Phase inversion sulfonated polysulfone membranes

The use of two nonsolvents serving as a cosolvent system, replacing the traditional volatile solvent plus less volatile nonsolvent system, in the formation of asymmetric phase inversion membranes was investigated. Specifically, asymmetric membranes of sulfonated polysulfone were cast from a cosolvent system consisting of tetrahydrofuran and formamide. The nonsolvents and the proportions in which they are mixed to produce the cosolvent system, as well as the gelation medium isopropyl alcohol, were selected based on the three-component solubility parameter concept of Hansen. The structure of each membrane was evaluated using scanning electron microscopy; the performance was evaluated for use in pressure-driven membrane separation processes. The membranes were found to be dependent on the composition of the original casting solution and the composition of the nascent membrane at the instant of gelation. These ideas are clearly represented through the use of a triangular polymer solubility diagram.     

Michael additions to steroidal 1-ene-3-ones

A reactivity pattern was established for Michael addition of aryl thiolates to 17-acetoxy 5α-androst-1-en-3-one. An abnormal bicyclic bridged adduct was obtained in the reaction of thiourea.     

Informational masking of speech in children: auditory-visual integration

The focus of this study was the release from informational masking that could be obtained in a speech task by viewing a video of the target talker. A closed-set speech recognition paradigm was used to measure informational masking in 23 children (ages 6-16 years) and 10 adults. An audio-only condition required attention to a monaural target speech message that was presented to the same ear with a time-synchronized distracter message. In an audiovisual condition, a synchronized video of the target talker was also presented to assess the release from informational masking that could be achieved by speechreading. Children required higher target/distracter ratios than adults to reach comparable performance levels in the audio-only condition, reflecting a greater extent of informational masking in these listeners. There was a monotonic age effect, such that even the children in the oldest age group (12-16.9 years) demonstrated performance somewhat poorer than adults. Older children and adults improved significantly in the audiovisual condition, producing a release from informational masking of 15 dB or more in some adult listeners. Audiovisual presentation produced no informational masking release for the youngest children. Across all ages, the benefit of a synchronized video was strongly associated with speechreading ability.     

Direct equilibration of soil water for delta(18)O analysis and its application to tracer studies

Current methods for stable oxygen isotopic (delta (18)O) analysis of soil water rely on separation of water from the soil matrix before analysis. These separation procedures are not only time consuming and require relatively large samples of soil, but also have been shown to introduce a large potential source of error. Current research at Queen's University Belfast is focused on using direct equilibration of CO(2) with the pore water to eliminate this extraction step using the automated Multiprep system and a Micromass Prism III isotope ratio mass spectrometer (IRMS). The findings of this research indicate the method is less time consuming, more reliable, and reproducible to within accepted limits (+/-0.1% per thousand delta (18)O). In this study the direct equilibration method is used to analyse delta (18)O tracer profiles in the unsaturated zone of field soils, concurrently with chloride tracer profiles, which can be used to assess infiltration rates and mechanisms through the unsaturated zone. Copyright 1999 John Wiley & Sons, Ltd.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

The study of the changes in the thermal properties of <Emphasis Type="Italic">Labeo rohita</Emphasis> bones due to arsenic exposure

The paper presents the changes in the thermal properties of control, arsenic exposed and DMSA treated Labeo rohita bones by using thermo analytical techniques. The result shows that the mass loss due to the thermal decomposition occurs in three distinct steps due to loss of water, organic and inorganic materials. The arsenic exposed bones present a different thermal behaviour compared to the control bones. The residue masses are increased due to arsenic exposure, while the DMSA treatment reduces the residue mass level. These thermal characteristics can be used as a qualitative method to check the metal accumulation in samples.     

Electroanalytical voltammetry in flowing solutions

A review is given of the principles, key developments and representative applications of small electrodes in flow-through electrochemical (ec) detectors having very low effective dead volume (<10 μl) for voltammetric and amperometric detection in flowing solutions. Emphasis is placed on factors contributing to high sensitivity, reliability and selectivity of ec detection as an integral part of larger analytical systems utilizing continuously flowing, unsegmented streams, e.g., flow-injection and liquid chromatographic analyses. Solid and mercury electrodes are considered under potentiostatic and potentiodynamic control. A review is given also of auxiliary chemical and photolytic derivatizations coupled to ec detection. The majority of the literature on the subject relates to liquid chromatography with electrochemical detection (l.c./ec); however, applications to these concepts to specific examples in flow-injection systems, as well as for on-line process control, should be obvious. Details of chromatographic separations and design of total analytical systems are not reviewed.     

Synthesis and spectroelectrochemistry of Ir(bpy)(phen)(phi)(3+), a tris(heteroleptic) metallointercalator

A tris(heteroleptic) phenanthrenequinone diimine (phi) complex of Ir(III), Ir(bpy)(phen)(phi)(3+), was synthesized through the stepwise introduction of three different bidentate ligands, and the Lambda- and Delta-enantiomers were resolved and characterized by CD spectroscopy. Like other phi complexes, this tris(heteroleptic) iridium complex binds avidly to DNA by intercalation. Electrochemical studies show that Ir(bpy)(phen)(phi)(3+) undergoes a reversible one-electron reduction at E(0) = -0.025 V in 0.1 M TBAH/DMF (versus Ag/AgCl), and spectroelectrochemical studies indicate that this reduction is centered on the phi ligand. The EPR spectrum of electrochemically generated Ir(bpy)(phen)(phi)(2+) is consistent with a phi-based radical. The electrochemistry of Ir(bpy)(phen)(phi)(3+) was also probed at a DNA-modified electrode, where a DNA binding affinity of K = 1.1 x 10(6) M(-1) was measured. In contrast to Ir(bpy)(phen)(phi)(3+) free in solution, the complex bound to DNA undergoes a concerted two-electron reduction, to form a diradical species. On the basis of UV-visible and EPR spectroscopies, it is found that disproportionation of electrochemically generated Ir(bpy)(phen)(phi)(2+) occurs upon DNA binding. These results underscore the rich redox chemistry associated with metallointercalators bound to DNA.     

Synthesis and characterization of sulfonated poly(acrylene ether sulfones)

Ionic groups incorporated into a polymer have a decided effect on its physical properties. A number of ionomers and polyelectrolytes have been widely applied. In particular, sulfonated bisphenol-A polysulfone (SPSF) has been used as a composite or single-component membrane for the desalination of water. In this article, the synthesis and physical characteristics of sulfonated polysulfone are addressed. A detailed synthesis route is provided and methods that yield determinable levels of sulfonation are described. These ion-containing polymers retain an excessive amount of residual salts, which, of course, are impurities to the system. Therefore, before any analyses were made the polymers were subjected to a thorough soxhlet extraction process with boiling water, which appeared to be quite effective. The degree of sulfonation was assessed by several methods such as ¹H NMR and FT-IR. A new ¹H NMR method was derived because the method cited in the literature proved to be too inconsistent for our work. The new ¹H NMR method used a quaternary ammonium counterion [N(CH₃)₄]. These methyl protons are easily measured and may be ratioed against the isopropylidene protons in the polymer backbone that act as an internal standard. Characterization of the physical properties of SPSF consisted of water uptake, differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and solubility studies. Its physical appearance and mechanical behavior were improved by the solution procedure. Also addressed were the effects of different counterions (Na⁺ & Mg⁺⁺) with SPSFs of low levels of sulfonation. The variation in physical properties between the divalent and monovalent counterions is dramatic, especially when observed by TMA in the rubber plateau above the apparent glass temperature.