Spin-trapped hydroxyl free radicals studied at low field by Field-Cycled Dynamic Nuclear Polarization

The technique of Field-Cycled Dynamic Nuclear Polarization (FC-DNP) involves the EPR irradiation of a free radical solution and the subsequent observation of the NMR signal, the experiment being carried out at a range of magnetic field strengths in order to measure the free radical’s EPR spectrum. In this work FC-DNP has been used to study the EPR spectrum of DMPO spin-trapped hydroxyl free radicals at magnetic field strengths between 0.5 mT and 13.0 mT (5–130 Gauss). The low-field EPR spectrum contains six separate EPR lines, in contrast to the well-known X-band spectrum where only four are seen. Knowledge of the spin-adduct’s EPR spectrum will be of use to workers involved in low-field EPR, especially those conducting biological or in-vivo spin-trapping experiments.     

Profiling of impurities in illicit methamphetamine by high-performance liquid chromatography and capillary electrochromatography

High performance liquid chromatography (HPLC) with photodiode array (PDA) UV and fluorescence (FL) detection, and capillary electrochromatography (CEC) with laser-induced fluorescence (LIF) detection were investigated for the analysis of acidic extracts derived from illicit methamphetamine. These compounds include major impurities from the hydriodic acid/red phosphorous reduction method, i.e., 1,3-dimethyl-2-phenylnaphthalene and 1-benzyl-3-methylnaphthalene, and other trace-level, structurally related impurities. For certain of these solutes, HPLC with conventional FL detection gave at least a 60× increase in sensitivity over UV detection. In addition, other highly fluorescent impurities were detected in methamphetamine produced via four other synthetic routes. The use of a rapid scanning FL detector (with acquisition of “on the fly” excitation or emission) provided structural information and gave “optimum” excitation and emission detection wavelengths. CEC with LIF detection using UV laser excitation provided greatly improved chromatography over HPLC, with good detection limits in the low ng/ml range. Both methodologies provide good run-to-run repeatability, and have the capability to distinguish between samples.     

Use of dynamically coated capillaries with added cyclodextrins for the analysis of opium using capillary electrophoresis

A rapid, precise, accurate, and robust method using capillary electrophoresis (CE) with dynamically coated capillaries for the analysis of the major opium alkaloids in opium is presented. Dynamic coating of the capillary surface is accomplished using a commercially available reagent kit (polycation coating followed by polyanion coating). The addition of dual cyclodextrins (hydroxypropyl-beta-cyclodextrin and dimethyl-beta-cyclodextrin) to the run buffer imparts excellent selectivity for the opium alkaloids. For the determination of morphine, papaverine, codeine, noscapine and thebaine in opium gum and opium latex samples (using tetracaine as an internal standard) good agreement with values obtained by gradient high-performance liquid chromatography is obtained. Compared to the latter technique, CE affords better resolution with significantly faster analysis time (12 min versus 29 min). Dynamically coated capillaries, which give rise to a relatively high and robust electroosmotic flow (EOF) at the background electrolyte pH of 2.5, allow for rapid analysis and excellent migration time and peak area precision (RSDs < or = 0.12% and < or = 1.2%, respectively). Reproducible separations (relative migration times) for over 500 samples have been obtained on a single capillary. The nature of the injection solvent, the injection time and the contents of the waste vials have a profound effect on the pressure injection precision of the relatively hydrophobic solutes. The CE conditions reported in this study are also applicable to the analysis of lysergic acid diethylamide (LSD) exhibits.     

New solution of the plane problem for an equilibrium crack

We consider the classical plane problem of elasticity about a crack in an isotropic elastic unbounded plane resulting in a singular solution for the stresses near the crack edge. Relations of generalized elasticity with a small parameter characterizing the medium microstructure are derived, and the higher order of these relations permits eliminating the singularity of the classical solution. An experimental method for determining the medium parameter is proposed, and the corresponding experimental results are given.     

On the solution singularity in the plane elasticity problem for a cantilever strip

The plane elasticity problem of bending of a cantilever strip whose material is assumed to be incompressible in the transverse direction is solved. It is shown that, in the classical statement of of the boundary condition for the fixed edge of the strip, the solution has a singularity at the corner points of the edge. Several cases of the strip fixation and loading characterized by the presence or absence of the solution singularity are considered. The strength of glass beams of three types, for which the theory of elasticity predicts whether the normal stress has a singularity, is studied experimentally. It is shown that the limit stresses for the beams of the types under study are practically the same, which testifies that the solution singularity does not have any physical nature.     

