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Kristin A Fletcher

Publications and source records attributed to Kristin A Fletcher.

10 recordsLinked to original sources
PubMed2007

Understanding chiral molecular micellar separations using steady-state fluorescence anisotropy, capillary electrophoresis, and NMR.

Chiral separations employing four diastereomers of poly sodium N-undecanoyl leucylvalinate (p-SULV) as chiral selectors are probed by use of MEKC, steady-state fluorescence anisotropy, and NMR. By employing diastereomers and thus altering the stereochemistry of a single amino acid in a systematic way, one may control the enantiorecognition ability of the chiral selector. As a result, one can gain a better understanding of the mechanisms of chiral recognition for the two classes of neutral or anionic chiral analytes studied. Evaluation of the chiral interactions leading to chiral separations confirmed our earlier observation of a strong relationship between the selectivity (alpha) observed using a chromatographic separation technique (MEKC) and that determined from the spectroscopic parameter, beta. A linear alpha versus beta relationship was observed for the molecular micelle p-(L)-SULV with all eight analytes included in this study. However, as we earlier predicted, different groups of analytes had different slopes, i.e., values of m, suggesting different chiral separation mechanisms. Evaluation of the data allowed a grouping of the analytes according to the primary site of chiral interaction with the leucine or valine moiety of molecular micelle chiral headgroup.

Anisotropy↗
PubMed2005

Detection of homocysteine and cysteine.

At elevated levels, homocysteine (Hcy, 1) is a risk factor for cardiovascular diseases, Alzheimer's disease, neural tube defects, and osteoporosis. Both 1 and cysteine (Cys, 3) are linked to neurotoxicity. The biochemical mechanisms by which 1 and 3 are involved in disease states are relatively unclear. Herein, we describe simple methods for detecting either Hcy or Cys in the visible spectral region with the highest selectivity reported to date without using biochemical techniques or preparative separations. Simple methods and readily available reagents allow for the detection of Cys and Hcy in the range of their physiologically relevant levels. New HPLC postcolumn detection methods for biological thiols are reported. The potential biomedical relevance of the chemical mechanisms involved in the detection of 1 is described.

Aldehydes↗
PubMed2005

Capillary electrochromatography using polyelectrolyte multilayer coatings.

This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed.

Journal Article↗
PubMed2004

Influence of the polydispersity of polymeric surfactants on the enantioselectivity of chiral compounds in micellar electrokinetic chromatography.

Poly(sodium undecenoyl-L-leucinate) (poly-L-SUL) was fractionated by the use of different molecular weight cutoff (MWCO) filters to narrow the polydispersity of the macromolecular sizes of the polymeric surfactant. The resulting polymeric surfactant fractions were characterized by the use of three techniques: (1) pulsed field gradient nuclear magnetic resonance (PFG-NMR) was used to determine the hydrodynamic radii, (2) analytical ultracentrifugation (AUC) was used to determine the molecular weights, and (3) steady-state fluorescence was used to determine the polarity of the nonfractionated and fractionated polymeric surfactants. From the data acquired from PFG-NMR, AUC, and fluorescence, it was noted that the hydrodynamic radii and molecular weight of the fractionated poly-L-SUL increased, while the polarity decreased with the increase in the size of the MWCO filter. However, a similarity in physical properties was observed between the nonfractionated and 10-30K fractionated poly-L-SUL except for the hydrodynamic radius and diffusion coefficients. The influence of different macromolecular sizes of poly-L-SUL on the chiral separation of phenylthiohydantion (PTH)-amino acids and coumarinic derivatives, as test analytes, was elucidated by the use of micellar electrokinetic chromatography (MEKC). The size of polymeric surfactants as a prerequisite for chiral separation was demonstrated by comparing the separation properties of fractionated versus nonfractionated polymeric surfactants. Fractionated poly-L-SUL resulted in enhanced resolution and separation efficiency of the test analytes as compared to the case of the nonfractionated poly-L-SUL. This observation indicates that minimizing polydispersity of polymeric surfactants may be important for some chiral separation applications.

