A Kirkwood-Buff Derived Force Field for Aqueous Alkali Halides

A classical nonpolarizable force field is presented for the simulation of aqueous alkali halide solutions (MX), where M = Li(+), Na(+), K(+), Rb(+), Cs(+) and X = F(-), Cl(-), Br(-), I(-), and their interactions with biomolecules. The models are specifically designed to reproduce the experimental Kirkwood-Buff integrals, and thereby the solution salt activities, as a function of salt concentration. Additionally, we demonstrate that these models reasonably reproduce other experimental properties including ion diffusion constants, dielectric decrements, and the excess heats of mixing. The parameters are developed by considering the properties of aqueous NaX and MCl solutions using a previously established model for NaCl. Transferability of the parameters to other salts is then established by the successful simulation of additional aqueous salt solutions, KI and CsBr, not originally included in the parameterization procedure.     

Mild and tunable benzoic acid catalysts for rearrangement reactions of allylic alcohols

An efficient and simple catalytic method for the isomerization of readily prepared allylic alcohols is described. We focus particularly on cyclic examples and the synthesis of unusual enyne and dienols. The benzoic acid catalysts employed are commercially available and very inexpensive and can be tuned for reactivity and substrate sensitivity.     

Surface functionalization of electro-deposited nickel

A new in situ electrochemical method of functionalizing an oxide-free Ni surface is demonstrated using octanethiol. Initial adsorption results in a multilayer molecular film, which blocks both the hydrogen evolution reaction (HER) and re-oxidation of the Ni by ambient oxygen. However, excess octanethiol can be removed by rinsing with ethanol, leaving behind a monolayer that continues to protect against re-oxidation but gives rise to an unexpected enhancement in the HER, with a greater enhancement for longer film formation times. The presence of an octanethiol monolayer on the surface was confirmed by spectroscopic observation of the CH(2), CH(3) and thiolate groups using infra red spectroscopy, while X-ray photo-electron spectroscopy demonstrated the effectiveness of the thiol layer as a barrier to surface oxidation. The electrochemically prepared octanethiol film impedes oxidation of the Ni in air more effectively than a film formed by immersion in a solution of octanethiol in ethanol.     

Novel nitration of estrone by metal nitrates

Nitration of estrone has been investigated with different types of metal salts in the presence of solid surfaces under various conditions.     

Diameter control of electrospun polyacrylonitrile/iron acetylacetonate ultrafine nanofibers

Electrospinning is the process of producing ultrafine fibers by overcoming the surface tension of a polymer solution using high voltage. In this work, the effects of both solution properties (viscosity, conductivity, and surface tension) and operational conditions (voltage, feed rate, and spinneret‐collector distance), on the structure of electrospun polyacrylonitrile nanofibers, were systematically investigated. Iron acetylacetonate was added to the electrospinning solution to control fiber diameter by selectively adjusting solution properties. It was found that, with increased salt concentration, the fiber diameter increases and then passes through a maximum due to changes in solution viscosity, conductivity, and surface tension. In addition, the fiber diameter increases with increase in voltage, feed rate, and spinneret‐collector distance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1611–1618, 2008     

The use of acrylic acid-co-nylon substrates for immobilizing enzymes

A number of poly(acrylic acid)-co-nylon graft copolymers were prepared. Two approaches were used. The first involved the direct, radiation-induced grafting of acrylic acid onto the nylon, while the second involved the hydrolysis of polyacrylonitrile-co-nylon graft copolymers. All the resulting poly(acrylic acid)-co-nylon graft copolymers coupled large amounts of protein when the carbodimides CMC and EDAC were used as coupling agents. However, when the enzymes β-galactosidase and trypsin were immobilized, the retention of activity was relatively low. A number of reasons for this effect can be postulated, some of which were investigated. From the evidence, it would appear that the major reason is that the carboxylic acid groups are fixed to a “rigid” backbone, which allows them to interact with the enzyme after the establishment of an initial covalent attachment. Additionally, with acid phosphatase, it was observed that the enzyme interacted with immobilized carboxylic acid groups before coupling occurred.     

Rapid comparison of diacetylmorphine on banknotes by tandem mass spectrometry

A procedure is described for the determination of the distribution of the contamination of banknotes with controlled drugs using tandem mass spectrometry. The method is illustrated using diacetylmorphine, which is the major active component of heroin. A series of banknotes is introduced into the mass spectrometer and the intensities of two product ions (m/z 328 and 268) derived from the precursor protonated molecule (m/z 370) are recorded. A banknote is considered contaminated if it shows a significant peak for both product ions, and if the ratio of intensities of these two peaks falls within accepted limits. The distribution of diacetylmorphine on sterling banknotes taken from general circulation within the UK can be modelled by an arcsin (square root) transformation of the data or by a log transformation of the data with a higher proportion of contamination. The two models were found to be in close agreement, predicting an upper limit (at 99.9% confidence) of contamination on banknotes from general circulation between 9 and 10%. The percentage contamination in a case study was calculated and compared to the background distribution using the two models proposed. This comparison revealed that the contamination present in the case study was inconsistent with that present on banknotes in general circulation.     

Analysis of ochres from Clearwell Caves: the role of particle size in determining colour

Three ochre samples (A (orange-red in colour), B (red) and C (purple)) from Clearwell Caves, (Gloucestershire, UK) have been examined using an integrated analytical methodology based on the techniques of IR and diffuse reflectance UV-visible-NIR spectroscopy, X-ray diffraction, elemental analysis by ICP-AES and particle size analysis. It is shown that the chromophore in each case is haematite. The differences in colour may be accounted for by (i) different mineralogical and chemical composition in the case of the orange ochre, where higher levels of dolomite and copper are seen and (ii) an unusual particle size distribution in the case of the purple ochre. When the purple ochre was ground to give the same particle size distribution as the red ochre then the colours of the two samples became indistinguishable. An analysis has now been completed of a range of ochre samples with colours from yellow to purple from the important site of Clearwell Caves.