Direct EPR detection of transient and continuous wave signals at 2.5 GHz

Direct detection of free induction decays and electron spin echoes, and the recording of echo-detected EPR spectra and electron spin echo envelope modulation patterns at a microwave frequency of 2.5 GHz is demonstrated. This corresponds to the measurement of the transverse magnetization in the laboratory frame, rather than in the rotating frame as usually done by down-converting the signal (homodyne detection). An oscilloscope with a 6-GHz analog bandwidth, a sampling rate of 20 GigaSamples per second, and a trigger frequency of 5 GHz for the edge trigger and 750 MHz for the advanced trigger, is used in these experiments. For signal averaging a 3-GHz microwave clock divider has been developed to synchronize the oscilloscope with the frequency of the EPR signal. Moreover, direct detection of continuous wave EPR signals at 2.5 GHz is described.     

Spectral anomalies and spectral switches of partially coherent and polychromatic light diffracted at an aperture

Inrecentyearsanewbranchofmodernphysicalopticscalledsingularoptics[1]hasbeendeveloped.In2002theworkinsingularopticswasextendedfrommonochromaticlighttospatiallyfullycoherentandpolychromaticlightbyGburetal.[2—4].Itwasfoundthat,whenaconverging,spatiallyfullycoherentandpolychromaticsphericalwaveisdiffractedatanaperture,anomalousspectralchangestakeplaceclosetozerosoftheintensityinthefarfield;i.e.thespectrumisredshiftedatsomepoints,blueshiftedatothers,andsplitintotwolineselsewhere.Thepredictionsofsp…     

Development of a Solid-Phase Extraction Procedure for the Simultaneous Determination of Polyphenols, Organic Acids and Sugars in Wine

A solid-phase extraction (SPE) procedure that fractionates wine samples into 2 sub-samples containing sugars and organic acids (sub-sample 1) and low molecular weight polyphenols (sub-sample 2), respectively, together with rugged LC procedures for their analyses are described. Wine is adjusted to pH 2.5 and loaded on a styrene-divinylbenzene (SDB) cartridge. The organic acids and sugars are eluted with 20 mM sulphuric acid and the monomeric polyphenols with ethyl acetate. Glucose and fructose are analysed by normal phase LC with evaporative light scattering detection and the organic acids by ion exclusion chromatography with UV detection at 210 nm. Analysis of the phenolic fraction is performed by reversed phase LC with diode array detection. Recoveries and repeatabilitys for 27 standard compounds (2 sugars, 7 organic acids and 18 polyphenols) are presented. The method represents an improvement in terms of productivity and robustness compared to currently used procedures.     

Microchip capillary electrophoresis with a boron-doped diamond electrochemical detector for analysis of aromatic amines

The attractive features of a boron-doped diamond (BDD) thin-film detector for microchip capillary electrophoretic (CE) separations of dye-related amino-substituted aromatic compounds are described. The diamond electrode was employed in the end-column amperometric detection of 4-aminophenol (4-AP), 1,2-phenylenediamine (1,2-PDA), 2-aminonaphthalene (2-AN), 2-chloroaniline (2-CA), and o-aminobenzoic acid (o-ABA), and its attractive behavior was compared to commonly used screen-printed carbon and glassy-carbon electrodes. These conventional electrode materials exhibit a significant degree of passivation and low sensitivity to the above-mentioned environmental pollutants. The diamond-based electrochemical detection system displayed a favorable analytical performance, including lower noise levels, higher peak resolution with enhanced sensitivity, and improved resistance against electrode passivation. Factors influencing the on-chip analysis were assessed and optimized. The diamond detector displayed detection limits of 2.0 and 1.3 microM for 4-AP and 2-AN, respectively, and a wide linear response for these compounds over the 2-50 microM range. The enhanced stability was demonstrated by relative standard deviation (RSD) values of 1.4% and 4.7% for 100 microM 1,2-PDA and 200 microM 2-CA, respectively, for repetitive detections (n = 7). Besides, the simultaneously observed current decrease was 2.4 and 9.1% for 1,2-PDA and 2-CA, respectively (compared to 21.8 and 41.0% at the screen-printed carbon electrode and 28.3 and 34.1% at the glassy carbon electrode, respectively). The favorable properties of the diamond electrode indicate great promise for environmental applications in CE and other microchip devices.     

Separation of proteins on surface-modified poly(dimethylsiloxane) microfluidic devices

Separation and detection of proteins have been realized on nonionic surfactant-modified poly(dimethylsiloxane) (PDMS) microfabricated devices with end-column amperometric detection. The hydrophobic PDMS channels are turned into hydrophilic ones after being modified with Brij35 and facilitate the separation of proteins. The coating can remarkably reduce the adsorption of large protein molecules and is stable in the range of pH 6-12. The detection of proteins in such channels needs less rinsing time and thus efficiency is raised. Even large molecules of proteins can also be detected with better reproducibility and enhanced plate numbers. The relative standard deviation (RSD) of the migration time for glucose oxidase (GOD) is 2.2% (n = 19). Separation of GOD and myoglobin has been developed in modified channels. Predominant operational variables, such as the coating conditions, the concentration of surfactant and buffer, are studied in detail.     

