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D W Armstrong

Publications and source records attributed to D W Armstrong.

At least 37 records · Page 2Linked to original sources
PubMed2000

High-performance liquid chromatographic separation of enantiomers of synthetic amino acids on a ristocetin A chiral stationary phase.

A macrocyclic glycopeptide, ristocetin A, was used as chiral stationary phase for the high-performance liquid chromatographic separation of enantiomers of 28 unnatural amino acids, such as analogues of phenylalanine, tyrosine and tryptophan, and analogues containing 1,2,3,4-tetrahydroisoquinoline, tetraline or 1,2,3,4-tetrahydro-2-carboline skeletons. Excellent resolutions were achieved for most of the investigated compounds by using reversed-phase or a new polar-organic mobile phase system. The conditions of separation were optimized by variation of the mobile phase composition, temperature and flow-rate.

Amino Acids↗
PubMed2000

Evaluation of the macrocyclic glycopeptide A-40,926 as a high-performance liquid chromatographic chiral selector and comparison with teicoplanin chiral stationary phase.

A new macrocyclic antibiotic of the vancomycin family, referred to by its industrial designation as A-40,926, was bonded to 5 microm silica particles and utilised as a chiral stationary phase (CSP). Since A-40,926 is structurally related to teicoplanin, the A-40,926 CSP was compared to a commercially available teicoplanin CSP. A set of 28 chiral compounds, including amino-acids and related compounds, compounds with a ring containing the stereogenic centre, compounds bearing aromatic structures near their stereogenic centres and alcohols, was tested for enantioseparation on the two CSPs. The results are compared and discussed in terms of enantioselective Gibbs energy difference. The A-40,926 CSP was able to resolve one compound that was not resolved by the teicoplanin CSP. However, it could not separate four compounds that the teicoplanin CSP did separate. It is shown that the A-40,926 CSP is complementary to the teicoplanin CSP, thereby enlarging the number of enantiomers that can be separated by the macrocyclic glycopeptide based CSPs.

Anti-Bacterial Agents↗
PubMed2000

Enantioselective reversed-phase and non-aqueous capillary electrochromatography using a teicoplanin chiral stationary phase.

Enantiomeric separation of chiral pharmaceuticals is carried out in aqueous and non-aqueous packed capillary electrochromatography (CEC) using a teicoplanin chiral stationary phase (CSP). Capillaries were slurry packed with 5 microm 100-A porous silica particles modified with teicoplanin and initially evaluated using a non-aqueous polar organic mode system suitability test for the separation of metoprolol enantiomers (Rs = 2.3 and 53000 plates m(-1)). A number of pharmaceutical drugs were subsequently screened with enantioselectivity obtained for 25 racemic solutes including examples of neutral, acidic and basic molecules such as coumachlor (Rs = 3.0 and 86000 plates m(-1)) and alprenolol (Rs = 3.3 and 135000 plates m(-1)) in reversed-phase and polar organic mode, respectively. A statistical experimental design was used to investigate the effects of non-aqueous polar organic mobile phase parameters on the CEC electroosmotic flow, resolution and peak efficiency for two model solutes. Results primarily indicated that higher efficiency and resolution values could be attained at higher methanol contents which is similar to findings obtained on this phase in liquid chromatography.

Chromatography, Micellar Electrokinetic Capillary↗
PubMed2000

Evaluation of a vancomycin chiral stationary phase in capillary electrochromatography using polar organic and reversed-phase modes.

A vancomycin chiral stationary phase (CSP) was fully evaluated in capillary electrochromatography (CEC) in reversed-phase and polar organic modes for a number of racemic pharmaceutical compounds. High efficiency and resolution values were obtained for a number of compound classes including thalidomide in both the polar organic mode (190000 plates meter(-1) and Rs = 13.8) and reversed-phase mode (125000 plates meter(-1) and Rs = 13.0). Experimental parameters, including organic modifier, organic solvent ratio, ionic strength, pH, temperature, and voltage, were examined in both the aqueous and nonaqueous modes to deduce their effect on the resultant EOF, retention times, resolution, and efficiency of chiral separations. All results were consistent with and found to be a combination of what is known from existing literature on CEC theory and experience obtained with macrocyclic antibiotic CSPs in LC. Column stability was excellent, and each column packed was found to offer repeatable separations even when switching from the aqueous to the nonaqueous mode.

Anti-Bacterial Agents↗
PubMed2000

Rapid identification of the bacterial pathogens responsible for urinary tract infections using direct injection CE.

