• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.49-62
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• 1990

In order to synthesize N,N-di-(polyoxyethylene) perfluoroacyl amines and the surface active monoperfluoroacyl aza crown ethers, it is performed as follow. Six of N,N-di(polyoxyethylene) perfluoro acyl amines were synthesized from perfluoroalkanoic acids with ethanol followed by oxyethylation with triethylene glycol mono chloride or tetra ethylene glycol mono chloride and six of N-perfluor acyl monoaza crown ethers by cyclization of corresponding N,N-di(polyoxy ethylene} perfluoro acyl amines with p-toluene suflonic chloride-NaOH/dioxane, p-toluene sulfonyl chloride KOH/dioxane and benzene sulfonic chloride-KOH/dioxane systems.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.773-778
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• 1993

Poly(vinyl chloride)(PVC) membrane electrodes based on the lipophilic neutral carrier, dibenzo-18-crown-6(DB18C6) and benzo-15-crown-5 (B15C5) as the active sensors for Tl$^+$ ion have been prepared and tested in different content of the potassium tetrakis(4-chlorophenyl)borate (KTClPB) as lipophilic salt. Dioctyl adipate (DOA), 2-nitrophenyl phenyl ether (NPPE) and o-nitrophenyl actyl ether (NPOE) were used as plasticizing solvent mediators. Electrodes exhibited good linear responses of 40∼55 mV decade$^{-1}$ for Tl$^+$ ion within the concentration ranges 10$^{-1}$∼10$^{-5}$M TlNO$_3$. Selectivity coefficients of interfering ions (alkali metal, alkaline earth metal and some transition metal ions) for Tl$^+$-ISE were determined by separate solution method and were sufficiently small for most of them. These crown ether type ion-selective electrodes are suitable for use with aqueous solution at pH > 3.

• KSBB Journal
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• v.27 no.4
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• pp.199-206
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• 2012

Chiral crown ethers are synthetic macrocyclic polyethers that bind protonated chiral primary amines with high selectivity and affinity. They have been widely used to separate or distinguish the enantiomers of chiral compounds containing a primary amino moiety by high-performance liquid chromatography, capillary electrophoresis, and NMR spectroscopy. In this paper, two important chiral crown ethers including chiral binaphthyl unit and (18-crown-6)-2,3,11,12-tetracarboxylic acid as chiral selectors are focused. And several chiral resolution techniques and their applications in chirotechnology using these chiral crown ethers with related chiral recognition mechanism studies are reviewed. Especially, it was shown that the commercially available HPLC columns based on (18-crown-6)-2,3,11,12-tetracarboxylic acid have been developed and successfully applied for the resolution of various primary amino compounds including amino acids.

• KSBB Journal
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• v.27 no.4
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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.

• Journal of the Korean Society of Industry Convergence
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• v.6 no.1
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• pp.73-80
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• 2003

We report herein synthetic results obtained six new types of bis-benzocrown ethers containing imine group. Bis crown ethers1~3 are aminobenzo-15-crown-5-ether linked with terephthalaldehyde, isophthalaldehyde, phthaldehyde respectively by imine reaction. Bis crown ethers1~3 are different distances in each crown ether rings. Bis crown ether 4 has large cavity in crown ethers. Functionalized crown ether 5 is synthesized amonobenzo-15-crown-5-ether and terephthaladehyde same ratio at one to one. Bis crown ether 6 has photosensitive linkage between crown ethers. Bis crown ether 7 is prepared by amonobenzo-15-crown-5-ether and triethyl ortho formate. 4'-Nitrobenzo-crown ethers and 3',4'-dinitrobenzo-crown ethers were prepared by nitration of benzo crown ethers, obtained from the reaction of catechol and oligoethylene glycol ditosylate. Crown ethers containing aldehyde group were synthesized from the reaction of 3,4-dihydroxybenzaldehyde and corresponding ditosylate respectively. The synthesized crown ethers were characterized respectively by IR, NMR, GC-Mass.