Modeling of the localy-functional properties of the material damaged by fields of defects

It is shown that for Mindlin media with fields of defects there is an alternative interpretation allowing to describe the material affected by defects as equivalent functionally-gradient material with varying properties for coordinates, modeled in the classical theory of elasticity. We establish clear relationships for determining the properties of functionally graded materials by the solutions, taking into account the availability of fields of defects. It is shown that, in general, the properties of equivalent functionally-gradient material depend on the coordinates, as well as on the loading and boundary conditions.     

Field-cycled PEDRI imaging of free radicals with detection at 450 mT

This paper describes the design, construction and use of a field-cycled proton-electron double-resonance imaging (FC-PEDRI) system for the detection and imaging of free radicals. The unique feature of this imager is its use of a 450-mT detection magnetic field in order to achieve good image quality and sensitivity. The detection magnetic field is provided by a superconducting magnet, giving high stability and homogeneity. Field cycling is implemented by switching on and off the current in an internal, coaxial, resistive secondary magnet that partially cancels the superconducting magnet's field at the sample; the secondary magnet is actively shielded to avoid eddy currents. EPR irradiation takes place at approximately 5 mT, following which the field is switched to 450 mT in 40 ms for NMR signal detection. Full details of the imager's subsystems are given, and experiments to image the distribution of stable free radical contrast agents in phantoms and in anesthetized rats are described.     

Eshelby integral formulas in gradient elasticity

Eshelby integral formulas play a fundamental role in mechanics of composite materials, because they provide an efficient tool for determining the average properties of dispersion-filled materials. For example, their use in the framework of the self-consistent averaging method actually gives a final and quite precise solution to the problem of determining effective physical and mechanical properties of filled composites up to large relative contents of inclusions and almost all relations between the phase characteristics of the composite. In the present paper, we generalize the Eshelby integral formulas to the gradient theory of elasticity. This provides the possibility for using efficient methods for estimating the average characteristics of micro and nano-structured materials in the framework of gradient theories, which permit taking the scale effects into account correctly, and hence find wider and wider applications in describing the mechanical and physical processes.     

Wave propagation and energy exchange in a spatio-temporal material composite with rectangular microstructure

We consider propagation of waves through a spatio-temporal doubly periodic material structure with rectangular microgeometry in one spatial dimension and time. Both spatial and temporal periods in this dynamic material are assumed to be of the same order of magnitude. A “double Floquet” solution is obtained in the special case when the wave equation t(ρut)−z(kuz)=0 allows for the separation of variables. We also consider a checkerboard microgeometry where variables cannot be separated. The squares in a space-time checkerboard are assumed to be filled with materials having equal impedance but different phase speeds. Within certain parameter ranges, we observe numerically the formation of distinct and stable limiting characteristic paths (“limit cycles”) that attract neighbouring characteristics after a few time periods. The average speed of propagation along the limit cycles remains the same throughout certain ranges of parameters of the microgeometry (the “plateau effect”). We formulate, as a hypothesis, the statement saying that a checkerboard structure is on a plateau if and only if it yields stable limit cycles. A dynamic material is a thermodynamically open system, as it is involved in a permanent exchange of energy and momentum with the environment. Material assemblages that produce the limit cycles are special in this aspect. Specifically, to make a wave travel through such an assemblage, we find analytically that an external agent may need to supply infinite energy and this may be so regardless of the wave frequency. For spatio-temporal laminates, however, an accumulation of energy (parametric resonance) may emerge only for frequencies that are not too low relative to some characteristic frequency of the system.     

Application of micellar electrokinetic capillary chromatography to the analysis of illicit drug seizures

The application of micellar electrokinetic capillary chromatography (MECC) to the analysis of illicit drug seizures is presented. Areas investigated include general screening and qualitative and, in some instances, quantitative analysis of various drugs, including heroin, opium, cocaine, amphetamines, LSD and anabolic steroids. Due to its high efficiency, high selectivity and general applicability, MECC is well suited for forensic drug analyses.