The use of high-performance capillary electrokinetic techniques for the separation, identification, and quantitation of intact microbes represents a new frontier for separation science. In this work, it is demonstrated that pathogens most responsible for urinary tract infections can be distinguished from one another after direct injection of untreated urine. High efficiencies (often exceeding 1000000 plates/m) and short analysis times (< 10 min) are characteristics of this approach. The concentration of the urine matrix appears to be able to cause a small, but definite, change in the electroosmotic flow velocity. This high-efficiency separation-based approach could prove to be invaluable for the diagnosis and tracking of certain diseases. It also could form the basis for a variety of rapid microbial assays.

Bacteriological Techniques↗
PubMed2000

High efficiency separation of microbial aggregates using capillary electrophoresis.

Recent advances in the technique of capillary electrophoresis have demonstrated fast, highly efficient separation of mixtures of intact microbes. This paper describes the application of this technique for the separation of microbial aggregates of Micrococcus luteus, Saccharomyces cerevisiae, or Alcaligenes faecalis. The aggregates of these microbes were resolved into several highly efficient peaks with analysis times under 10 min and efficiencies approaching 1000000 plates m(-1) in some cases. A reproducible relationship was found between the electrophoretic mobility and the aggregation number or size of the cluster under a given set of experimental conditions. Often, cellular aggregation was reversible with brief immersion in an ultrasound bath. This reversibility was confirmed by visual microscopy and electrophoretic data.

Alcaligenes↗
PubMed2000

Role of the carbohydrate moieties in chiral recognition on teicoplanin-based LC stationary phases.

For this study, we used the macrocyclic antibiotic teicoplanin, a molecule consisting of an aglycone peptide "basket" with three attached carbohydrate (sugar) moieties. The sugar units were removed and the aglycone was purified. Two chiral stationary phases (CSPs) were prepared in a similar way, one with the native teicoplanin molecule and the other with the aglycone. Twenty-six compounds were evaluated on the two CSPs with seven RPLC mobile phases and two polar organic mobile phases. The compounds were 13 amino acids or structurally related compounds (including DOPA, folinic acid, etc.) and 13 other compounds (such as carnitine, bromacil, etc.). The chromatographic results are given as the retention, selectivity, and resolution factors along with the peak efficiency and the enantioselective free energy difference corresponding to the separation of the two enantiomers. The polarities of the two CSPs are similar. It is clearly established that the aglycone is responsible for the enantioseparation of amino acids. The difference in enantioselective free energy between the aglycone CSP and the teicoplanin CSP was between 0.3 and 1 kcal/mol for amino acid enantioseparations. This produced resolution factors 2-5 times higher with the aglycone CSP. Four non amino acid compounds were separated only on the teicoplanin CSP. Six and five compounds were better separated on the teicoplanin and aglycone CSPs, respectively. Although the sugar units decrease the resolution of alpha-amino acid enantiomers, they can contribute significantly to the resolution of a number of non amino acid enantiomeric pairs.

Anti-Bacterial Agents↗
PubMed2000

High-performance liquid chromatographic separation of the enantiomers of unusual alpha-amino acid analogues.

The direct and indirect stereochemical resolution of the enantiomers of ring- and alpha-methyl-substituted phenylalanines and phenylalanine amides was attempted by high-performance liquid chromatographic methods. The direct separation was carried out on two chiral stationary phases, the crown-ether-based Crownpak CR(+), and the teicoplanin-based Chirobiotic T, while the indirect resolution was performed by applying pre-column derivatization with 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl isothiocyanate (GITC) and Nalpha-(2,4-dinitro-5-fluorophenyl)-L-alanine amide (Marfey's reagent, FDAA). The Chirobiotic T column was efficient in the separation of ring- and alpha-methyl-substituted phenylalanine analogues, but was ineffective for the amides of these analogues. The Crownpak CR(+) column separated the ring-substituted phenylalanines and amides, whereas the alpha-methylated analogues were coeluted. Of the two indirect methods, GITC derivatization seemed more effective than FDAA derivatization.

Amino Acids↗
PubMed2000

Dual X-ray absorptiometry total body bone mineral content and bone mineral density in 18- to 22-year-old caucasian men.

Eighty-six healthy, young Caucasian 18-year-old men with no known disease or bone injury were recruited to this study at the United States Naval Academy. Change in bone mineral density (BMD) of the hip, lumbar spine, and distal tibia, and total body bone mineral content (TBMC) was measured by dual-energy X-ray absorptiometry (DXA). BMD and TBMC of these men were measured within 2 months (67 +/- 3 days) of entering the Academy, and, at the end of their first, second, and fourth years. Hip BMD was unchanged during the study period (p > 0.05). Lumbar spine BMD increased 3% (p < 0.001) and distal tibia BMD increased 5% (p < 0.001). TBMC showed a 7.5% increase over the study period. In this group of young men, gain in BMD and TBMC is greatest to age 21 years, with minimal further increase after age 21. The significance of this rise in bone mass during early adulthood on risk for osteoporotic fractures in later life or its impact on exercise-related bone injuries is unknown and warrants further examination.