• Journal of the Korean Society of Industry Convergence
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• v.6 no.2
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• pp.109-113
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• 2003

We report herein synthetic results obtained new types of crown ethers containing coumarin group. Crown ethers containing coumarin group 1~3 are hydroxymethyl-15-crown-5-ether linked with 4-hydroxy coumarin-4-acetic acid by esterification reaction. Crown ethers containing coumarin group 1~3 have different cavity in each crown ether rings. The 12-crown-4 ether with coumarin 1 has the smallest cavity size. The 15-crown-5 ether with coumarine 2 has the medium cavity size. The 18-crown-6 ether with coumarin 3 has the largest cavity size. Therefore each crown ether with coumarin group will recognize different ionic radius meta. Because of different hole size in crown ethers, these crown ethers seem to be had different selectivity in luminescent sensors. The crown ethers with coumarine 1~3 synthesized hydroxymethyl-15-crown-5-ether and 4-hydroxy coumarin-4-acetic acid same ratio at one to one. The synthesized crown ethers were characterized respectively by IR, NMR. GC-Mass.

• Journal of the Korean Chemical Society
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• v.40 no.2
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• pp.117-121
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• 1996

Two new crown ethers containing nitrogen and sulfur atoms adjacent to the crown rings were prepared. 4'-Benzothiazolylbenzo-12-crown-4 (1) or 4'-benzothiazolylbenzo-15-crown-5 (2) were synthesized by reaction of 2-aminothiophenol with 4'-formylbenzo-12-crown-4 (3) or 4'-formylbenzo-15-crown-5 (4) respectively. (3) and (4) were obtained by reaction of 3, 4-dihydroxybenzaldehyde with tri- or tetraethyleneglycol ditosylate. Triethyleneglycol ditosylate or tetraethyleneglycol ditosylate were synthesized by reaction of p-toluenesulfonylchloride with triethyleneglycol or tetraethyleneglycol in the presence of sodium hydroxide.

• Journal of the Korean Chemical Society
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• v.40 no.8
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• pp.557-564
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• 1996

FAB CAD MS/MS(Fast Atom Bombardment Collision Activated Dissociation Mass Spectrometry/Mass Spectrometry) was used to study different degree of bond stability according to the linkage positions of alkali cationized $(Na^+, Li^+, K^+, NH_4^+)$ stereoisomeric and synthetic oligosaccharides. The alkali metal cations were much more stable, requiring over -40 eV of collision energy vs. only -10 eV for the protonated forms. Of the cations, the potassium cationized trisaccharides were more stable than the others. They would not yield fragment ions under the conditions of collision available in triple quadrupole. Other cationized species exhibited decreasing stability in the series $Nap^+>Li^+>NH_4^+$ using 0.8 mTorr argon pressure in the collision cell. Metal cations of the oligosaccharides maintained charge principally on the amino sugar as shown by shift of all the fragment ions containing the amino sugar. The reason for the higher stability of the metal cationized form is the formation of crown ether-like bond around metal cations, N-acetyl group on GlcNAc and oxygens on fucose moiety. Depending on the metal sizes and the conformation of linkage-isomeric region, cationized species gave linkage dependent fragment patterns and exhibited stability in the series 1-6 > 1-4 > 1-3 linkage.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.669-673
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• 1992

The stability constants, K for the complexation of alkali metal cations(Li^+, Na^+, K^+, Rb^+, and Cs^+) with both 4,5: 13,14-dibenzo-6,9,12-triaza-bicyclo [15,3,1] heneicosa-1 (21),7,19-trioxa-2,16-dione (DBPDA) and 6,9,12-trioxa-3,15,21-triaza bicyclo [15,3,1] heneicosa-1 (21),17,19-triene-2,16-dione (PDA) in N,N-Dimethylformamide (DMF) were determined conductomatically at various temperatures. At all the experiment temperatures, the K value sequences of the alkali metal ions with DBPDA and PDA are Cs^+ > K^+ > Rb^+ > Li^+ > Na^+ and Cs^+ > K^+ > Rb^+ > Li^+ > Na+, respectively. The K values for DBPDA are larger those of PDA for alkali metal ions. The widely recounted "hole-size-selectivity" principle is not applicable to these complexation systems. From the K values obtained at different temperatures, {\delta}H and T{\delta}S for these complexation reactions were determined. The enthalpy change plays principal important role in the complex formation by DBPDA. However, in the case of PDA, the entropy change also contributes to its complex formation.

• Journal of the Korean Applied Science and Technology
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• v.32 no.1
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• pp.31-39
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• 2015

The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded $MLR_3{\cdot}3RH$ form when added the crown ether.