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S. L. Abidi

Publications and source records attributed to S. L. Abidi.

At least 19 recordsLinked to original sources
USGS2009

Optical resolution of rotenoids

Optical resolution of selected rotenoids containing 1-3 asymmetric centers in dihydrobenzopyranofuroben-zopyranone and dihydrobisbenzopyranopyranone series has been achieved on two chiral high-performance liquid chromatographic (hplc) stationary phases. In most cases, the absolute stereochemistry at the cis -B/C ring junction of the rotenoidal antipodes can be related to their elution order. Generally, the 6aα,12aα-enantiomers were more strongly retained by the chiral substrate than their corresponding optical antipodes. The elution-configuration relationship provides potential utility for predicting the absolute configuration of related rotenoidal compounds. Chiral phase hplc on amino-acid-bonded-silica yielded results explicable in terms of Pirkle's bonding schemes for chiral recognition. Resolution data for 12a-hydroxy-, 12a-methoxy-, and 12-hydroxyiminorotenoids further corroborate the mechanistic rationale, and demonstrate that nonpolar π-π interactions appeared to be important for enantiomeric separation on helic poly-triphenylmethylacryl-ate-silica (CPOT). In the latter system, steric effects and conformational factors in association with the modification of E-ring structures might play significant roles in the chiral separation process in view of the reversal to the elution order observed for all methoxylated rotenoids and elliptone derivatives including the parent deguelin. The unique separability (α = 1.44) of 12a-hydroxyelliptone on CPOT was suggestive of structural effects of the 5-side chain on the resolution of the rotenoids having a five-membered-E-ring. The results obtained with two different types of chiral phases are complementary and useful for optical resolution of a wide variety of natural and synthetic rotenoidal compounds.

Journal of Heterocyclic Chemistry↗
USGS2009

13C NMR spectral characterization of epimeric rotenone and some related tetrahydrobenzopyranofurobenzopyranones

The 13 C nuclear magnetic resonance (nmr) spectra of epimers of rotenone and four 12a-hydroxy-analogues were examined to determine the stereochemical effect of the B/C ring fusion involving the 6a- and 12a-carbon centers. Chemical shift differences between the epimeric carbon resonances of cis- and trans-6a,12a-compounds were notably larger than those of diastereoisomers derived from the same B/C ring junction stereochemistry. Results of the spectral analysis have been useful for the quantification of mixtures of epimers and for the measurement of rates of epimerization and oxygenation.

Journal of Heterocyclic Chemistry↗
USGS2006

Synthesis of carbon-14 and deuterium labeled N-nitroso-2 (3',7'-dimethyl-2',6'-octadienyl) aminoethanols

Methods of preparation of carbon-14 and deuterium labeled N-nitroso-2(3,7-dimethyl-2,6-octadienyl) aminoethanols are described. The primary synthetic method involved alkylation of ethanolamine or ethylglycine with suitable chlorides and subsequent mild nitrosation. Isomeric 14 C-nitrosamines were also prepared by selective -cleavage of the di-substituted ethanolamine with nitrous acid.

Journal of Labelled compounds and Radiopharmaceuti↗
USGS2005

1H and 13C resonance designation of antimycin A1 by two-dimensional NMR spectroscopy

Complete 1 H and 13 C resonance assignments of antimycin A 1 were accomplished by two-dimensional NMR techniques, viz. 1 H homonuclear COSY correlation, heteronuclear 13 C- 1 H chemical shift correlation and long-range heteronuclear 13 C- 1 H COLOC correlation. Antimycin A 1 was found to consist of two isomeric components in a 2:1 ratio based on NMR spectroscopic evidence. The structure of the major component was newly assigned as the 8-isopentanoic acid ester. The spectra of the minor component were consistent with the known structure of antimycin A 1 .

