• Bulletin of the Korean Chemical Society
• /
• v.16 no.4
• /
• pp.305-309
• /
• 1995

The enantiomeric separation of several amino acid derivatives by reversed-phase liquid chromatography using two (R)-and (S)-naphthylethylcarbamate-β-cyclodextrin(NEC-β-CD) bonded stationary phases was studied to illustrate the chiral recognition model of the enantiomeric separation. The retention and enantioselectivity of the chiral separations with (R)-and (S)-NEC-β-CD bonded phases were compared with similar separations with the native β-CD stationary phases. Especially, the enantioselectivity and elution orders between the derivatized amino acid enantiomers are carefully examined. These results can be illustrated by the chiral recognition models involving inclusion complexation, π-π interaction, and/or hydrophobic interaction. Inclusion complexation and hydrophobic interaction of the naphthyl group of the NEC moiety seem to be major chiral recognition components in the enantiomeric separation of 2,4-dinitrophenyl amino acids and dabsyl amino acids on (R)-and (S)-NEC-β-CD columns. For dansyl amino acids, only the inclusion complexation is the dominant factor. Three different chiral recognition models containing π-π interaction, inclusion complexation and hydrogen bonding were proposed for the separation of the 3,5-dinitrobenzoyl amino acid enantiomers, depending on the size and shape of amino acids.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.6
• /
• pp.1551-1554
• /
• 2010

Two diastereomeric chiral stationary phases (CSPs) were applied to the liquid chromatographic resolution of various racemic ${\alpha}$-amino methyl esters, ${\alpha}$-amino N,N-diethylamides and ${\alpha}$-amino N-propylamides. The CSP incorporating (R)-3,3'-diphenyl-1,1'-binaphtyl and (R,R)-tartaric acid unit as chiral barriers did not show any chiral recognition. In contrast, the CSP incorporating (R)-3,3'-diphenyl-1,1'-binaphtyl and (S,S)-tartaric acid unit as chiral barriers was found to show excellent chiral recognition especially for the two enantiomers of ${\alpha}$-amino N-propylamides. Some of ${\alpha}$-amino methyl esters and ${\alpha}$-amino N,N-diethylamides were also resolved on the CSP incorporating (R)-3,3'-diphenyl-1,1'-binaphtyl and (S,S)-tartaric acid unit. From these results it was concluded that the two chiral units composing the diastereomeric CSPs can show "matched" or "mismatched" effect on the chiral recognition according to their absolute stereochemistry.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.6
• /
• pp.491-495
• /
• 1989

Resolution of enantiomers of DNS-amino acids has been achieved by a reversed phase liquid chromatography with an addition of a copper(Ⅱ) complex of N-benzyl-L-hydroxyproline to the mobile phase. N-Benzyl-L-hydroxyproline was prepared and used as a chiral ligand of copper(Ⅱ) chelate for the optical resolution. The pH and the concentration of copper(Ⅱ) chelate, organic solvent, and buffer agent in the mobile phase all affect the optical resolutions of dansyl amino acids. The elution orders between D and L-DNS-amino acids were different depending on the structure of the side chain of the amino acids. The retention mechanism for the chiral separation of the dansyl amino acids can be illustrated by the equilibrium of ligand exchange and by hydrophobic interaction with $C_{18}$ stationary phase. The chiral separation can be illustrated with cis and trans effect of the ligand exchange reaction.

• Archives of Pharmacal Research
• /
• v.27 no.1
• /
• pp.35-39
• /
• 2004

The method for the chiral analysis of (-)-yatein was developed and the distribution of this component in the plants of three genera like Juniperus, Thuja and Chamaecyparis belonging to Cupressaceae family was examined. The chiral analysis of (-)-yatein from the plants was carried out by high performance liquid chromatography on (R,R)-Whelk-O1 column using 81 v/v% methanol as mobile phase. The yatein content in the leaves of Juniperus was the highest in compare with that of the other two genera, providing the possibility of the chemical discrimination of the plants in Juniperus from the other plants in the Cupressaceae family. In general, the yatein content in the leaves was much higher than that in the twigs. This method could be applied for the quality control of (-)-yatein in the plants belonging to Cupressaceae family.

