• Bulletin of the Korean Chemical Society
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• 제22권4호
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• pp.409-412
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• 2001

Poly(p-tert-butyltrimethoxymonopropyloxycalix[4]arene-methylsiloxane) (TBCX-MS) has been prepared and used as a stationary phase in isothermal capillary gas chromatographic separation of some positional isomers. Retention factors (k) and separatio n factors $(\alpha)$ for the isomers were measured and compared with those on poly(p-tert-butyl-dimethoxydipropyloxycalix[4]arene-tetramethyldisiloxane) (TBCX-TMDS), poly(dimethoxydipropyloxycalix[4]arenetetramethyl-disiloxane) (CX-TMDS). Most of the isomers investigated are well resolved on TBCX-MS. Retention of all the compounds decreases on the three phases in the order, TBCX-TMDS ${\geq}$ TBCX-MS > CX-TMDS. Similar retention values on TBCX-TMDS and TBCX-MS seem to indicate that retention property of the two phases is not significantly affected by the spatial position of the calixarene moiety.

• Bulletin of the Korean Chemical Society
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• 제27권8호
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• pp.1222-1224
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• 2006

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.999-1004
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• 2007

Spherical porous silica supports modified with titanium or zirconium alkoxides were prepared, and allyl groups were chemically attached to the titanized or zirconized silica supports, and the product was cross-polymerized with a double bond containing cellulose derivative to yield new CSPs (chiral stationary phases). Magic angle spinning 13C solid state NMR and elemental analysis were used to characterize the CSPs. The performances of the chiral stationary phases were examined in comparison with a conventional chiral stationary phase. Spherical porous silica particles modified with 3,5-dimethylphenylcarbamate of cellulose were prepared and used as the conventional chiral stationary phase. Chromatographic data were collected for a few pairs of enantionmers in heptane/2-propanol mixed solvents of various compositions with the three chiral columns and the results were comparatively studied. The separation performance of the chrial phase made of the titanized silica was better than the others, and the separation performance of the chiral phase of the zirconized silica was comparable to that of the conventional chiral phase. The superiority of titanized silica over bare or zirconized silica in chiral separation seemed to be owing to the better yield of crosslinking (monitored by increase of carbon load) for titanized silica than for the others.

• 약학회지
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• 제33권2호
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• pp.129-139
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• 1989

New diamide chiral stationary phases of four systematically substituted optically active N-(N-benzoyl-L-amino acid)-anilide synthesized from L-valine, L-leucine, L-isoleucine, and L-phenylalanine were described. The behaviors of these diamides as optically active stationary phases for the separation of N-trifluoroacetyl-D,L-amino acids were examined with respect to separation factors(${\alpha}$) and thermodynamic properties of interaction. The separation of twelve N-trifluoroacetyl-D,L-amino acid isopropyl esters were improved by the order of N-(N-benzoyl-L-leucyl)-anilide>N-(N-benzoyl-L-isoleucyl)-anilide>N-(N-benzoyl-L-valyl)-anilide>N-(N-benzoyl-L-phenylalanyl)-anilide. Eight amino acid derivatives with non-polar R-group and threonine, serine, aspartic acid, and glutamic acid enantiomers were separated on N-(N-benzoyl-L-leucyl)-anilide as chiral stationary phase with good separation factor between 1.07-1.25. The separation factors decreased with respect to increasing column temperature. Possible working temperature of diamide phase was between $130-190^{\circ}C$ for N-(N-benzoyl-L-phenylalanyl)-anilide and $130-180^{\circ}C$ for other three diamide phases. The differential Gibb's free energy (${\Delta}{\Delta}G$) of enantiomers was in the range of -100--180 cal/mol for ten amino acids and -40--60 cal/mol for alanine and aspartic acid.

• Archives of Pharmacal Research
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• 제12권1호
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• pp.58-61
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• 1989

Studies of selectivity of hydrogen bond formation in chiral solute-solvent systems have been performed by $^1H\;and\;^{13}C$ nuclear magnetic resonance techniques. These data are correlated with the results of gas chromatographic investigations of the same systems. Interactions between the optically active solvent(N-(N-benzoyl-L-amino acid)-anilide) and optically active solute (N-trifluoroacetyl -L-alanyl isopropyl ester) were examined. NMR evidence indicated that hydrogen bonding interaction occurred between two N-H portion and on peptidyl carbonyl portion in stationary phase and solute molecule on three points. The association constants of solvent-solute interaction were calculated and the structure of the diastereomeric association complex between N-(N-benzoyl-L-valyl)-anilide and N-TFA-L-alanyl isopropyl ester was proposed.

