanol at low ethanol contents

The solubility of ibuprofen was measured in water (W) - ethanol (E) mixtures from 0 to 50% w/w ethanol at 10, 25 and 40 °C by the dissolution method using UV spectrophotometry to determine the ibuprofen concentrations. The UV calibration for ibuprofen in different water - ethanol mixtures showed Beer - Lambert linearity, however the slopes differed, which indicated the structure of the drug is influenced by the solvent system i.e. the water - ethanol ratio. The ibuprofen solubility in water (zero ethanol) is low (~ 50 ppm) but increases near exponentially with increasing ethanol content. At 40 °C, there is phase separation between 34% and 63% w/w E/(E+W). The solubility data will be used to select precipitation crystallizer conditions to directly produce free flowing ibuprofen particles (<5 m) for developing a dry powder inhaler (DPI) formulation for lung delivery.

Nanostructured Peptide Fibrils Formed at the Organic-Aqueous Interface and Their Use as Templates To Prepare Inorganic Nanostructures

Formation of fibril-type nanostructures of the Alzheimer's beta-amyloid diphenylalanine (L-Phe-L-Phe, FF) at the organic-aqueous interface and the factors affecting their structures have been investigated. Such nanostructures are also formed by bovine serum albumin and bovine pancreas insulin. The concentration of the precursor taken in the aqueous layer plays an important role in determining the morphology of the nanostructures, The addition of curcumin to the organic layer changes the structure of the self-assembled one-dimensional aggregates of diphenylalanine. By coating the diphenylalanine dipeptide fibrils with appropriate precursors followed by calcination in air, it has been possible to obtain one-dimensional nanostructures of inorganic materials.

Mordenite-incorporated PVA-PSSA membranes as electrolytes for DMFCs

Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm2 is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm2 with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.

Surface-enhanced Raman scattering of molecules adsorbed on nanocrystalline Au and Ag films formed at the organic-aqueous interface

Surface-enhanced Raman scattering (SERS) of pyridine adsorbed on ultrathin nanocrystalline Au and Ag films generated at the liquid-liquid interface has been investigated. The shifts and intensification of bands formed with these films comprising metal nanoparticles are comparable to those found with other types of Au and Ag substrates. SERS of rhodamine 6G adsorbed on Ag films has also been studied. The results demonstrate that nanocrystalline metal films prepared by the simple method involving the organic-aqueous interface can be used effectively for SERS investigations.

Fluorescent alamethicin fragments A study of membrane activity and aqueous phase aggregation

The linear polypeptide antibiotic alamethicin is known to form channels in artificial lipid membranes. Synthetic 13- and 17-residue alamethicin fragments, labelled with a fluorescent dansyl group at the N-terminus, have been shown to translocate divalent cations across phospholipid membranes and to uncouple oxidative phosphorylation in rat liver mitochondria, in a manner analogous to the parent peptides. From studies of the aqueous phase aggregation behavior of the peptides, as well as their interaction with rat liver mitochondria, it is concluded that the interaction of the peptides with membranes is a complex process, probably involving both aqueous and membrane phase aggregation.

Dendritic structures produced on solidification of multicomponent aqueous solutions

Dendrite structures of ice produced on undirectional solidification of ternary and quaternary aqueous solutions have been studied. Upon freezing, solutions containing more than one solute produce plate-shaped dendrites of ice. The spacing between dendrites increase linearly with the distance from the chill surface and the square root of local solidification time (or square root of inverse freezing rate) for any fixed composition. For fixed freezing conditions, the dendrite spacings from multicomponent aqueous solutions were a function of the concentrations and diffusion coefficients of the individual solutes. The dendrite spacing produced by freezing of a solution was changed by the addition of a solute different from those already present. If the main diffusion coefficient of the added solute is higher than that of solutes already present, the dendrite spacing is increased and vice versa. The dendrite spacing in multi-component systems increases with the total solute concentration if the constituent solutes are present in equal amounts. The dendrite spacing obtained on freezing of these dilute multicomponent solutions can be expressed by regression equations of the type Image Full-size image (2K) where L is the dendrite spacing in microns, C1, C2 and C3 are concentrations of individual solutes, Θf is the total freezing time and A1 −A8 are constants. A Yates analysis of the dendrite spacings in a factorial design of quaternary solutions indicates that there are strong interactions between individual solutes in regard to their effect on the dendrite spacings. A mass transport analysis has been used to calculate the interdendritic supersaturation ΔC of the individual solutes, the supercooling in the interdendritic liquid ΔT, and the transverse growth velocity of the dendrites, VT. In ternary solutions if two solutes are present in equal amount the supersaturation of the solute with higher main diffusion coefficient is lower, and vice versa. If a solute with higher main diffusion coefficient is added to a binary solution, the interface growth velocity, the interdendritic supersaturation of the base solute and the interdendritic supercooling increase with the quantity of solute added.

