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Biomedical subjects

A M Stalcup

Publications and source records attributed to A M Stalcup.

At least 19 recordsLinked to original sources
PubMed2005

Retention characteristics of a new butylimidazolium-based stationary phase.

A new HPLC stationary phase has been synthesized based on the ionic liquid n-butylimidazolium bromide. Imidazolium was covalently immobilized on a silica substrate through an n-alkyl tether and the retention characteristics of the resulting stationary phase were evaluated systematically. Using 28 small aromatic test solutes and reversed phase conditions, the linear solvation energy relationship approach was successfully used to characterize this new phase. The retention characteristics of the test solutes show remarkable similarity with phenyl stationary phases, despite the presence of a positive charge on the new imidazolium phase. Operated in the reversed phase mode, this new stationary phase shows considerable promise for the separation of neutral solutes and points to the potential for a truly multi-modal stationary phase.

Chromatography, High Pressure Liquid↗
PubMed2003

Capillary electrophoretic and nuclear magnetic resonance studies of interactions between halophenols and ionic liquid or tetraalkylammonium cations.

Aqueous capillary electrophoretic studies were performed to investigate interactions between halophenols and 1-ethyl-3-methylimidazolium tetrafluoroborate or tetraethylammonium tetrafluoroborate electrolytes. In both cases, increased halogen size correlated with increased affinity for the electrolyte cation. For isomers, the ortho substituted isomer exhibited higher affinity than the para isomer. Irreproducible CE results for analyte pairs in the presence of the ionic liquid stimulated investigations of the interactions between halophenols as well as with the cations of the electrolyte. These interactions were explored by proton and fluorine one-dimensional NMR. The NMR results indicated differences in the interactions between tetraethylammonium/iodophenols and imidazolium/iodophenols. The NMR results indicate hydrophobic stacking interactions between the iodophenols and possible similar interaction among phenols and imidazolium.

Cations↗
PubMed2001

Impact of triethylamine as a mobile phase additive on the resolution of racemic amino acids on an (+)-18-crown-6-tetracarboxylic acid-derived chiral stationary phase.

Recently, a new HPLC chiral stationary phase (CSP) prepared by covalently bonding (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid on silica gel was successfully employed in resolving various racemic natural and unnatural amino acids containing a primary amino group. Current work details on-going efforts to improve the effectiveness of this type of material. The analytes used in this study included various substituted phenylalanines, phenylglycine homologues and other primary amino acids. In an attempt to increase enantioselectivity, the effect of methanol and triethylamine modifiers was evaluated in an aqueous mobile phase containing sulfuric acid. In general. retention time increased with increasing methanol and triethylamine concentration. In addition, highest enantioselectivities were obtained with high methanol and high triethylamine; however, these conditions produced excessively long retention. All of the analytes were well resolved on the CSP with a mobile phase of 20% methanol containing 14.3 mM triethylamine and 10.0 mM sulfuric acid.

Amino Acids↗
PubMed2001

Use of dyes to investigate migration of the chiral selector in CFFE and the impact on the chiral separations.

Continuous free flow electrophoresis was investigated as a tool for the preparative chiral separation of piperoxan enantiomers using sulfated beta-cyclodextrin (sbeta-CD) as the chiral additive. Bulk migration of sbeta-CD was confirmed using LC-MS analysis of the individual fractions collected and visualized with the addition of crystal violet to the separation buffer. In the absence of sbeta-CD, the crystal violet-containing buffer was reddish/purple and the crystal violet was deflected cathodically in the chamber. In the presence of sbeta-CD, the crystal violet-containing buffer was blue and was deflected anodically. However, formation of accumulation and depletion zones was apparent in both cases. The addition of sbeta-CD to the cathodic wash solution allowed for almost complete resolution of the piperoxan enantiomers with a processing rate of 0.45 mg/ h.

Coloring Agents↗
PubMed2001

Capillary electrophoretic application of 1-alkyl-3-methylimidazolium-based ionic liquids.

