A chemiluminescence-based continuous flow aqueous ozone analyzer using photoactivated chromotropic acid

Ozone has become the oxidant of choice for water disinfection, especially in large water treatment facilities. This paper describes a fast and sensitive method for the determination of ozone content by reaction with photoactivated chromotropic acid (CA, 4,5-dihydroxynaphthalene-2,7-disulfonic acid), which results in intense chemiluminescence (CL). Freshly ozonated water from a recirculating ozonizer/reservoir is injected into a carrier stream of deionized water in the flow-injection mode. This flow mixes with a stream of photoactivated CA solution in a spiral cell placed directly on top of an inexpensive miniature (8 mm diameter active area) photomultiplier tube (PMT). Alkaline CA is photoactivated by passing it through a FEP-Teflon^® coil (residence time ∼ 50 s) wrapped around a 1 W UV lamp emitting at 254 nm; without photoactivation, the signal is ∼70-fold lower. The S/N = 3 limit of detection for aqueous ozone is 3 μg l⁻¹ and good response slope is obtained up to an ozone concentration of 1.4 mg l⁻¹, the highest that could be made in this study. The response obeyed a quadratic equation with r² = 0.9984. No interference from permanganate ion is observed. The proposed system was applied to the monitoring of ozonation status of a playa lake water that exhibited significant ozone demand.     

Transport in boundary layer of divertor tokamaks

Study of transport in the boundary layer of tokamak plasma in presence of magnetic divertors is extended to the second order in ion collision frequency. Numerical results for ion and energy losses to the collector plates are presented for toroidal and poloidal divertors. For the toroidal case, the Wiener-Hopf solution for the second order distribution function is obtained. An error occurring in an earlier first order calculation is pointed out and corrected first order fluxes are also given. For the poloidal divertor, asymmetry observed in ion and energy transport is found to persist in the second order result.     

Fluorescence Spectroscopic and Calorimetry Based Approaches to Characterize the Mode of Interaction of Small Molecules with DNA

Ethidium bromide displacement assay by fluorescence is frequently used as a diagnostic tool to identify the intercalation ability of DNA binding small molecules. Here we have demonstrated that the method has pitfalls. We have employed fluorescence, absorbance and label free technique such as isothermal titration calorimetry to probe the limitations. Ethidium bromide, a non-specific intercalator, netropsin, a (A-T) specific minor groove binder, and sanguinarine, a (G-C) specific intercalator, have been used in our experiments to study the association of a ligand with DNA in presence of a competing ligand. Here we have shown that netropsin quenches the fluorescence intensity of an equilibrium mixture of ethidium bromide - calf thymus DNA via displacement of ethidium bromide. Isothermal titration calorimetry results question the accepted interpretation of the observed decrease in fluorescence of bound ethidium bromide in terms of competitive binding of two ligands to DNA. Furthermore, isothermal titration calorimetry experiments and absorbance measurements indicate that the fluorescence change might be due to formation of ternary complex and not displacement of one ligand by another.     

Two distinct quasifission modes in the 32S + 232Th reaction

Comprehensive fission measurements, including mass-angle distributions, for the reaction of 32S with the prolate deformed nucleus 232Th at near-barrier energies show two distinct components in both mass and angle; surprisingly, both have characteristics of quasifission. Their relative probabilities vary rapidly with the ratio of the beam energy to the capture barrier, suggesting a relationship with deformation aligned (sub-barrier), or antialigned (above-barrier), configurations at contact.     

Chromatographic peak resolution using Microsoft Excel Solver. The merit of time shifting input arrays

Resolution of overlapped chromatographic peaks is generally accomplished by modeling the peaks as Gaussian or modified Gaussian functions. It is possible, even preferable, to use actual single analyte input responses for this purpose and a nonlinear least squares minimization routine such as that provided by Microsoft Excel Solver can then provide the resolution. In practice, the quality of the results obtained varies greatly due to small shifts in retention time. I show here that such deconvolution can be considerably improved if one or more of the response arrays are iteratively shifted in time.     

Isobaric metabolite interferences and the requirement for close examination of raw data in addition to stringent chromatographic separations in liquid chromatography/tandem mass spectrometric analysis of drugs in biological matrix

In addition to matrix effects, common interferences observed in liquid chromatography/tandem mass spectrometry (LC/MS/MS) analyses can be caused by the response of drug-related metabolites to the multiple reaction monitoring (MRM) channel of a given drug, as a result of in-source reactions or decomposition of either phase I or II metabolites. However, it has been largely ignored that, for some drugs, metabolism can lead to the formation of isobaric or isomeric metabolites that exhibit the same MRM transitions as parent drugs. The present study describes two examples demonstrating that interference caused by isobaric or isomeric metabolites is a practical issue in analyzing biological samples by LC/MS/MS. In the first case, two sequential metabolic reactions, demethylation followed by oxidation of a primary alcohol moiety to a carboxylic acid, produced an isobaric metabolite that exhibits a MRM transition identical to the parent drug. Because the drug compound was rapidly metabolized in rats and completely disappeared in plasma samples, the isobaric metabolite appeared as a single peak in the total ion current (TIC) trace and could easily be quantified as the drug since it was eluted at a retention time very close to that of the drug in a 12-min LC run. In the second example, metabolism via the ring-opening of a substituted isoxazole moiety led to the formation of an isomeric product that showed an almost identical collision-induced dissociation (CID) MS spectrum as the original drug. Because two components were co-eluted, the isomeric product could be mistakenly quantified and reported by data processing software as the parent drug if the TIC trace was not carefully inspected. Nowadays, all LC/MS data are processed by computer software in a highly automated fashion, and some analysts may spend much less time to visually examine raw TIC traces than they used to do. Two examples described in this article remind us that quality data require both adequate chromatographic separations and close examination of raw data in LC/MS/MS analyses of drugs in biological matrix.