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Biomedical subjects

D W Armstrong

Publications and source records attributed to D W Armstrong.

At least 91 records · Page 5Linked to original sources
PubMed1991

Determination of the enantiomeric purity of scopolamine isolated from plant extract using achiral/chiral coupled column chromatography.

The optical purity of scopolamine derived from Datura sanguinea was determined using coupled column chromatography. A C18 column was used to separate scopolamine from the additional alkaloids and other biological material present in the vegetal extract. The C18 column was coupled through a six-port switching valve to two beta-cyclodextrin columns in series which were used to resolve the scopolamine enantiomers. A single acetylated beta-cyclodextrin column gives equivalent results to the native cyclodextrin columns because of slightly higher enantioselectivity for scopolamine. A multistep extraction procedure is used to isolate scopolamine from the vegetal material. 4-6% of the scopolamine in the final extract was found to be the d enantiomer. Sample extracts as well as commercial scopolamine hydrobromide were treated under various conditions commonly encountered during typical commercial extraction procedures and analyzed in order to determine if the d enantiomer was present in the original material or if it was produced during the extraction process and, if so, determine which step and conditions contribute to racemization. Both the salt and the extract were found to be susceptible to racemization under basic conditions (greater than or equal to pH 9) although the extract appeared to be more susceptible than the salt. Tropic acid formed from the hydrolysis of scopolamine seemed to be completely racemized even though the remaining scopolamine was only partially racemized. Within experimental error, no d enantiomer was found in the original fresh plant material.

Acetylation↗
PubMed1991

[The pharmacokinetics of antilipemic agents. 8. Unequivocal characterization of ciprofibrate-O-beta-d-glucuronide].

After an oral single dose Ciprofibrate (1) is eliminated mainly (greater than 90%) as its glucuronide renally and to a small amount on the biliary route. This conjugate could be extracted out of the urine of volunteers. By methylation of the carboxy group and acetylation of the three hydroxy groups of the glucuronic acid the hydrophobic methyl-(2,3,4-tri-O-acetyl-beta-D-glucopyrano)-uronate was formed. This derivative could be identified unequivocally by HPLC using the reference substance which can be obtained easily. Due to the chirality of 1 its glucuronide and the corresponding hydrophobe derivative (melting range 67-78 degrees C) are a mixture of diastereomeres. The latter could be separated analytically into the diastereomeres using a cyclobond I-column.

Chromatography, High Pressure Liquid↗
PubMed1990

(S)-2-hydroxypropyl-beta-cyclodextrin, a new chiral stationary phase for reversed-phase liquid chromatography.

(S)-2- and (R,S)-2-hydroxypropyl-beta-cyclodextrin have been bonded to silica gel and evaluated as stationary phases for reversed-phase liquid chromatography. Stationary phases also were prepared on two silicas having different pore sizes and surface areas. Dissimilarities were observed in enantiomeric selectivities between these columns and also between these and the native beta-cyclodextrin columns. With the exception of compounds 5 and 10, all other racemates reported here which have been successfully resolved on the new phases are enantiomers which have not been previously reported as separated on the beta-cyclodextrin stationary phase. In some cases, there were also differences in enantioselectivities observed between the (S)- and the (R,S)-hydroxypropyl-beta-cyclodextrin phases on the same silica. The results are discussed in terms of the retention mechanism and compared to results reported earlier for beta-cyclodextrin columns.

Chemical Phenomena↗
PubMed1990

Polar-liquid, derivatized cyclodextrin stationary phases for the capillary gas chromatography separation of enantiomers.

A new class of hydrophilic, relatively polar liquid, cyclodextrin (CD) derivatives have been used as highly selective chiral stationary phases (CSPs) for capillary gas chromatography (GC). Several possible requirements for liquidity in CD derivatives are discussed. O-(S)-2-Hydroxypropyl derivatives of alpha-, beta-, and gamma-cyclodextrins were synthesized, exclusively characterized, permethylated, and evaluated for enantioselectivity. Seventy pairs of enantiomers were resolved. They represent a wide variety of structural types and classes of compounds including chiral alkyl amines, amino alcohols, epoxides, pyrans, furans, sugars, diols, esters, ketones, bicyclic compounds, alcohols, and so on. Many of these compounds were not aromatic and cannot be resolved on any known liquid chromatographic CSP. Often, these enantiomers had far less functionality than required for LC separation. General properties of these CSPs as well as possible insights into the separation mechanism are discussed.

Chromatography, Gas↗
PubMed1990

Separation of carotenes on cyclodextrin-bonded phases.

The separation of carotenoids and retinoids on a beta-cyclodextrin-bonded stationary phase with conventional mobile phases is reported. Compounds studied include beta-carotene (all-trans), 15,15'-cis-beta-carotene, 7,8,7',8'-dihydro-beta-carotene, alpha-carotene, lycopene, lutein, zeaxanthin, retinal, retinol, retinol palmitate and retinol acetate. The best resolution of carotenes was obtained with low concentrations (less than or equal to 1%) of polar solvents (e.g., 2-propanol or ethyl acetate) in hexane or cyclohexane. Xanthophylls required much higher concentrations of polar solvents. The best solvent for the resolution of lutein and zeaxanthin was found to be dichloromethane. The resolution of cis/trans-isomers and the tentative identification of other isomers present in newly synthesized carotenoid standards is also reported. All-trans-isomers were found to be eluted before cis-isomers.

Carotenoids↗
PubMed1990

Cyclodextrin chiral stationary phases for liquid chromatographic separations of drug stereoisomers.