Ionic substances with melting points at or close to room temperature are referred to as ionic liquids. Interest in ionic liquids for their potential in different chemical processes is increasing, because they are environmentally benign and are good solvents for a wide range of both organic and inorganic materials. In this study, a capillary electrophoretic method for resolving phenolic compounds found in grape seed extracts is reported. The method, in which 1-alkyl-3-methylimidazolium-based ionic liquids are used as the running electrolytes, is simple and reproducible. The separation mechanism seems to involve association between the imidazolium cations and the polyphenols. The role of the alkyl substituents on the imidazolium cations was investigated and will be discussed.

Journal Article↗
PubMed2001

A comparison of phosphated and sulfated beta-cyclodextrins as chiral selectors for capillary electrophoresis.

The enantioseparation capabilities of three different functionalized beta-cyclodextrins, two sulfated beta-cyclodextrins with 4 and 15 nominal degrees of substitution and a phosphated beta-cyclodextrin with 8 degrees of substitution, were compared. While anodic detection was used with both sulfated cyclodextrins, the phosphated cyclodextrin required cathodic detection suggesting either lower ionization of the phosphated cyclodextrin or generally lower affinity of the analytes for the phosphated cyclodextrin. The effects of several experimental parameters were evaluated with respect to enantioseparation. The degrees of substitution of the cyclodextrin, pH of the background electrolyte as well as the concentration of the functionalized beta-cyclodextrin, each had a significant influence on the successful enantiomeric separation of the chiral drugs investigated.

Cyclodextrins↗
PubMed2001

Quantitative determination of clenbuterol, salbutamol and tulobuterol enantiomers by capillary electrophoresis.

Enantiomers of clenbuterol, salbutamol and tulobuterol were directly separated and quantitated from a spiked sample by capillary electrophoresis (CE) using sulfaited beta-cyclodextrin (SCD) as chiral selector and phosphate as running buffer. The SCD and buffer concentration, pH and field strength were the parameters studied to optimize the separation. Optimal separation was obtained using 50 mM of phosphate monobasic at pH = 2.24, 0.25% (w/w) of sulfated cyclodextrin and a field strength of 10 kV, with 20 min total time analysis. Comparison between two different injection modes (hydrodynamic and electrokinetic) was made. In the hydrodynamic mode, repeatability (expressed as relative standard deviation, RSD) was less than 1.2% for migration times for all the analyte peaks and less than 2% for peak area percentages. With respect to reproducibility, RSD was less than 3.8% for migration time and less than 3% for peak area percentages. Calibration curves were set up for two different sample concentration ranges (1 to 10 microg mL(-1) and 160-800 ng mL(-1), of each of the racemates studied). Although the electrokinetic injection mode for an aqueous sample appeared to suffer from some enantiodiscrimination, calibration curves were linear in the range between 1 and 10 ng mL(-1) with regression coefficients ranging from 0.9996 to 0.9952. As in the case of hydrodynamic injection, the method was tested with a spiked sample.

Albuterol↗
PubMed2000

Cyclodextrins: a versatile tool in separation science.

Cyclodextrins have been used extensively in separation science because they have been shown to discriminate between positional isomers, functional groups, homologues and enantiomers. This property makes them one of the most useful agents for a wide variety of separations. The main goal of this review is a discussion of somewhat more exotic applications of cyclodextrins to separation methods. Techniques examined in detail include gel electrophoresis, isotachophoresis, isoelectric focusing, preparative scale electrophoretic techniques, thin-layer chromatography, electrochemically modulated liquid chromatography, use of monolithic media in liquid chromatography, microdialysis, separation on hollow fibers, foam flotation enrichment, solid- and liquid-phase extractions, countercurrent chromatography, separation through liquid and composite membranes, and cyclodextrin applications in molecularly imprinted polymers. Since a lot of attention has been paid to use of cyclodextrins in capillary electrophoresis, liquid, gas and supercritical fluid chromatography, these techniques will be only briefly discussed. The second goal of this review is a discussion of a scaling-up the analytical separations to semi-preparative or preparative techniques. It was found that despite a need for large scale separations in the industry, development of these techniques has been somewhat lagging behind development of miniaturized analytical separations. It is hoped that the focus on areas outside more traditional separation applications might stimulate further research.

Chromatography↗
PubMed2000

Development of chiral HPLC for selenoamino acids with ICP-MS detection:application to selenium nutritional supplements.