Chromatography, Micellar Electrokinetic Capillary↗
PubMed2004

Correlation between the fluorescent response of microfluidity probes and the water content and viscosity of ionic liquid and water mixtures.

Accurate data on transport properties such as viscosity are essential in plant and process design involving ionic liquids. In this study, we determined the absolute viscosity of the ionic liquid + water system at water mole fractions from 0 to 0.25 for three 1-alkyl-3-methylimidazolium ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide and 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide. In each case, the excimer to monomer ratio for 1,m-bis(1-pyrenyl)alkanes (m= 3 or 10) was found to increase linearly with the mole fraction of water. Of the probes studied only PRODAN and rhodamine 6G, both of which have the ability to participate in hydrogen bonding, exhibited Perrin hydrodynamic behavior in the lower viscosity bis(trifluoromethane sulfonyl)imides. As a result, these probes allow for the extrapolation of the absolute viscosity of the ionic liquid mixture from the experimental fluorescence steady-state polarization values.

Journal Article↗
PubMed2004

Surfactant aggregation within room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

On the basis of the response of solvatochromic probes [Reichardt's betaine dye, pyrene, and 1,3-bis(1-pyrenyl)propane], we have investigated the aggregation behavior of common anionic, cationic, and nonionic surfactants when solubilized within a low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (emimTf2N). We observed possible aggregate formation by all nonionic surfactants included in the study (Brij-35, Brij-700, Tween-20, and Triton X-100), while no aggregation was observed for the cationic surfactant cetyltrimethylammonium bromide. The anionic surfactant sodium dodecyl sulfate does not appear to solubilize within emimTf2N at ambient conditions.

Imidazoles↗
PubMed2003

Characterization of the solvation environment provided by dilute aqueous solutions of novel siloxane polysoaps using the fluorescence probe pyrene.

Solubilization environment afforded by several of the novel allyl glycidyl ether-modified methylhydrosiloxane polymers are investigated using a common polycyclic aromatic hydrocarbon fluorescence probe, pyrene. The backbone of the polymer has been modified by the addition of an alkyl chain of varying length (either C8, C12, or C18) and to differing degrees of substitution. The nomenclature adopted for the purposes of these studies is as follows: "AGENT" represents the backbone polymer with no alkyl substitution, and "OAGENT", "DAGENT", and "SAGENT" are substituted with n-octyl, n-dodecyl, and n-octadecyl, respectively. The percentage of alkyl substitution is designated as 10, 15, and 20%. The pyrene polarity scale (defined as the ratio of the intensity of peak I to peak III) was used to determine the relative dipolarity of the cybotactic region provided by approximately 1 w/w% aqueous polymer solutions compared to 10 mM sodium dodecylsulfate (SDS) micellar solution. Results indicate that 10-15% DAGENT afforded the most hydrophobic solubilization site, followed by 15% OAGENT and 15% SAGENT. In addition, as the degree of alkyl substitution of DAGENT increased from 10 to 20%, the cybotactic region appeared to become more hydrophobic. Furthermore, a deeper investigation into the relative size of the solubilization site revealed that all alkyl-substituted polymers promoted excimer formation at relatively low pyrene concentrations, indicating the possibility of localized concentration enhancement within the solvation pockets and/or compartmentalization of the solute molecules. The pyrene fluorescence excitation data strongly indicates ground-state heterogeneity that is most prominent in AGENT and decreases as the alkyl chain length is increased. This provides a relative sense of the size and shape of the solvation pockets afforded by each polymer solution. An overall analysis of the collected data indicated that these alkyl-substituted polymers may provide a more selective and efficient pseudostationary phase in electrokinetic chromatography with better solvation capacity for hydrophobic compounds compared to SDS.

Chromatography, Micellar Electrokinetic Capillary↗