Magnetic Resonance in Chemistry↗
USGS2002

Direct conversion of terpenylalkanolamines to ethylidyne N -nitroso compounds

A series of mono- and diterpenylalkanolamines bearing isopropylidene functionality on the terpene group was reacted with sodium nitrite in aqueous acetic acid to yield ethylidyne N -nitroso analogues. The key feature of this direct conversion involved initial N-nitrosation followed by apparent elimination of a "CH 4 " unit (not necessarily methane) from the isopropylidene double bond. The product distribution data for ethylidyne nitrosamines derived from tertiary terpenyl alkanolamines reflect the conformational outcome of the nitrosative dealkylation process. For β , γ -unsaturated allylic diterpenylethanolamines, electronic effects appeared to be important for controlling the product distribution of ethylidyne nitrosamines in light of the highly selective α -cleavage observed in the nitrosation reactions.

Journal of Organic Chemistry↗
USGS1990

Liquid-chromatography thermospray mass-spectrometric study of n-acylamino dilactones and 4-butyrolactones derived from Antimycin-A

Reversed-phase high-performance liquid chromatography—thermospray mass spectrometric (HPLC—MS) characteristics of four sets of lactonic complexes (one 4-butyrolactones and three dilactone complexes) derived from antimycin A were investigated. Three types of 8-hydroxy analogues were also included in the study. Pairs of a–b structures isomeric at the 8-acyloxy ester side-chains were best separated with a high-efficiency octadecylsilica column prior to analysis by HPLC—MS. Mass spectra of the a–b pairs each with identical molecular weights exhibited virtually indistinguishable fragmentation patterns, although their relative intensities were not superimposable. In some cases, HPLC—MS of the title compounds yielded mass chromatograms showing the minor components more easily recognizable than the HPLC—UV counter parts because of the apparent higher ionization efficiency of the minor isomers and increased resolution of subcomponents in the MS system. Under the mobile phase conditions employed, analyte ionization occurred with variable degrees of gas phase ammonolysis depending upon the ammonia concentration of the buffer. Potential applicability of the on-line HPLC—MS technique for the characterization of components in mixtures of antimycin analogues and isomers is demonstrated.

Journal of Chromatography↗
USGS1989

Reversed-phase high-performance liquid chromatography of unsubstituted aminobenzoic acids

High-performance liquid chromatographic (HPLC) characteristics of three position isomers of aminobenzoic acids (potential metabolites of important anesthetic drugs), were delineated with respect to their interactions with various mobile phases and stationary phases. HPLC with five hydrocarbonaceous phase, I?-cyclodextrin silica (CDS), macrophase MP-1 polymer (MP), macroporous polystyrene/divinylbenzene (MPD), octadecylsilica (ODS), and propylphenylsilica (PPS), yielded results explicable in terms of substituent effects derived from the bifunctional amino- and carboxy groups. For cases where mobile phases contained sulfonates or quaternary ammonium salts both having longer chain alkyls, retention of analytes on all but CDS appeared to proceed predominantly via an ion-pairing mechanism. The extent of the corresponding counter-ion effects decreased in the order: MPD > ODS > PPS > MP, while the analyte retention order paralleled thier pH 2 values. On the other hand, an inverse relationship between the magnitude of capacity factors (k') and pK 1 values of the title compounds was observed in experiments that produced retention data incompatible with ion-pair interaction rationales. The unique HPLC results obtained with the CDS phase are compared with those obtained with other phases.

Journal of Liquid Chromatography↗
USGS1988

High-performance liquid-chromatographic separation of subcomponents of antimycin-A

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, A 1a , A 1b , A 2a , A 2b , A 3a , A 3b , A 4a , and A 4b . Although a base-line resolution of the known four major antimycins A 1 , A 2 , A 3 , and A 4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