The enantiomeric separation of three underivatized seleno-amino acids, D,L-selenocystine, and D,L-selenomethionine, and D,L-selenomethionine, with UV and ICP-MS detection is described. An HPLC column with a chiral crown ether stationary phase and a mobile phase of 0.10 M HCIO4 was used. Absolute detection limits obtained with UV detection ranged from 34.5 to 47.1 ng whereas those obtained with the plasma detector were ca. 40-400 times better. The separations with either detector were good, with the little detector effect on the resolution. Ten commercially available dietary selenium supplements were analyzed using the chiral column to identify and quantify the selenium species present with both detection modes. Selenium species were easily identified using ICP-MS detection, whereas UV detection was not viable because of interferences from the sample matrix and inadequate sensitivity. Selenium species that were unretained using the chiral column were identified using anion exchange chromatography. Total amounts in the samples were also measured using a conventional digestion and enzymatic digestion with ICP-MS detection.

Chromatography, High Pressure Liquid↗
PubMed2000

A comparison of vancomycin and sulfated beta-cyclodextrin as chiral selectors for enantiomeric separations of selenoamino acids using capillary electrophoresis with UV absorbance detection.

The enantiomeric separation of three selenoamino acids, D,L-selenomethionine, D,L-selenoethionine and D,L-selenocystine is described. Both sulfated beta-cyclodextrin and vancomycin have been successfully used to separate all enantiomers of the compounds with UV detection. Reproducible separations, in terms of peak area and migration time were obtained using sulfated beta-cyclodextrin with reversed polarity and UV detection. With vancomycin as a chiral selector, reversed polarity was found to be more reproducible than positive polarity in terms of peak migration times.

Cystine↗
PubMed2000

Continuous free flow electrophoresis for preparative chiral separations of piperoxan using sulfated beta-cyclodextrin.

Continuous free flow electrophoresis was investigated as a tool for the preparative chiral separation of piperoxan using a sulfated cyclodextrin chiral additive. In the absence of chiral additive, the sample stream was deflected cathodically. However, the presence of sulfated cyclodextrin in the run buffer caused anodic deflection and splitting of the sample stream into two streams, each enriched in one enantiomer. Although the sulfated cyclodextrin used was comprised of a mixture of homologues and isomers, this polydispersity did not seem to significantly impact band dispersion. Sample introduction rates ranged from approximately 0.9-7.2 mg h-1. Maximum resolution was 0.53, using an applied voltage of 220 V, buffer composition of 0.075% sulfated cyclodextrin, 7.6 mM citrate (pH 3), 4.5 degrees C.

Adrenergic alpha-Antagonists↗
PubMed2000

Tetraethylammonium tetrafluoroborate: a novel electrolyte with a unique role in the capillary electrophoretic separation of polyphenols found in grape seed extracts.

A capillary electrophoretic method for resolving phenolic compounds found in grape seed extracts was developed using a quaternary ammonium salt as the main electrolyte solution. Seven polyphenols were separated and identified. The separation mechanism seems to involve association between quaternary ammonium cations and the polyphenols. Migration times roughly correlate with the size of the known phenols. The role of the alkyl substituents on the quaternary ammonium ions was investigated and is discussed. The method of analysis proposed herein exhibits high reproducibility in terms of migration times for a complex mixture using a single component background electrolyte.

Electrolytes↗
PubMed1999

Charged cyclodextrin-mediated sample stacking in micellar capillary electrophoresis. A simple method for enhancing the detection sensitivity of hydrophobic compounds.

The development of on-line sample stacking techniques for enhancing limits of detection of neutral analytes in micellar capillary electrophoresis (MCE) has recently gained much attention. Utilizing high-conductivity sample matrices to invoke sample stacking is promising, but requires the limited use of sample solubilizing agents such as alcohols in the sample matrix. In this study, we show how simple replacement of the sample solvent (methanol) with a solution of sulfated beta-cyclodextrin (s beta-CD) allows a significant increase in the sensitivity of detection of model hydrophobic analytes. This increase in sensitivity is accompanied by significant peak sharpening. Sulfated CDs in the sample matrix allow for effective solubilization of hydrophobic analytes without the use of organic solvents such as methanol. The testing of various sample matrix s beta-CD concentrations for their effect on peak sharpening identified 3 to 5% as optimal for the estrogen standards. The use of a s beta-CD sample matrix allowed for hydrostatic injections (3.5 kPa) of 297 s, compared with 4 s when the analytes were dissolved in methanol. A mechanism explaining the s beta-CD-induced effect involves an analyte transfer mechanism where the s beta-CDs, despite providing anodic mobility to analytes in the sample zone, are able to transfer analytes to trailing separation buffer micelles for "recycling" back into the sample zone without compromising the stacking process. The overall improvement in sensitivity allows detection of estrogens in the parts-per-billion range and stands to improve the utility of MCE as a bioanalytical technique.

