Modifying infrared scattering effects of single yeast cells with plasmonic metal mesh

The scattering effects in the infrared (IR) spectra of single, isolated bread yeast cells (Saccharomyces cerevisiae) on a ZnSe substrate and in metal microchannels have been probed by Fourier transform infrared imaging microspectroscopy. Absolute extinction [(3.4±0.6)×10(-7) cm(2) at 3178 cm(-1)], scattering, and absorption cross sections for a single yeast cell and a vibrational absorption spectrum have been determined by comparing it to the scattering properties of single, isolated, latex microspheres (polystyrene, 5.0 μm in diameter) on ZnSe, which are well modeled by the Mie scattering theory. Single yeast cells were then placed into the holes of the IR plasmonic mesh, i.e., metal films with arrays of subwavelength holes, yielding "scatter-free" IR absorption spectra, which have undistorted vibrational lineshapes and a rising generic IR absorption baseline. Absolute extinction, scattering, and absorption spectral profiles were determined for a single, ellipsoidal yeast cell to characterize the interplay of these effects.     

N-Picolinamides as ligands in Ullman type C–O coupling reactions

Copper-catalyzed modified Ullmann coupling reactions creating C–O bonds, including diaryl ethers or phenols, are vital to organic synthesis. Synthesized N-phenyl-2-pyridinecarboxamide and its derivatives were used as ligands in conjunction with catalytic copper sources in the formation of various diaryl ethers and phenols. Various aryl and heteroaryl halides with electron donating and withdrawing groups were reacted with various phenols under mild reaction conditions providing moderate to excellent yields.     

A rearrangement-cycloaddition approach to spiro-fused indanones

Spiro-fused indanones were constructed using a [4 + 2]-cycloaddition approach from α-methylene indanone dienophiles, which were elaborated from 4-chromanone in a number of steps including a key rearrangement process. This type of spiro-fused structure forms the central core ring system found in natural products such as coleophomone A. The cycloaddition reactions using an α-methylene indanone dienophile led to the exo diastereoisomer as the major cycloadduct, whereas the 1,4-dione based dienophile predominantly led to the endo diastereoisomer.     

Electromigration in integrated circuits

We review the mechanism of integrated circuit failure known as “electromigration.” Electromigration is a physical wearout process that operates primarily in the on-chip interconnections of an integrated circuit. It is caused by the currents that run through those interconnections. The first part of the review introduces the founding principles of electromigration and the research history upon which those principles are based. The second part introduces and reviews the increasingly relevant issue of pulsed current electromigration, and the final part contains a relatively detailed review of a recent study of pulsed current electromigration.     

Enzyme-catalysed synthesis and absolute configuration assignments of cis-dihydrodiol metabolites from 1,4-disubstituted benzenes

A series of ten cis-dihydrodiol metabolites has been obtained by bacterial biotransformation of the corresponding 1,4-disubstituted benzene substrates using Pseudomonas putida UV4, a source of toluene dioxygenase (TDO). Their enantiomeric excess (ee) values have been established using chiral stationary phase HPLC and 1H NMR spectroscopy. Absolute configurations of the majority of cis-dihydrodiols have been established using stereochemical correlation and X-ray crystallography and the remainder have been tentatively assigned using NMR spectroscopic methods but finally confirmed by circular dichroism (CD) spectroscopy. These configurational assignments support and extend the validity of an empirical model, previously used to predict the preferred stereochemistry of TDO-catalysed cis-dihydroxylation of ten 1,4-disubstituted benzene substrates, to more than twenty-five examples.     

L2(R) Solutions of Dilation Equations and Fourier-Like Transforms

We state a novel construction of theFourier transform on L²(R) based on translation and dilation properties which makes use of the multiresolution analysis structure commonly used in the design of wavelets. We examine the conditions imposed by variants of these translation and dilation properties. This allows other characterizations of the Fourier transform to be given, and operators which have similar properties are classified. This is achieved by examining the solution space of various dilation equations, in particular we show that the L²(R) solutions of f (x) = f (2x) + f (2x - 1) are in direct correspondence with L²(-[1, 2)).     

