Elimination of methane from protonated acetaldehyde: The Ab initio transition state

The transition state (TS) for loss of CH₄ from protonated acetaldehyde has been located at the second-order Moller-Plesset (MP2)/6-31G(d,p) level of theory. The activation energy is predicted to be 263.9 kJ/mol starting from the more stable form (methyl and hydrogen E) and 261.6 kJ/mol starting from the less stable form (methyl and hydrogen Z) that is required for reaction. The products (methane and the formyl ion) are predicted to lie 136.6 kJ/mol below the TS for their formation. MP2 methods underestimate the heats of formation of both the TS and the reaction products by about 40 kJ/mol when compared with experiment. Restricted Hartree-Fock (RHF) calculations give much more accurate relative energies. The MP2 TS leads directly to fragmentation and is described as a protonation of the methyl group by the acidic proton on oxygen. Under RHF theory the reaction is stepwise. An RHF TS similar to the MP2 TS leads to a nonclassical intermediate (which is stable at this level of theory) that has one of the C---H bonds protonated. This mechanism (protonation of an alkyl group) appears to be a general one for high energy 1,2 eliminations from organic cations. (J Am Soc Mass Spectrom 1994, 5, 1102-1106)     

Optimization of solid-phase clean-up prior to liquid chromatographic analysis of ochratoxin A in roasted coffee

An extraction and clean-up method for ochratoxin A (OA) in roasted coffee has been developed and the HPLC method optimized. An interfering compound with a similar retention time as OA was adsorbed by the aminopropyl (NH2) material at < or = 5% NaHCO3. Residual OA on the column was recovered by washing with the extraction solution followed with methanol. Fractions were mixed together for further clean-up with Ochratest immunoaffinity columns (IACs). Analysis by HPLC resulted in a well resolved OA peak and reduction in matrix interferences. Recoveries ranged from 72 to 84% and the detection limit was 1 ng/g.     

Fast Dimension Reduction Using Rademacher Series on Dual BCH Codes

The Fast Johnson–Lindenstrauss Transform (FJLT) was recently discovered by Ailon and Chazelle as a novel technique for performing fast dimension reduction with small distortion from ℓ ₂ ^d to ℓ ₂ ^k in time O(max {dlog d,k ³}). For k in [Ω(log d),O(d ^1/2)], this beats time O(dk) achieved by naive multiplication by random dense matrices, an approach followed by several authors as a variant of the seminal result by Johnson and Lindenstrauss (JL) from the mid 1980s. In this work we show how to significantly improve the running time to O(dlog k) for k=O(d ^1/2−δ ), for any arbitrary small fixed δ. This beats the better of FJLT and JL. Our analysis uses a powerful measure concentration bound due to Talagrand applied to Rademacher series in Banach spaces (sums of vectors in Banach spaces with random signs). The set of vectors used is a real embedding of dual BCH code vectors over GF(2). We also discuss the number of random bits used and reduction to ℓ ₁ space. The connection between geometry and discrete coding theory discussed here is interesting in its own right and may be useful in other algorithmic applications as well.     

Development of a colloidal gold-based lateral-flow immunoassay for the rapid simultaneous detection of zearalenone and deoxynivalenol

A multianalyte lateral-flow technique using colloidal gold-labeled monoclonal antibodies was developed for the rapid simultaneous detection of deoxynivalenol (DON) and zearalenone (ZEA). The results of this qualitative one-step test were interpreted visually. A very simple and fast sample preparation was used, and the assay procedure could be accomplished within 10 min. When applied to spiked wheat samples, the technique gave accurate and reproducible results. Cut-off levels of 1500 and 100 μg kg⁻¹ for DON and ZEA, respectively, were observed. The described multianalyte format can be used as a reliable, rapid and cost-effective on-site screening technique for the simultaneous determination of mycotoxins in grain samples.     

Dense Fast Random Projections and Lean Walsh Transforms

Random projection methods give distributions over k×d matrices such that if a matrix Ψ (chosen according to the distribution) is applied to a finite set of vectors x _i ∈ℝ ^d the resulting vectors Ψx _i ∈ℝ ^k approximately preserve the original metric with constant probability. First, we show that any matrix (composed with a random ±1 diagonal matrix) is a good random projector for a subset of vectors in ℝ ^d . Second, we describe a family of tensor product matrices which we term Lean Walsh. We show that using Lean Walsh matrices as random projections outperforms, in terms of running time, the best known current result (due to Matousek) under comparable assumptions.     

