The objective of the present work was systematic investigation of water-based headspace single-drop microextraction (SDME) technique, its conjunction with capillary electrophoresis, and application for the analysis of volatile inorganic compounds (cyanide and ammonium) in biomedical and environmental samples. Theoretically evaluated and experimentally confirmed that the manipulation in the volatility of the analyte by its chemical modification in the sample and/or in the acceptor phase is the most effective way to enhance the extraction performance in headspace SDME. Maximum extraction efficiency for cyanide was observed in the pH range 4.5–7.5, where cyanide anion is completely transferred into volatile HCN. Complete cyanide recoveries (≥96%) from metal-cyanide complexes were obtained by using two ligand-exchange reagents (ethylenediamine and dithizone). Maximum extraction efficiency was observed by the extraction of ammonia from alkaline samples (pH≥11) with neutral or slightly acidic acceptor phase (pH 3-7). Compared to existing methods water-based headspace SDME is significantly faster and simpler. In addition, proposed technique does not require any sample pre-treatment (deproteinization, acidic/alkaline distillation, etc.) and thus is much less susceptible to interferences. Finally, it offers possibility to choice of a wider variety of solvents and, consequently, enhances the range of extractable analytes as well as the range of analytical methods that can be coupled... [to full text] / Daktaro disertacijoje nuodugniai ištirtas mikroekstrakcijos iš viršerdvės vandens lašu metodas, apjungtas su kapiliarine elektroforeze bei pritaikytas lakių neorganinių junginių (cianido ir amonio) koncentravimui ir nustatymui biomedicininiuose ir aplinkos objektuose. Teoriniais skaičiavimais parodyta ir eksperimentiškai patvirtinta, kad efektyviausias būdas mikroekstrakcijos iš viršerdvės efektyvumui pagerinti – analitės lakumo didinimas chemiškai modifikuojant ją prieš ekstrakciją ir/arba jos lakumo mažinimas modifikuojant ją akceptorinėje fazėje. Maksimalus cianido mikroekstrakcijos efektyvumas pasiekiamas pH srityje 4,5- 7,5, kur cianidas kiekybiškai pervedamas į lakų HCN. Ištyrus cianido mikroekstrakciją tirpiklio lašu iš metalų cianidinių kompleksų tirpalų nustatyta, kad kiekybiškas silpnai surišto cianido suardymas (cianido išgavos siekia ≥96%) pasiekiamas panaudojus ligandų mainus etilendiamino ir ditizono mišiniu. Maksimalus amonio mikroekstrakcijos efektyvumas pasiekiamas ekstrahuojant jį iš pašarmintų mėginių (pH≥11) akceptorine faze, kurios pH 3-7. Lyginant su standartiniais metodais, siūlomas metodas yra greitesnis ir paprastesnis, visiškai eliminuojama mėginio matricos įtaka, nereikalingos jokios drastiškos (deproteinizacija, veikimas rūgštimis/šarmais, distiliacija ir pan.) manipuliacijos su mėginiu, todėl išvengiama mėginio matricos įtakos. Mikroekstrakcija iš viršerdvės vandens lašu praplečia mikroekstrakcijos metodų taikymo sritis: atveriama galimybė labai... [toliau žr. visą tekstą]

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The focus of this dissertation centers on the development and applications of gas chromatography/mass spectrometry and capillary electrophoresis methodologies to quantify monomeric compositions of the β-O-4 linkages in lignin. Pretreatment is a required step in the utilization of lignocellulosic biomass for biofuels. Lignin is the target of pretreatment because it hinders the accessibility of enzymes and chemicals to cellulose. The effects of pretreatment are commonly assessed utilizing enzymatic saccharification and lignin assays. However, these techniques do not elucidate the effects of pretreatment on the monomeric make up of lignin. The overarching hypothesis of this dissertation is that changes in individual monolignol content upon pretreatment can be observed from quantification. To test the hypothesis, a pretreatment, solution phase Fenton chemistry, was conducted on various lignocellulosic biomass feedstocks. Enzymatic saccharification studies showed a significant increase in glucose production upon Fenton pretreatment, however, lignin assays did not show a significant decrease in lignin content. Project two of this dissertation aimed to synthesize analytical standards in order to develop a quantitative thioacidolysis technique. The successful synthesis of the three arylglycerols were conducted utilizing and epoxidation reaction scheme which was hypothesized to produce a single diastereomer, as supported by GC/MS and chiral CE analysis. Upon method development, a quantitative thioacidolysis GC/MS method was applied to untreated and Fenton treated biomass. Results from this project revealed there was no significant change in the three lignin monomers. To verify the method, quantitative thioacidolysis GC/MS method was applied to a pretreatment method known to degrade lignin, alkaline peroxide pretreatment. The results of this project showed a significant change in monolignol concentrations upon alkaline peroxide pretreatment. Analytical degradative techniques, such as thioacidolysis, has traditionally assessed lignin as monomeric ratios. However, as this dissertation showed, upon alkaline peroxide pretreatment, no significant change was seen in the monomeric ratios, but there was a significant difference in all three monolignol concentrations. These results support the overall hypothesis that changes in individual monolignol content upon pretreatment can be observed from quantification. The works of this dissertation provides an analytical method which contributes to the elucidation of lignin.

A method for the separation and detection of standard resin acids (RAs), commonly found in pulp mill effluent and known to bioaccumulate in fish bile, was optimized using cyclodextrin modified electrokinetic capillary electrophoresis (CD-EKC) with ultra violet (UV) and laser induced fluorescence (LIF) detection. Optimal separation conditions were found with RA standards using UV detection at 214 nm, with a 72 mM sodium borate buffer pH 9.25, containing 35 mM beta-cyclodextrin sulfobutyl ether (SPCD), 15 mM of methyl-beta-cyclodextrin (MECD) and a 37 cm capillary with an internal diameter of 50pm. This resulted in a 12-min separation and the identification of 9 peaks, with a LOD of 10 ppm. To enable increased sensitivity, RAs were derivatized using the fluorescent label 4-BrMMc. A method for extracting resin acids from spiked fish bile and pulp mill effluent was developed, the extracted samples were derivatized, separated and identified using CD-EKC with LIF detection. The method of extraction and derivatization using CD-EKC was applied to biological samples of contaminated effluent and fish bile. (Abstract shortened by UMI.)

Thesis (Ph.D.)--Ohio University, November, 2004. / Includes bibliographical references (p. 163-171)

Thesis (Ph. D.)--Rutgers University, 2007. / "Graduate Program in Chemistry and Chemical Biology." Includes bibliographical references (p. 269-270).

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 159-174).

Thesis (Ph. D. (Pharmacy))--Rhodes University, 2006.

Thesis (Ph.D.)--Ohio University, November, 2004. / Title from PDF t.p. Includes bibliographical references (p. 163-171)