Journal of Chromatography↗
USGS1987

Chiral-phase high-performance liquid chromatography of rotenoid racemates

The high-performance liquid chromatograhic (HPLC) behavior of parent rotenoids (type I) and the hydroxyl-analogues (type II) on three different chiral stationary phases (CSPs) was studied. Separations of optical isomers were achieved in various degrees depending largely upon the rotenoidal structures and the CSP types employed. Enantiomers of all but elliptone compounds were separable on β-cyclodextrin-bonded silica (CDS). Without exception, the 12a-hydroxyrotenoid antipodes were resolved on Pirkle's phenylglycine-bonded silica (PGS) despite unsuccessful attenmpts to resolve the type I rotenoidal racemates. Conversely, optical resolution of the latter rotenoids was accomplished by using a helical polytriphenylmethylacrylate-coated silica (TPS) column and the observed separation factors (α values) ranged from 1.14 to 1.90. The results from HPLC of type II rotenoids on TPS (α = 1.00–1.63) suggested that variations in E-ring structures had profound influence on the resolution outcome. Conjugated double bonds on the E-ring and the desisopropylation of the five-membered E-ring ot type II rotenoids appeared to be important structural features for chiral recognition involving the TPS substrate. In both reversed-phase (CDS) and normal-pahse (PGS and TPS) HPLC modes, the less polar enantiomers were the 6aβ,12aβ-rotenoids as observed in most cases, though this relationship was reversed in the cases of deguelin and hydroxyelliptone probably due to conformational effects of rotenoidal ring systems.

Journal of Chromatography↗
USGS1986

Liquid chromatography of hydrocarbonaeous quaternary amines on cyclodextrin bonded silica

Mixtures of n -alkylbenzyldimethylammonium chloride ( ABDAC ) were resolved into homologous components by high-performance liquid chromatography ( HPLC ) with a cyclodextrin-bonded silica stationary phase. With a few exceptions, results from this study are similar to those obtained from traditional reversed-phase HPLC . It was found that the presence of electrolytes in aqueous mobile phases is not a critical factor in determining the success of HPLC separation. Under normal HPLC conditions, a mobile phase consisting of either methanol—water (50:50) or acetonitrile—water (30:70) was employed for obtaining adequate resolution of the quaternary ammonium mixtures. Although the percent organic modifier—water profiles were similar to those in previous studies with these compounds, resolution ( R ) and selectivity (α) parameters were found to be quite susceptible to changes in the mobile phase solvent composition. The retention behavior of the cationic analytes in the homologous series is consistent with the hydrophobic-interaction concept proposed for the retention mechanism via dominant inclusion complex formation. Several electolytes were chosen for a study of the counter ion effect on the chromatographic characteristics of ABDAC components. Among the electrolytes examined, the perchlorate ion was found most likely to act as an ion-pairing counter ion for ammonium cations in the HPLC system studied. A correlation study established linear relationships between the chain length of ABDAC and the logarithmic capacity factor ( k ′). The analytical utility of the HPLC method was demonstrated by the analysis of various unknown mixtures.

Journal of Chromatography↗
USGS1986

Potential for nitrosamine formation in seven fishery chemicals

In recent years, nitrosamines have been reported as possible causes of cancer, mutations, or birth defects. Inasmuch as these compounds may be formed by the interaction of certain amines with nitrite in the aquatic environment, we evaluated seven fishery chemicals for their potential to form nitrosamines: the experimental fish toxicant digeranylethanolamine (GD‐174); the four therapeutants Terramycin, erythromycin, Hyamine 1622, and Hyamine 3500; and the two tracer dyes rhodamine B and rhodamine WT. The results indicate that the controlled use of the seven fishery chemicals in natural environments will not lead to the formation of nitrosamines.

Progressive Fish-Culturist↗
USGS1985

Retention behavior of long chain quaternary ammonium homologues and related nitroso-alkymethylamines

Several chromatographic methods have been utilized to study the retentionbehavior of a homologous series of n -alkylbenzyldimethylammonium chlorides (ABDAC) and the corresponding nitroso- n -alkylmethylamines (NAMA). Linear correlation of the logarithmic capacity factor ( k ') with the number of carbons in the alkyl chain provides useful information on both gas chromatographic (GC) and high-performance liquid chromatographich (HPLC) retention parameters of unknown components. Under all conditions empolyed, GC methodology has proved effective in achieving complete resolution of the homologous mixture of NMA despite its obvious inadequacy in the separation of E-Z configurational isomers. Conversely, normal-phase HPLC on silica demonstrates that the selectivity (a) value for an E-Z pair is much higher than that for an adjacent homologous pair. In the reversed-phase HPLC study, three different silica-based column systems were examined under various mobile phase conditions. The extent of variation in k ' was found to be a function of the organic modifier, counter-ion concentration, eluent pH, nature of counter-ion, and the polarity and type of stationary phase. The k '—[NaClO 4 ] profiles showed similar trends between the ABDAC and the NAMA series, supporting the dipolar electronic structures of the latter compounds. Mobile phase and stationary phase effects on component separation are described. The methodology presented establishes the utility of HPLC separation techniques as versatile analytical tools for practical application.