Lateral-flow colloidal gold-based immunoassay for the rapid detection of deoxynivalenol with two indicator ranges

A lateral-flow immunoassay using a colloidal gold-labelled monoclonal antibody was developed for the rapid detection of deoxynivalenol (DON). Different parameters, such as the amount of immunoreagents, type of the materials, composition of the blocking solution and of the detector reagent mixture, were investigated to provide the optimum assay performance. The experimental results demonstrated that such a visual test had an indicator range rather than a cut-off value. Thus, tests for DON determination with two different indicator ranges of 250-500 and 1000-2000 μg kg⁻¹ were designed. The method allowed detection of DON at low and high concentration levels, which could be useful for research and practical purposes. The assay applied to spiked wheat and pig feed samples demonstrated accurate and reproducible results. The applicability of the developed lateral-flow test was also confirmed under real field conditions. The test strips prepared in Belgium were sent to Mexico, where they were used for the screening of DON contamination in different bread wheat entries from Fusarium Head Blight inoculated plots. The results were compared with those obtained by ELISA and LC-MS/MS. A poor correlation between ELISA and LC-MS/MS was observed. Visual results of the dipstick tests were in a good agreement with the results of the LC-MS/MS method. Coupled with a simple and fast sample preparation, this qualitative one-step test based on the visual evaluation of results did not require any equipment. Results could be obtained within 10 min. The described assay format can be used as a simple, rapid, cost-effective and robust on-site screening tool for mycotoxin contamination in different agricultural commodities.     

A study of some matrix effects in the determination of beryllium by atomic-absorption spectroscopy in the nitrous oxide-acetylene flame

A study has been made of a number of interferences observed in the trace determination of beryllium by atomic-absorption in the nitrous oxide-acetylene flame. The major negative interference caused by the presence of excess of aluminium salts may be overcome by the use of 8-hydroxyquinoline. Magnesium and silicon also depress the Be signal, but most other metals cause enhancement. In most instances the enhancements may be made uniform by the addition of potassium ions to the sample solution.     

Cost Cumulant Control: State-Feedback,Finite-Horizon Paradigm with Application to Seismic Protection

The paper is concerned with the study of the optimal control which minimizes a finite linear combination of the first k cost cumulants of a finite-horizon integral quadratic form associated with a linear stochastic system, when the controller measures the states. The solution is investigated by adapting dynamic programming techniques to the nontraditional forms evidenced by cumulant representations. The performance of this k-cost cumulant (kCC) controller is compared to that of the best control paradigms published for the American Society of Civil Engineers first-generation structure benchmark for seismically excited buildings; the simulation results indicate that the newly developed control paradigm makes better use of the available control limits and achieves uniform improvement in the officially defined performance statistics for floor vibrations and accelerations.     

Expanding the synthesis of Stöber spheres: towards the synthesis of nano-magnesium oxide and nano-zinc oxide

In order to synthesise Stöber spheres of different diameters, fixed amounts of ethanol, ammonia and water were used with varying amounts of tetraethyl orthosilicate. This simple method was further applied to the synthesis of nano-ZnO and nano-MgO from their respective precursors, zinc methoxide and magnesium ethoxide. The spherical nano-SiO₂, nano-ZnO and nano-MgO synthesised in this way were characterised by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. Preliminary investigations found that nano-ZnO and nano-MgO showed good catalytic activity in the trans-esterification reaction that converts vegetable oil to biodiesel.     

First-Passage-Time Distribution for Variable-Diffusion Processes

First-passage-time distribution, which presents the likelihood of a stock reaching a pre-specified price at a given time, is useful in establishing the value of financial instruments and in designing trading strategies. First-passage-time distribution for Wiener processes has a single peak, while that for stocks exhibits a notable second peak within a trading day. This feature has only been discussed sporadically—often dismissed as due to insufficient/incorrect data or circumvented by conversion to tick time—and to the best of our knowledge has not been explained in terms of the underlying stochastic process. It was shown previously that intra-day variations in the market can be modeled by a stochastic process containing two variable-diffusion processes (Hua et al. in, Physica A 419:221–233, 2015). We show here that the first-passage-time distribution of this two-stage variable-diffusion model does exhibit a behavior similar to the empirical observation. In addition, we find that an extended model incorporating overnight price fluctuations exhibits intra- and inter-day behavior similar to those of empirical first-passage-time distributions.