• Bulletin of the Korean Chemical Society
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• 제13권4호
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• pp.407-413
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• 1992

The chromatographic separation of the stereoisomers of the N-(3,5-dinitrobenzoyl) derivatives of fifteen dipeptide methyl esters and nine dipeptide alkyl esters was investigated on three different chiral stationary phases derived from N-acylated ${\alpha}-arylalkylamines$. Two of these CSPs contain second stereogenic centers. These secondary stereogenic centers of CSPs were proposed to provide secondary effects in terms of chiral recognition. From the elution orders of the four dipeptide stereoisomers and the separation factors of the enantiomeric pairs of the N-(3,5-dinitrobenzoyl) derivatives of the dipeptide alkyl esters having different alkoxy substituents, it was proposed that the intercalation of the alkoxy substituents of dipeptide derivatives between the connecting arm of CSPs may control the magnitude of chiral separations of dipeptide derivatives.

• Bulletin of the Korean Chemical Society
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• 제21권1호
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• pp.105-109
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• 2000

High-performance liquid chromatography is suitable for getting thermodynamic information about solute-solvent interactions. We used a squalane impregnated $C_{18}$ phase as a presumably bulk-like stationary phase to secure a simple partition mechanism for solute retention in reversed phase liquid chromatographic system. We measured retention data of some selected solutes (benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, phenol, benzylalcohol, phenethylalcohol, benzylacetone, acetophenone, benzonitrile, benzylcyanide) at 25, 30, 35, 40, 45, and 50 $^{\circ}C$ in 30/70, 40/60, 50/50, 60/40 and 70/30 (v/v%) acetonitrile/water eluents. The van't Hoff plots were nicely linear, thus we calculated dependable thermodynamic values such as enthalpies and entropies of solute transfer from the mobile phase to the stationary phase based on more than four retention measurements on different days (or weeks). We found that the cavity formation effect was the major factor in solute distribution between the mobile and stationary phases in the system studied here. Our data were com-pared with some relevant literature data.

• KSBB Journal
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• 제26권4호
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• pp.323-327
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• 2011

The convenient derivatization method of chiral amino alcohols as 9-anthraldimine Schiff base derivatives for chiral resolution was developed and the liquid chromatographic enantiomer separation of chiral amino alcohols as 9-anthraldimine derivatives was investigated on several coated and covalently bonded polysaccharide-derived chiral stationary phases (CSPs). In general, the performance of Chiralcel OD-H (or Chiralcel OD) (${\alpha}$ = 1.24-2.89), the coated CSP derived from cellulose derivative was superior to the other CSPs for resolution of 9-anthraldimine derivatives of several amino alcohols. The results of enantioseparation depending on the structure of 9-anthraldimine analytes like the steric bulky group and the polar moiety etc were discussed. The analytical method was applied to measure the enantiomeric purity of commercially available chiral amino alcohols. It is expected that the convenient analytical method will be very efficient for determination of enantiomeric purity of amino alcohols as 9-anthraldimine Schiff base derivatives with strong UV absorption.

• KSBB Journal
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• 제27권4호
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• pp.232-236
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• 2012

Comparative liquid chromatographic enantiomer separation of ${\alpha}$-amino acids, their esters and primary amino compounds was performed using two chiral stationary phases (CSPs) prepared by covalently bonding (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (18-C-6-TA) of the same chiral selector. In general, the separation factors and resolution factors for these analytes on CSP 1 were greater than on CSP 2, while these capacity factors on CSP 2 were quite greater than on CSP 1. Except for leucine methyl ester and phenylalanine methyl ester, the elution orders of all analytes including ${\alpha}$-amino ${\alpha}$-alkyl acids and phenylglycine alkyl esters on CSP 1 are identical to those on CSP 2. This study showed that different connecting structures for these two CSPs might influence their ability to resolve the analytes depending on their structures related to the chiral recognition mechanism.

• Bulletin of the Korean Chemical Society
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• 제31권6호
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• pp.1551-1554
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• 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.