Chromatography, Micellar Electrokinetic Capillary↗
PubMed1998

Enantiomeric separations of terbutaline by CE with a sulfated beta-cyclodextrin chiral selector: a quantitative binding study.

Sulfated beta-cyclodextrin, a negatively charged chiral selector, was used for the enantiomeric separation of racemic terbutaline by capillary electrophoresis. Chiral separation was found to increase with decreasing cyclodextrin concentration. Host-guest complex binding constants for this system were determined by UV difference spectroscopy (Kav = 1490 M-1) and by CE under conditions of minimal EOF and reversed polarity (K1 = 1730 M-1, K2 = 1590 M-1, alpha = 1.09). The effect of organic modifiers, methanol, and acetonitrile was also studied over a wide range of modifier concentrations. Binding constants decreased while selectivity increased with increasing organic modifier concentration (10% MeOH: K1 = 1590 M-1, K2 = 1130 M-1, alpha = 1.41. 10% ACN: K1 = 1320 M-1, K2 = 870 M-1, alpha = 1.52). Experimental results are discussed in the context of existing separation models.

Carbohydrate Sequence↗
PubMed1998

Application of classical gel electrophoresis to the chiral separation of milligram quantities of terbutaline.

Although the last couple of decades has been tremendous progress in the ability to do chiral separations, the ability to do larger scale chiral separations has lagged somewhat behind the current analytical chiral separation state of the art. The potential of classical gel electrophoresis for chiral separation of milligram quantities of chiral material is examined. A protocol for the chiral separation of milligram quantities of terbutaline using sulfated cyclodextrin as a chiral additive is demonstrated. The possible advantages of the approach are discussed.

Adrenergic beta-Agonists↗
PubMed1998

Application of heparin to chiral separations of antihistamines by capillary electrophoresis.

A study of the chiral separations of antihistamines, including pheniramine, chlorpheniramine, brompheniramine, carbinoxamine and doxylamine in capillary electrophoresis (CE) was accomplished using heparin as a chiral additive (CA) and phosphate buffer as the background electrolyte. Several factors were shown to affect both the selectivity and the migration time, including concentration of heparin, concentration of buffer, and the pH. A dual mechanism involving both inclusion complexation and ionic interactions with heparin is thought to be responsible for the chiral recognition. In the pH range of 2.6-3.5 and reversed polarity, baseline resolutions were obtained using a wide range of buffer and heparin concentrations. Typically, chiral resolution was obtained within 50 min.

Brompheniramine↗
PubMed1998

Charged chelate-capillary electrophoresis of endogenous corticosteroids.

Separation of endogenous 17- or 18-hydroxylated corticosteroids (of the 21-hydroxylated 4-pregnen series) as charged chelates in capillary electrophoresis with borate as the ligand is demonstrated. Aldosterone, 18-hydroxycorticosterone, 18-hydroxy-11-deoxycorticosterone, cortisone, cortisol, and 11-deoxycortisol are separated and resolved by 400 mM borate buffer at pH 9.0. Separation characteristics of the corticosteroid charged chelates were examined by varying the separation buffer borate concentration, pH, ionic strength, and addition of organic modifiers. The borate ion [B(OH)4]- is identified as the critical buffer component. Corticosteroids chelate borate with proximal hydroxyls composed of either the 17- or 18-hydroxyl in combination with the 21-position hydroxyl. Corticosteroid/borate chelation as indicated by CE results is corroborated with 11B-nuclear magnetic resonance (11B-NMR) spectra. Chelation is a readily reversible process, with the strength of the resultant chelate, as opposed to the charge-to-mass ratio, predominantly determining analyte mobility in charged chelate - capillary electrophoresis (CC-CE).

18-Hydroxycorticosterone↗