Absorptiometry, Photon↗
PubMed1999

Separating microbes in the manner of molecules. 1. Capillary electrokinetic approaches.

Selective, high-efficiency separations of intact bacteria may, in some cases, allow them to be identified and quantified in much the same way that molecules are done today. Two different capillary electrokinetic approaches were utilized. The first approach used a dissolved polymer-based CE separation that may be affected by size and shape considerations. Another approach uses capillary isoelectric focusing to separate bacteria by their surface charge or isoelectric point. Good peak shapes and extremely high efficiencies are observed (up to approximately 1,600,000 theoretical plates/m). Careful sample preparation and separation runs are essential in order to obtain reproducible separations. Expansion of these types of rapid, efficient microbial separations could have profound effects on many branches of science and technology.

Electrophoresis, Capillary↗
PubMed1999

Examination of ionic liquids and their interaction with molecules, when used as stationary phases in gas chromatography.

Stable room-temperature ionic liquids (RTILs) have been used as novel reaction solvents. They can solubilize complex polar molecules such as cyclodextrins and glycopeptides. Their wetting ability and viscosity allow them to be coated onto fused silica capillaries. Thus, 1-butyl-3-methylimidazolium hexafluorophosphate and the analogous chloride salt can be used as stationary phases for gas chromatography (GC). Using inverse GC, one can examine the nature of these ionic liquids via their interactions with a variety of compounds. The Rohrschneider-McReynolds constants were determined for both ionic liquids and a popular commercial polysiloxane stationary phase. Ionic liquid stationary phases seem to have a dual nature. They appear to act as a low-polarity stationary phase to nonpolar compounds. However, molecules with strong proton donor groups, in particular, are tenaciously retained. The nature of the anion can have a significant effect on both the solubilizing ability and the selectivity of ionic liquid stationary phases. It appears that the unusual properties of ionic liquids could make them beneficial in many areas of separation science.

Chromatography, Gas↗
PubMed1999

High-performance liquid chromatographic separation of novel atropic alpha,alpha-disubstituted-beta-amino acids, either on different beta-cyclodextrin-bonded phases or as their 1-fluoro-2,4-dinitrophenyl-5-L-alanine amide derivatives.

The high-performance liquid chromatographic enantioresolution of free and N- and/or C-protected derivatives of (R,S)-2',1':1,2;1",2":3,4-dinaphthcyclohepta-1,3-diene-6-aminometh yl-6- carboxylic acid (beta 2-Bin) by direct and indirect methods is reported. The direct separation was carried out on native and different derivatized beta-cyclodextrin-bonded phases. The indirect resolution was achieved by applying pre-column derivatization with 1-fluoro-2,4-dinitrophenyl-5-L-alanine amide. The effects of different parameters such as the mobile phase composition and the structures of the compounds on the enantiomeric resolution are discussed.

Alanine↗
PubMed1999

Plant and soil enantioselective biodegradation of racemic phenoxyalkanoic herbicides.

The biodegradation of the chiral phenoxyalkanoic herbicides 2-(2,4-dichlorophenoxy)propionic aid (2,4-DP) and 2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) was investigated using enantioselective HPLC and chiroptical detection. Racemic mixtures of 2,4-DP and MCPP were applied to three species of turf grass, four species of broadleaf weeds, and soil. Preferential degradation of the S-(-) enantiomer of each herbicide was observed in most species of broadleaf weeds and soil, while the degradation in all species of grass occurred without enantioselectivity. The biodegradation in all systems appeared to follow pseudo first-order kinetics with the fastest degradation occurring in broadleaf weeds, followed by the grasses. The slowest degradation was observed in soil. The results of this work illustrate the need to characterize both enantiomers of chiral agrochemicals in order to have an accurate understanding of their distribution and fate in the environment.

2,4-Dichlorophenoxyacetic Acid↗
PubMed1999

Evaluation of the enantiomeric composition of amino acids in tobacco.