Miniaturized CE System Based on Amperometric Detection and Horizontal Sampling

A novel miniaturized capillary electrophoresis (CE)-amperometric detection system has been fabricated by integrating a self-positioning electrode system and a 10-cm piece of fused silica capillary on a Plexiglas base plate. The self-positioning electrode system was composed of a disc working electrode positioned opposite the outlet of the capillary, with an Ag/AgCl reference electrode, a platinum auxiliary electrode, and a platinum grounding electrode accommodated in a rectangular detection cell on the plate. The platinum wire, close to the inlet of capillary, served as a contact to the high-voltage power supply. Alternate placement of the capillary inlet in vials containing sample or buffer solutions permits volume-defined electrokinetic sample introduction in a horizontal arrangement. Performance of this unique system was demonstrated by separating sugars, amino acids, and two phenols used in the pharmaceutical industry. The factors influencing the analytical performance of the new microsystem for the separation of p-aminophenol and acetaminophen have been characterized and optimized. The two analytes could be separated on baseline within 160s in 50mM acetate buffer (pH 5.0). Responses for p-aminophenol and acetaminophen were linear over the range of 10 to 1000µM with detection limits (S/N=3) of 2.1 and 2.9µM.     

Gauge-Invariant Regularization of Quantum Field Theory on the Light Front

We briefly describe problems of the Hamiltonian approach for quantizing gauge fields on the light front for space–time bounded by the inequality |x ^–|L with periodic boundary conditions in the variable x ^– imposed on all fields (the DLCQ method). With these restrictions, we consider the gauge-invariant ultraviolet regularization by passing to a lattice in transverse coordinates. We remove the remaining ultraviolet divergences in the longitudinal momentum p _– by imposing a gauge-invariant finite-mode regularization. It turns out that the canonical formalism on the light front with such a regularization imposed does not contain the usual most complicated second-class constraints between zero and nonzero modes of fields. The described scheme can be used both to regularize the standard gauge theory and to provide a gauge-invariant formulation of effective low-energy models on the light front. Because the manifest Lorentz invariance is broken in our formalism, the vacuum state is poorly defined. We discuss this problem, in particular, in relation to the problem of passing to the continuous space limit.     

Initial attempts at directly detecting alpha wave activity in the brain using MRI

The “direct detection” of neuronal activity by MRI could offer improved spatial and temporal resolution compared to the blood oxygenation level-dependent (BOLD) effect. Here we describe initial attempts to use MRI to detect directly the neuronal currents resulting from spontaneous alpha wave activity, which have previously been shown to generate the largest extracranial magnetic fields. Experiments were successfully carried out on four subjects at 3 T. A single slice was imaged at a rate of 25 images per second under two conditions. The first (in darkness with eyes-closed) was chosen to promote alpha wave activity, while the second (eyes-open viewing a visual stimulus) was chosen to suppress it. The fluctuations of the phase and magnitude of the resulting MR image data were frequency analysed, and tested for the signature of both alpha wave activity and neuronal activity evoked by the visual stimulus.

Regions were found that consistently showed elevated power in fluctuations of the phase of the MR signal, in the frequency range of alpha waves, during the eyes-closed condition. It was conservatively assumed that if oscillations occurred at the same frequency in the magnitude signal from the same region or at the same frequency in the phase or magnitude signal from other regions overlying large vessels or cerebrospinal fluid (CSF), then the phase changes were not due to neuronal activity related to alpha waves. Using these criteria the data obtained were consistent with direct detection of alpha wave activity in three of the four volunteers. No significant MR signal fluctuations due to evoked activity were identified.     

Simple and extractionless high-performance liquid chromatographic determination of rosiglitazone in human plasma and application to pharmacokinetics in humans

A simple and extractionless HPLC method using fluorescence detection was developed for the determination of rosiglitazone in human plasma. After deproteinization using perchloric acid the plasma samples were directly injected onto the HPLC system. The mobile phase was composed of acetonitrile (52%) and 20 mm ammonium acetate (48%, pH 7.5), and analysis was run at a flow rate of 0.2 mL/min with the detector operating at 247 nm for excitation wavelength and at 367 nm for emission wavelength, respectively. The method has a mean recovery of 97%, while the intra-day and inter-day precisions were all less than 7%. This method is simple, specific, sensitive and requires only a small plasma volume with short analytical time, and is suitable for the determination of plasma rosiglitazone in routine measurements for pharmacokinetic studies.