Tear analysis of ascorbic acid,uric acid and malondialdehyde with capillary electrophoresis

Tears have a significant role in antioxidant defense in ocular tissues and since their collection is quick and noninvasive, their analysis would facilitate monitoring of pathophysiological changes. However, their low volume and low content of antioxidants makes analysis difficult; methods of high sensitivity are needed. In this paper, we present a method for tear analysis of two antioxidant molecules (ascorbic and uric acid) and of a lipid peroxidation indicator (malondialdehyde) with capillary electrophoresis. Tears were collected with Schirmer strips, extracted with a low‐pH phosphate buffer, centrifuged through membrane filters and an antioxidant was added. They were stable at ?70°C for 15 days. After pilot experiments, optimum electrophoretic separation was achieved in a 25 mm borate buffer, pH 10.0, containing 100 mm sodium dodecyl sulfate at 25°C and 20 kV. The developed method has good repeatability (<5% RSD), precision (<15% relative error values) and high sensitivity (LLOQ values of 20, 2.3 and 2.5 μM for ascorbate, urate and malondialdehyde, respectively). It was applied to the analysis of tears from healthy individuals and the antioxidant levels are in agreement with those obtained with other techniques. This method might serve as a tool to clarify the role of endogenous antioxidants in the pathophysiology of ocular diseases. Copyright © 2009 John Wiley & Sons, Ltd.     

The relation between relaxed enthalpy and volume during physical aging

Several papers have recently presented results of measurements of physical aging by studying the behavior of glassy materials quenched from temperatures above their glass transition temperature T_g. The evolution of the aging process is usually followed by plotting the relaxed enthalpy versus the accompanying decrease in volume. Here, we focus on the slope of such plots, which are found to be similar to the inverse value of the isothermal compressibility close to T_g. An explanation of this empirical result is attempted in the frame of a model that interconnects the defect Gibbs energy with properties of the bulk material.     

Analytical and Structural Tools of Lipid Hydroperoxides: Present State and Future Perspectives

Mono- and polyunsaturated lipids are particularly susceptible to peroxidation, which results in the formation of lipid hydroperoxides (LOOHs) as primary nonradical-reaction products. LOOHs may undergo degradation to various products that have been implicated in vital biological reactions, and thus in the pathogenesis of various diseases. The structure elucidation and qualitative and quantitative analysis of lipid hydroperoxides are therefore of great importance. The objectives of the present review are to provide a critical analysis of various methods that have been widely applied, and more specifically on volumetric methods, applications of UV-visible, infrared, Raman/surface-enhanced Raman, fluorescence and chemiluminescence spectroscopies, chromatographic methods, hyphenated MS techniques, NMR and chromatographic methods, NMR spectroscopy in mixture analysis, structural investigations based on quantum chemical calculations of NMR parameters, applications in living cells, and metabolomics. Emphasis will be given to analytical and structural methods that can contribute significantly to the molecular basis of the chemical process involved in the formation of lipid hydroperoxides without the need for the isolation of the individual components. Furthermore, future developments in the field will be discussed.     

Exploring an unknown graph

We wish to explore all edges of an unknown directed, strongly connected graph. At each point, we have a map of all nodes and edges we have visited, we can recognize these nodes and edges if we see them again, and we know how many unexplored edges emanate from each node we have visited, but we cannot tell where each leads until we traverse it. We wish to minimize the ratio of the total number of edges traversed divided by the optimum number of traversals, had we known the graph. For Eulerian graphs, this ratio cannot be better than two, and two is achievable by a simple algorithm. In contrast, the ratio is unbounded when the deficiency of the graph (the number of edges that have to be added to make it Eulerian) is unbounded. Our main result is an algorithm that achieves a bounded ratio when the deficiency is bounded. © 1999 John Wiley & Sons, Inc. J Graph Theory 32: 265–297, 1999     

Designing an all-optical packet filtering module for WDM broadcast-and-select star networks

An all-optical packet filtering module for WDM broadcast-and-select star networks is introduced. At each time instant, only one packet per wavelength is allowed to pass to the star coupler. Therefore, collisions are avoided and the network performance is improved. The proposed module is based on the use of optical logic circuits for controlling the passing of the transmitted packets to the star coupler, without the need of optical to electronic translation or electronic processing of the network feedback information. In this way, the processing time is drastically reduced, while the need for slowly tunable optical filters is eliminated. Furthermore, due to the all-optical nature of the network hub, the reliability of the system is improved.     

The adjacency relation on the traveling salesman polytope is NP-Complete

We consider the problem of determining whether two traveling salesman tours correspond to non-adjacent vertices of the convex polytope associated with the traveling salesman problem. This problem is shown to be NP-Complete for both the symmetric and nonsymmetric traveling salesman problem. Several implications are discussed.This Research was supported by NSF Grant GK-420488, the U.S. Army Research Office-Durham under Grant DAHC04-75-G0192, and an IBM Fellowship.     

On negative cycles in mixed graphs

We show that, for mixed graphs, i.e., graphs having both directed and undirected edges, with a length function defined on the edges, the problems of detecting negative cycles and of finding the shortest path in the absence of negative cycles are NP-complete.     

An unexpected base-induced rearrangement of tritylamine

An unexpected rearrangement was observed during the treatment of tritylamine with n-butyllithium, leading to the formation of an imine.     

A simple method for the alkaline hydrolysis of esters

A very mild and rapid procedure for the efficient alkaline hydrolysis of esters in non-aqueous conditions has been developed, by the use of dichloromethane/methanol (9:1) as solvent. This method conveniently provides both carboxylic acids and alcohols from the corresponding esters and sodium hydroxide in a few minutes at room temperature. A plausible reaction mechanism is proposed.     

The effect of acidification on the determination of organic carbon, total nitrogen and their stable isotopic composition in algae and marine sediment

We investigated the effects of sample acidification on the stable carbon and nitrogen isotopic composition (delta13C and delta15N), as well as the organic carbon (OC) and total nitrogen (TN) composition, of an algal culture and a marine sediment. Replicate measurements of untreated and acid-treated samples were made using 1 M, 2 M and 6 M HCl, 6% H2SO3 and 1 M H3PO4. For all treatments the precision of the analysis for the acid-treated sample was equal to or less than that in the non-acidified sample. For the algae, analysis of variance (ANOVA) indicated no significant differences in the mean OC and TN concentration, or delta13C and delta15N composition, between any acid treatment and non-acidified samples. For the sediment sample a comparison could only be made between the different acid treatments because the untreated contained significant amounts ( approximately 30%) of carbonate carbon. ANOVA indicated that the mean OC determined in sediment samples after the 1 M HCl treatment and the mean delta13C values after the 6% H2SO3 and 1 M H3PO4 treatments were significantly different (p < 0.013 and < .05, respectively) from all other treatments. Mass balance calculations indicate that in some instances delta13C values were biased due to a contribution from unreacted carbonate carbon. There were no significant differences in the mean TN between any acid-treated and non-acidified samples. The mean delta15N values after 6 M HCl, 6% H2SO3 and 1 M H3PO4 treatments were significantly different from the untreated sediment sample (p < 0.044). Based on the significant bias observed for the delta15N and delta13C values, a weak (1-2 M) HCl solution is confirmed as the most appropriate acid for the removal of inorganic carbon from natural materials requiring elemental and isotopic analysis.