Recent advances in the direct electrochemical detection of drugs of abuse

In the last decade, the trafficking and use of illicit drugs showed a continuous incremental trend, remaining worldwide a challenging problem for the consequences on society, health, criminality, and environment. The introduction on the market of new products and of illicit synthetic compounds represents a new challenging task for analytical chemistry, looking for rapid and accurate methods for the detection of illicit substances in seized street samples, biological fluids, and wastewater. In this context, electrochemical sensors have shown promising results as an alternative to standard chromatographic and spectroscopic methods. This review aims at highlighting the most recent progresses in the use of electrochemistry for the detection of drugs of abuse, mainly including well consolidated substances like cannabinoids, cocaine, opioids, ecstasy, and methamphetamine as well as new psychoactive molecules widely diffused at the present time. Different strategies have been described particularly consisting in the direct electrochemical oxidation of the target analyte. The implementation of tailor-made portable instruments with electrochemical detection methods constitutes an added value to improve the effectiveness of electrochemical sensors for the identification of psychoactive substances when performing large-scale sampling tests.

     

High-performance capillary electrophoresis to determine intact keratan sulfate and hyaluronic acid in animal origin chondroitin sulfate samples and food supplements

Chondroitin sulfate is extracted from animal cartilaginous tissues and is commercialized as active principle against osteoarthritis. Its biological activity depends on its purity grade and could be altered by the presence of other glycosaminoglycans like keratan sulfate that could be contemporarily extracted from animal tissues or like hyaluronic acid that, instead, is added on purpose in food supplements. Although numerous methods are reported in literature for quality control analyses of chondroitin sulfate, few of them are able to detect other glycosaminoglycans. In this paper, for the first time, a new high-performance CE method was set up to quantify the chondroitin sulfate, the eventual keratan sulfate, and hyaluronic acid as intact chains: five chondroitin sulfate standards and 13 animal origin samples or food supplements from six different suppliers were analyzed. The new method was able to determine keratan sulfate similarly to a previously reported high-performance anion-exchange chromatography method, but in addition it showed the advantage to determine also the hyaluronic acid as never reported before.     

A lumped approach to the kinetic modeling of pyrolysis and combustion of biodiesel fuels

The aim of this work is to discuss a lumped approach to the kinetic modeling of the pyrolysis and oxidation of biodiesel fuels, i.e. rapeseed and soybean methyl esters. The lumped model is the natural extension of the kinetic scheme of methyl butanoate and methyl decanoate and takes also a great advantage from the detailed kinetic scheme of biodiesel fuels [Westbrook et al. Combustion and Flame 158 (2011) 742–755]. The combustion of methyl palmitate and methyl stearate is very similar to the one of methyl decanoate, while large unsaturated methyl esters are significantly less reactive at low and intermediate temperatures. The formation of resonantly stabilized allylic radicals from unsaturated methyl esters constitutes a critical element very useful to characterize the reactivity of the different fuels. The extension of the previous kinetic model of hydrocarbon and oxygenated fuel combustion to the methyl esters required the introduction of ～60 lumped species and ～2000 reactions. The dimension of the overall kinetic scheme (～420 species involved in ～13,000 reactions) allows a more flexible and direct application of the model without the need of kinetic reductions. The comparison of model predictions and different sets of experimental data from one side allows to verify the reliability of the proposed model, from the other side calls for further experimental and theoretical work on this subject.     

Global analytic regularity for non-linear second order operators on the torus

Assuming a subelliptic a-priori estimate we prove global analytic regularity for non-linear second order operators on a product of tori, using the method of majorant series.

     

On the three-dimensional Wigner-Poisson problem with inflow boundary conditions

We study the Wigner-Poisson problem in a bounded spatial domain, with non-homogeneous and time-dependent “inflow” boundary conditions. This system is a quantum model of charge transport in a semiconductor device coupled with reservoirs, in presence of a self-consistent potential and of an external one. We state a local-in-time well-posedness result for the problem. The main difficulty is proving in the three-dimensional case that the non-linear potential term is a Lipschitz perturbation of the “affine” streaming operator, in an appropriately weighted L²-space.     

Synthesis of polyarylacetylenes by γ‐ray‐induced polymerization of terminal alkynes. Nanostructures of ortho‐substituted derivatives

Terminal aryl alkynes RC₆H₄C?CH with substituents of different electronic properties and ring position (R = H, 4‐CF₃, 4‐OMe, 2‐CF₃, 2‐OMe, 2‐Me) were exposed to γ‐radiation (50–400 kGy) in organic solvents (hexane, 1,4‐dioxane, ethylacetate, methanol, tetrahydrofuran), at room temperature. The effects arising from substituent, solvent, dilution, and radiation dose allowed to define the conditions suitable for polymerization, which was favored in methanol at increasing dilution of the alkyne. Ortho‐substitution represented the key structural element in the substrate, and the derived polyarylacetylenes were characterized in detail, including gel permeation chromatography, thermal analysis, infrared, NMR, UV–vis, fluorescence, and scanning electron microscope spectroscopy. The results are consistent with the formation of irregular polymers mainly composed of trans‐transoid chains. Controlled aggregation of the polymers by means of an osmosis‐based procedure in solvent/non‐solvent mixtures allowed the formation of nanostructured materials, in particular of hollow nanospheres from THF/water. The methodology sets the basis for the development of γ‐rays‐induced polymerization of alkynes, in a transition metal catalyst‐free environment. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012