Journal of Chromatography↗
USGS1984

Chromatographic investigations of the configurational and geometrical isomerism of allylic N-terpenyl-N-hydroxyethyl-nitrosamines

A preparative adsorption column chromatographic method is reported for the separation of cis and trans geometrical isomers of two types of N-nitrosamines derived from allylic terpenyl ethanolamines (experimental fish toxicants). Column eluates were monitored by gas chromatography in which a Carbowax 20M stationary phase was used. Further separation of E and Z configurational isomers was achieved by reversed-phase and normal-phase high-performance liquid chromatography. In the reversed-phase high-performance liquid chromatography system (acetonitrilewater), the 6′,7′-acetylenic nitrosamines (NMOA) were efficiently resolved by using an argentous (AgNO 3 ) mobile phase, whereas the presence of sodium alkanesulfonate in the aqueous acetonitrile mobile phase favored the base-line resolution of the 6′,7′-olefinic nitrosamines (NDOA). For normal-phase separation on a silica column, addition of tetrahydrofuran to the mobile phase (methylene chloride-2-propanol) resulted in a varying degree of improvement in peak resolution ( R ) and column selectivity (α). Effects of temperature on the chromatographic behavior of the nitrosamine components are described. The high-performance liquid chromatographic separation method has proved to be applicable for the trace analysis of the title nitrosamines in organic tissues by way of thermal energy analysis.

Journal of Chromatography↗
USGS1983

High-performance liquid chromatography of quinoidal imminium compounds derived from triphenylmethanes

A series of eleven p -aminotriphenylmethane dyes have been studied by high-performance liquid chromatography (HPLC). The combined use of HPLC and spectrophotometry permits specific detection of these compounds in the visible range around 600 nm. As the high affinity of the imminium cations for the active sites of the hydrocarbonaceous stationary phase has presented difficulties for reversed-phase HPLC with pure solvents, organic electrolytes were added to the mobile phase to facilitate the elution of the components with improved selectivity, sensitivity (minimum detection limit, 0.1 μg/ml), and peak symmetry. The effects of chromatographic variables on the component retentivity were investigated. Retention times of the dye analytes decreased with increasing concentration of the added ionic reagent and with decreasing number of the hydrophobic alkyl substituents on the nitrogen atom. The influence of pH on the retention parameters appears to parallel that observed previously for cationic quaternary ammonium compounds. Among the acidic reagents employed, naphthalenesulfonic acid yielded the most satisfactory results. The use of binary electrolyte systems invariably improved the chromatographic behavior of the imminium solutes analyzed. Results obtained with two different octadecylsilica columns have been compared.

Journal of Chromatography↗
USGS1982

High-performance liquid chromatographic resolution and quantification of a dilacton antibiotic mixture (antimycin A)

High-performance liquid chromatographic (HPLC) conditions are presented for the separation and quantitative determination of a homologous antibiotic complex (antimycin A). Combined HPLC and chemical ionization mass spectrometry proved to be exceptionally useful for the structural identification of chromatographic components. Using electrochemical, fluorescence, and ultraviolet detectors, the minimum detectable amounts of the antibiotics were found to be in the ranges 0.10–1.12, 0.31–1.69, and 4.10–28.2 ng, respectively. Advantages of the preparation of Dns derivatives for use in fluorescence detection are discussed. Application of the HPLC technique to the analysis of the antibiotic mixture in organic tissues is demonstrated.

Journal of Chromatography↗