Many active drugs are racemic mixtures. Because the two enantiomers of a racemate often cause different pharmacological responses, the use of optically pure isomers is desirable and may be soon required. Cyclodextrin-bonded silica gel can be used as chiral stationary phase (CSP) in liquid chromatography. The enantiomers of 25 different racemic drugs were separated on such CSPs in the reversed-phase mode. The principal features of the cyclodextrin chiral recognition mechanism are recalled and some information on future trends for cyclodextrin CSPs is provided.

Chromatography, Liquid↗
PubMed1989

Evaluation of the liquid chromatographic separation of monosaccharides, disaccharides, trisaccharides, tetrasaccharides, deoxysaccharides and sugar alcohols with stable cyclodextrin bonded phase columns.

Both alpha- and beta-cyclodextrin (CD) bonded phase columns were evaluated for their ability to separate carbohydrates and related molecules. Chromatographic data on approximately 50 solutes are reported. Mobile phases consisting of acetonitrile-water or acetone-water produce the best separations. Separations could be run in isocratic or gradient modes. The alpha-CD column produced slightly more efficient separations than the beta-CD column. Both cyclodextrin columns seemed to be more efficient and selective than alkylamine and ion-exchange columns. The stability and reproducibility of the CD columns were excellent and showed little deterioration after several thousand injections. The retention of saccharides on CD bonded phases seems to be related to the number of available hydroxy groups per solute and to the size of the solute. Analysis times and detection sensitivity are discussed.

Chromatography, Liquid↗
PubMed1989

Liquid chromatographic separation of anomeric forms of saccharides with cyclodextrin bonded phases.

A brief review of sugar stereochemistry is given. The separation of 34 different pairs of anomers was accomplished on both alpha- and beta-cyclodextrin columns. Five different mobile phases were evaluated. The separation of anomers could be enhanced or suppressed by altering the mobile-phase composition, column temperature, flow rate, and so on. The separation of anomers that mutarotate is somewhat more difficult than those that do not. Prior knowledge as to the rate of mutarotation is useful so that the chromatographic conditions can be arranged to minimize any deleterious effects on the separation.

Carbohydrates↗
PubMed1989

Optical enrichment of dansyl-rac-amino acids by formation of crystalline inclusion complexes with cyclodextrins.

Optical enrichment from racemic dansyl-leucine, dansyl-norleucine, and dansyl-phenylalanine with both beta- and gamma-cyclodextrins in water is reported. Initial crystallization yielded the dansyl-L-Leucine isomer complexed in excess with beta-cyclodextrin with an optical purity of 62-78% depending on experimental conditions. The optical purities obtained for L-norleucine and L-phenylalanine were 71 and 64%, respectively. The optical purity can be increased with continued recrystallization. The dansyl-D-leucine isomer was obtained in the mother liquor with an optical purity of 54-93% depending on experimental conditions. The optical purities obtained for D-norleucine and D-phenylalanine were 72 and 58%. The optical purity of the isomer depended on the molar ratio of host:guest and the pH value of the solution. Optimum enrichment of both enantiomers was achieved with host:guest ratios of 2:1 and 3:1. Although maximum crystalline yield of the dansyl-leucine/CD inclusion complex was obtained at a pH of 3.5, optical purity of both enantiomers was less than that obtained at other pHs. The influence of the molar ratio of host:guest and the pH value of the solution are discussed. This method is suitable for large-scale enantiomeric separations.

Amino Acids↗
PubMed1988

Use of hydroxypropyl- and hydroxyethyl-derivatized beta-cyclodextrins for the thin-layer chromatographic separation of enantiomers and diastereomers.

Partially substituted hydroxypropyl-beta-cyclodextrin and hydroxyethyl-beta-cyclodextrin proved to be effective chiral mobile phase additives (CMAs) for the thin-layer chromatographic (TLC) resolution of racemic benzyl-2-oxazolidinone, 5-(4-methyl-phenyl)-5-phenylhydantoin, mephenytoin and several dansyl and beta-naphthylamide amino acids. Several diastereomeric compounds including steroid epimers and alkaloids were separated as well. The derivatized beta-cyclodextrins tended to be much more soluble in water and hydro-organic solvents than native beta-cyclodextrin. Their chromatographic selectivity also was somewhat different. The use of CMAs in TLC is a potentially useful and powerful method that has not been considered adequately. The relative lack of chiral stationary phases available in planar format makes the use of CMAs particularly attractive.

2-Hydroxypropyl-beta-cyclodextrin↗
PubMed1988

Planar chromatographic separation of enantiomers and diastereomers with cyclodextrin mobile phase additives.

A variety of racemic compounds were resolved using reversed-phase thin-layer chromatography (TLC) with mobile phases containing highly concentration solutions of beta-cyclodextrin (beta-CD). These include the drugs labetalol and mephenytoin, metallocenes, crown ethers, methyl-p-toluenesulfinate, nornicotine derivaties and several dansyl and beta-naphthylamide substituted amino acids. It was possible to resolve some racemates that could not be separated on beta-CD bonded phase liquid chromatography (LC) columns with this technique. Likewise there were some compounds that could be resolved with the LC approach that failed to separate with the present TLC method. In cases of racemates that could be resolved by either approach, it was found that the retention order was exactly opposite for the two methods. Enantiomeric resolution is highly dependent on mobile phase composition. In particular, the type and amount of organic modifier as well as the concentration of beta-CD affect the observed resolution. Possible reasons for the chromatographic behavior are discussed. Several diastereoisomeric compounds were separated as well, including steroid epimers and pharmaceutical compounds.

Amino Acids↗