Fluorescent probe and NMR studies of the aggregation of bile salts in aqueous solution

The binding of the fluorescent probes 1-anilino-8-naphthalene sulfonate and dansyl cadaverine to the sodium salts of cholic, deoxycholic and dehydrocholic acids has been investigated. Enhanced probe solubilisation accompanies aggregation. Monitoring of fluorescence intensities as a function of bile salt concentration permits the detection of primary micelle formation, as well as secondary association. The transition concentrations obtained by fluorescence are in good agreement with values determined for the critical micelle concentrations, by other methods. Differences in the behaviour of cholate and deoxycholate have been noted. Fluorescence polarisation studies of 1,6-diphenyl-1,3,5-hexatriene solubilised in bile salt micelles suggest a higher microviscosity for the interior of the deoxycholate micelle as compared to cholate. 1H NMR studies of deoxycholate over the range 1–100 mg/ml suggest that micelle formation leads to a greater immobilisation of the C18 and C19 methyl groups as compared to the C21 methyl group. Well resolved 13C resonances are observed for all three steroids even at high concentration. Both fluorescence and NMR studies confirm that dehydrocholate does not aggregate.

Elevated levels of PFOS and PFHxS in firefighters exposed to aqueous film forming foam (AFFF)

Exposure to aqueous film forming foam (AFFF) was evaluated in 149 firefighters working at AFFF training facilities in Australia by analysis of PFOS and related compounds in serum. A questionnaire was designed to capture information about basic demographic factors, lifestyle factors and potential occupational exposure (such as work history and self-reported skin contact with foam). The results showed that a number of factors were associated with PFAA serum concentrations. Blood donation was found to be linked to low PFAA levels, and the concentrations of PFOS and PFHxS were found to be positively associated with years of jobs with AFFF contact. The highest levels of PFOS and PFHxS were one order of magnitude higher compared to the general population in Australia and Canada. Study participants who had worked ten years or less had levels of PFOS that were similar to or only slightly above those of the general population. This coincides with the phase out of 3M AFFF from all training facilities in 2003, and suggests that the exposures to PFOS and PFHxS in AFFF have declined in recent years. Self-reporting of skin contact and frequency of contact were used as an index of exposure. Using this index, there was no relationship between PFOS levels and skin exposure. This index of exposure is limited as it relies on self-report and it only considers skin exposure to AFFF, and does not capture other routes of potential exposure. Possible associations between serum PFAA concentrations and five biochemical outcomes were assessed. The outcomes were serum cholesterol, triglycerides, high-density lipoproteins, low density lipoproteins, and uric acid. No statistical associations between any of these endpoints and serum PFAA concentrations were observed.

Effect of magnetic and electrical fields on dendritic freezing of aqueous solutions of sodium chloride

Aqueous solutions of sodium chloride were solidified under the influence of magnetic and electrical fields using two different freezing systems. In the droplet system, small droplets of the solution are introduced in an organic liquid column at −20°C which acts as the heat sink. In the unidirectional freezing system the solutions are poured into a tygon tube mounted on a copper chill, maintained at −70°C, from which the freezing initiates. Application of magnetic fields caused an increase in the spacing and promoted side branching of primary ice dendrites in the droplet freezing system, but had no measurable effect on the dendrites formed in the unidirectional freezing system. The range of electric fields applied in this investigation had no measurable effect on the dendritic structure. Possible interactions between external magnetic and electrical fields have been reviewed and it is suggested that the selective effect of magnetic fields on dendrite spacings in a droplet system could be due to a change in the nucleation behaviour of the solution in the presence of a magnetic field.