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J D Stuart

Publications and source records attributed to J D Stuart.

26 records · Page 2Linked to original sources

High-performance liquid chromatography of substituted p-benzoquinones and p-hydroquinones. I. Interplay of on-column redox reaction and the chromatographic retention process.

Chromatograms exhibiting unusual elution profiles were obtained in the reversed-phase chromatography of methoxy-substituted hydroquinones with hydro-organic mobile phases. The dependence of the elution profiles on the flow-rate and the mass of injected sample indicated that peaks were caused by the interplay of the chromatographic retention process and the concomitant oxidation of hydroquinones in the chromatographic column. The reaction was first investigated in free solution and the first-order rate constants and equilibrium constants were estimated for the oxidation of 2-methoxy-, 2,5-dimethoxy-, 2,6-dimethoxy-, 2,3,5-trimethoxy- and 2,3,5,6-tetramethoxyhydroquinones. The effect of Fe3+ and Cu2+ on the oxidation of 2,6-dimethoxyhydroquinone was also examined and it was found that Fe3+ caused a ten-fold increase in the reaction rate. The oxidation of 2-methoxy- and 2,6-dimethoxyhydroquinones in the chromatographic column showed first-order and zerothorder kinetic behavior at low and high sample loads, respectively. Such change in reaction order is typical for heterogeneous reactions that follow Langmuir-Hinshelwood kinetics and suggests the existence of catalytically active sites on the silica. Upon purging the columns with EDTA, on-column oxidation of the hydroquinones was attenuated so that no reaction zones appeared on the chromatogram. Subsequent loading of the column with Fe3+, however, gave rise to broad reaction zones and possibly to total conversion of the hydroquinones to benzoquinones in the column. In all cases investigated the rate of oxidation was much higher in the column than in free solution. On the basis of the results obtained here, heavy mental-catalyzed reaction at the stationary phase surface is proposed to be the dominant mechanism for the oxidation reaction examined here.

Benzoquinones↗

HPLC analysis of underivatized fatty acids in margarines.

The composition of the underivatized fatty acids in margarines was determined by high performance liquid chromatography (HPLC). A 50-min analysis gave not only the distribution of the cis- and trans-isomers of the 18 carbon-length, but also a quantitative measure of seven of the underivatized fatty acids studied. High concentrations of the essential fatty acid, linoleic acid, were found in the four margarine samples. Results of the quantitation, reproducability of the HPLC analysis, and stability of the standards are discussed. It was found that the developed HPLC analysis was able to adequately separate the geometric isomers, linoleic acid (18:2 delta 9c, 12c) from linolelaidic acid (18:2 delta 9t, 12t). However, a mixture of the other two isomers, 18:2 delta 9c, 12t and 18:2 delta 9c, 12c coeluted together between the peaks due to the 18:2 delta 9c, 12c and 18:2 delta 9t, 12t isomers. This study did not attempt to separate the various positional isomers of underivatized fatty acids.

Chromatography, High Pressure Liquid↗

Effect of antacids on absorption of clorazepate.

The effect of a magnesia and alumina antacid suspension on the absorption of clorazepate dipotassium was studied in 15 normal healthy adult subjects who ingested a 15-mg dose of clorazepate alone or with single or multiple doses of antacid. The results of this three-period randomized complete crossover study showed a trend of initially slower absorption and lower peak nordiazepam plasma levels when administered with the antacid suspension. However, there were no significant differences among treatments in the extent of absorption as measured by the area under the plasma level-time curves. Clorazepate plasma levels were of relatively short duration and similar for all treatments. The urinary excretion pattern was likewise comparable with conjugated oxazepam, the major species measured. Plasma elimination half-lives of nordiazepam and clorazepate were not affected by the antacid treatments.

Adult↗

Fluorescent assay of total serum cholesterol, with use of gas-liquid chromatography to study saponification efficiency.

We describe a fluorescent determination of total cholesterol in serum for which the accuracy and precision are comparable to that for the method of Abell-Kendall, a method of generally accepted accuracy. By the use of quality reagents and the rigorous exclusion of water, the strong fluorophor that develops on reacting concentrated sulfuric acid with cholesterol can be used to quantitatively determine the total cholesterol in serum. We used gas-liquid chromatography to monitor the extent of saponification of the cholesterol esters, because we found them to have fluorescent efficiencies that differed from that of free cholesterol. Sodium methoxide in methanol/methylene chloride (1/3 by vol) was shown by gas-liquid chromatography to very effectively saponify the cholesterol esters in serum.

Cholesterol↗

Application of single-donor fibrin glue to burns.

Early tangential excision and immediate grafting of the burn-injured patient has been shown to be effective. Along with the use of this technique, however, comes the potential for significant blood loss, prolonged operative time, and partial loss of graft due to underlying hematoma formation. Based on experience using a pooled fibrinogen preparation, European and Japanese surgeons have provided evidence for the positive hemostatic and skin transplant fixation effects of fibrin glue. This commercial preparation, however, has not been approved by the U.S. Food and Drug Administration for use in the United States because of high risk of hepatitis and HIV transmission. Using a method of preparing highly concentrated fibrinogen utilizing standard blood bank techniques developed at the University of Virginia, we have applied single-donor fibrin glue as an adjunct in the early excision and grafting of 26 patients. Since we have been using fibrin glue, we have noted a marked reduction in operative blood loss and time involved in obtaining hemostasis. Additionally, we have found the application of the grafts to be facilitated by the "stickiness" of the recipient bed. In follow-up, grafts applied utilizing the fibrin glue technique have proceeded to uncomplicated wound healing with an overall 98% graft take.

Adult↗