The application of reporter gene assays for the detection of endocrine disruptors in sport supplements

The increasing availability and use of sports supplements is of concern as highlighted by a number of studies reporting endocrine disruptor contamination in such products. The health food supplement market, including sport supplements, is growing across the Developed World. Therefore, the need to ensure the quality and safety of sport supplements for the consumer is essential. The development and validation of two reporter gene assays coupled with solid phase sample preparation enabling the detection of estrogenic and androgenic constituents in sport supplements is reported. Both assays were shown to be of high sensitivity with the estrogen and androgen reporter gene assays having an EC(50) of 0.01 ng mL(-1) and 0.16 ng mL(-1) respectively. The developed assays were applied in a survey of 63 sport supplements samples obtained across the Island of Ireland with an additional seven reference samples previously investigated using LC-MS/MS. Androgen and estrogen bio-activity was found in 71% of the investigated samples. Bio-activity profiling was further broken down into agonists, partial agonists and antagonists. Supplements (13) with the strongest estrogenic bio-activity were chosen for further investigation. LC-MS/MS analysis of these samples determined the presence of phytoestrogens in seven of them. Supplements (38) with androgen bio-activity were also selected for further investigation. Androgen agonist bio-activity was detected in 12 supplements, antagonistic bio-activity was detected in 16 and partial antagonistic bio-activity was detected in 10. A further group of supplements (7) did not present androgenic bio-activity when tested alone but enhanced the androgenic agonist bio-activity of dihydrotestosterone when combined. The developed assays offer advantages in detection of known, unknown and low-level mixtures of endocrine disruptors over existing analytical screening techniques. For the detection and identification of constituent hormonally active compounds the combination of biological and physio-chemical techniques is optimal.     

Chemoenzymatic synthesis of a mixed phosphine-phosphine oxide catalyst and its application to asymmetric allylation of aldehydes and hydrogenation of alkenes

The chemoenzymatic synthesis of a Lewis basic phosphine-phosphine oxide organocatalyst from a cis-dihydrodiol metabolite of bromobenzene proceeds via a palladium-catalysed carbon-phosphorus bond coupling and a novel room temperature Arbuzov [2,3]-sigmatropic rearrangement of an allylic diphenylphosphinite. Allylation of aromatic aldehydes were catalysed by the Lewis basic organocatalyst giving homoallylic alcohols in up to 57% ee. This compound also functioned as a ligand for rhodium-catalysed asymmetric hydrogenation of acetamidoacrylate giving reduction products with ee values of up to 84%.     

Impact on school assessment where use of graphics calculators is mandatory in a related public examination

This paper reports an inquiry into assessment items classed as 'extended pieces of work' in Applicable Mathematics, in Western Australia. The principal purpose was to identify opportunities for graphics calculator use in 'extended pieces' implemented in schools. Ownership of the technology is widespread because it is mandated for the Applicable Mathematics tertiary entrance examination, which students sit at the end of the Year 12 course. Twenty-one of the twenty-eight pieces that were collected allowed for calculator use and, frequently, choosing to use the technology would have advantaged students, for instance, in supporting conjecture. Practical applications that would not be feasible to solve without the technology were included. Regression analysis and the random number generator were utilized. Overall, availability of the technology has widened the scope of approaches in 'extended pieces of work' in potentially valuable ways. Issues are how conjectures were elicited and calls for 'black box' use of the calculator.     

Separating forces in blade coating of viscous and viscoelastic liquids

Coating of viscous and viscoelastic liquids is examined both theoretically and experimentally. A single simple geometry, a blade over a rotating roll, is considered. A perturbation solution to the Navier-Stokes equations yields a lubrication theory with first order corrections for curvature and inertia. A numerical solutions by the Finite Element Method (FEM) is compared to the analytical solutions. For Newtonian fluids, agreement between these mathematical models, and data on blade loading, is quite good.The effect of a non-Newtonian viscosity is explored by adopting a purely viscous power law model. The zeroth-order (lubrication) equations are solved by the method of Steidler and Horowitz, and predictions for coating thickness and blade loading agree quite well with those obtained from a FEM solution of the full equations of motion for a power law fluid. Data on blade loading, obtained using a strongly elastic polymer solution, are compared to these mathematical models, and discrepancies are noted.