Despite the fact that several studies have reported the concentrations of various free amino acids in tobacco, their enantiomeric composition is unknown. Both the absolute and enantiomeric compositions of proline, alanine, asparagine, aspartic acid, valine, methionine, leucine,and phenylalanine were determined for three strains of tobacco leaf, three types of smokeless tobacco, and six different blended filtered and nonfiltered reference cigarettes. Some of the highest levels of D-amino acids ever found in agricultural products were observed. Possible mechanisms for the production of these D-amino acids are considered. The relevance of D-amino acids in tobacco is discussed.

Amino Acids↗
PubMed1999

Separation of enantiomers by capillary electrophoresis using pentosan polysulfate.

Pentosan polysulfate, a semisynthetic polysaccharide, was employed as a chiral run buffer additive in capillary electrophoresis. Twenty-eight racemic analytes were resolved. The separations were successful only at low pH when the analytes were significantly protonated. This suggests that ionic interactions were the dominant associative interactions between the anionic pentosan polysulfate and the positively charged analytes. Compared to other linear, carbohydrate-based chiral selectors (i.e., chondroitin sulfates, heparin and dextran sulfate) pentosan polysulfate has some characteristics common of anionic polysaccharides; yet it has several differences in its structure and properties which account for its unusual enantioselectivity. The effects of pH, concentration of phosphate buffer, concentration of pentosan polysulfate and the type and concentration of organic modifier on the enantiomeric separations were investigated. The optimization of these separations were dependent on the nature of the analytes and could be achieved by the proper choice of experimental conditions.

Buffers↗
PubMed1999

Avoparcin, a new macrocyclic antibiotic chiral run buffer additive for capillary electrophoresis.

Avoparcin, like vancomycin, teicoplanin, and ristocetin A, belongs to the family of macrocyclic glycopeptide antibiotics. These antibiotics have all been used as effective chiral selectors for capillary electrophoresis (CE), thin-layer chromatography (TLC), and high performance liquid chromatography (HPLC). The present work focuses on avoparcin, which has been shown to be an excellent chiral selector for the CE enantioseparation of many N-blocked amino acids, as well as several anti-inflammatory drugs of pharmaceutical importance. The use of avoparcin as a chiral run buffer additive in CE is discussed, as well as the effects of changing experimental parameters, like avoparcin concentration, pH, organic modifiers, etc. Comparisons of enantioseparations of some N-3,5-dinitrobenzoyl-derivatized amino acids, using either avoparcin, ristocetin A, teicoplanin, or vancomycin in the run buffer, are also made. In general, vancomycin had the longest migration times, and ristocetin A the shortest, while avoparcin was intermediate. Generally, at least one of the four chiral selectors produced an excellent separation, while a different macrocyclic antibiotic produced a poor separation. Currently, we see no way to predict which chiral run buffer additive will be best or worst for an individual solute.

Anti-Bacterial Agents↗
PubMed1999

Comparison of pure nicotine- and smokeless tobacco extract-induced toxicities and oxidative stress.

The toxicities and oxidative stress-inducing actions of (-)-nicotine and smokeless tobacco extract (STE), containing equivalent amounts of nicotine, were studied. Toxicities were determined by colony formation assays using Chinese hamster ovary (CHO) cells. Results indicated that nicotine is less toxic than smokeless tobacco extract that contained the same amount of nicotine. The generation of reactive oxygen species, following treatment with smokeless tobacco extract and nicotine, was assessed by measurement of changes in glutathione (GSH) and malondialdehyde (MDA) levels. CHO cells (5 x 10(5) cells/5 ml media) were incubated with 4, 0.8, and 0.08 mg of nicotine and STE containing the same amounts of nicotine. All preparations of smokeless tobacco extract significantly decreased GSH levels and increased MDA generation. However, 0.08 mg of nicotine treatment did not result in a significant change in GSH level, and only 4 mg of nicotine were sufficient to increase MDA generation. Addition of free radical scavenging enzymes, superoxide dismutase (SOD) and catalase (CAT), and an intracellular GSH precursor, N-acetyl-L-cysteine (NAC), replenished the GSH levels in nicotine-treated cells. GSH levels in cells exposed to smokeless tobacco extract containing 4 and 0.8 mg nicotine remained significantly lower than the control with the addition of SOD and CAT. However, co-addition of NAC with smokeless tobacco extract preparations returned the GSH levels to the control level. Lactate dehydrogenase (LDH) activities were measured in the media to establish the membrane damage following exposure to smokeless tobacco extract and nicotine. Treatment of cells with 4 mg nicotine caused a significant increase in LDH activity, which was returned to control level in the presence of the antioxidant enzymes and NAC. Smokeless tobacco extract did not change the LDH activity. http://link.springer-ny. com/link/service/journals/00244/bibs/37n4p434.html</++ +HEA

3,4-Methylenedioxyamphetamine↗