• Biotechnology and Bioprocess Engineering:BBE
• /
• v.9 no.4
• /
• pp.285-291
• /
• 2004

A simulated moving bed (SMB) chromatography system is a powerful tool for preparative scale separation, which can be applied to the separation of chiral compound. We have de-signed our own lab-scale SMB chromatography using 5 HPLC pumps, 6 stainless steel columns and 4 multi-position valves, to separate a racemic mixture of ketoprofen in to its enantiomers. Our design has the characteristics of the low cost for assembly for the SMB chromatography and easy repair of the unit, which differs from the designs suggested by other investigators. It is possible for the flow path through each column to be independently changed by computer control, using 4 multi-position rotary valves and 5 HPLC solvent delivery pumps. In order to prove the operability of our SMB system, attempts were made to separate the (S)-ketoprofen enantiomer from a ketoprofen racemic mixture. The operating parameters of the SMB chromatography were calculated for ketoprofen separation from a batch chromatography experiment as well as by the triangle theory. With a feed concentration of 1 mg/mL, (S)-ketoprofen was obtained with a purity of 96% under the calculated operating conditions.

• Proceedings of the PSK Conference
• /
• 2002.10a
• /
• pp.163-164
• /
• 2002

In the past two decades, separations of enantiomers (optical isomers) by high-performance liquid chromatography (HPLC) have remarkably advanced ［1］. Among many commercially available chiral stationary phases (CSPs) for HPLC, polysaccharide-based CSPs are the most popular ones, which can cover the resolution of a wide range of the chiral compounds ［2, 3, 4］. Here, I will explain mainly the HPLC separation of enantiomers using these CSPs. (omitted)

• Bulletin of the Korean Chemical Society
• /
• v.25 no.11
• /
• pp.1707-1710
• /
• 2004

• Proceedings of the PSK Conference
• /
• 2003.04a
• /
• pp.275.2-276
• /
• 2003

Several ${\beta}$-agonists were investigated for the possible separation of the enantiomers by reversed-phase high-performance liquid chromatography after derivatization with a new chiral derivatization agent, GATC. The derivatization proceeded quantitatively within 1 h at room temperature. The corresponding diastereomers were well resolved an ODS column with acetonitrile-acetate buffers a mobile phase and monitored at UV 254nm. (omitted)

• Bulletin of the Korean Chemical Society
• /
• v.11 no.5
• /
• pp.411-415
• /
• 1990

The dabsylation of amino acids has been applied to resolve their optical isomers with the use of chiral mobile phase in high performance liquid chromatography. The dabsyl amino acids were successfully separated on reversed phase column($C_{18}$) by adding a chiral L-benzylproline-Cu(II) chelate to the mobile phase. The separation selectivity of the dabsyl amino acid enantiomers was not less than that of dansyl amino acids. The retention order of the dabsyl amino acid enantiomers was as those of the dansyl amino acid enantiomers except dabsyl threonine. The optical selectivity of the dabsyl amino acids increase with pH of the mobile phase and concentration of the chelate, but slightly decreases with concentration of buffer and organic solvent composition. However serine, methionine, valine, and leucine showed a slight decrease in the optical selectivity with increase in pH. The retention times of the dabsyl amino acids decreases with increasing pH and acetonitrile concentration but increases with the concentration of the chiral chelate added. The mechanism of the optical resolution is based on a stereospecific interaction including a intramolecular hydrophobic effect and SN-2 reactivity of the ligand exchange chromatography.It is advantageous to detect absorption at 436 nm, which is less interferent them the other detection systems. The derivatized dabsyl amino acids are stable for a month.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.4
• /
• pp.524-528
• /
• 2006

Three different style capillary columns, a packed capillary with temporary quartz wool frit, a packed capillary with immobilized frit, and an immobilized packed-capillary, were easily prepared with a commercially available (S)-N-(3,5-dinitro-benzoyl)leucine-N-phenyl-N-alkylamide derived chiral stationary phase. Liquid chromatographic chiral separations of some racemic amino acid derivatives on these columns were performed and the results were compared to each other. The packed capillary with immobilized frit showed some merits in chiral chromatography.