• Analytical Science and Technology
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• v.6 no.1
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• pp.1-8
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• 1993

The purpose of this study is to investigate the elution behavior of monosubstituted phenols and benzenes in micellar liquid chromatographic system, $C_{18}$ column-anionic surfactant, sodium dodecyl sulfate(SDS). The partition coefficients between the micellar pseudophase-water and modified stationary phase-water are calculated by the relationship between solute retention and micellar mobile phase(SDS) composition. The free energy of transfer of solute from water to micelle is also calculated from these values. There is a direct correlation between the hydrophobicity parameters in MLC and corresponding partition data for 1-octanol-water, which indicates that the hydrophobicity of molecules plays an important role in the partition for both systems and that quantitative structure activity relationships(QSAR) are available from studies on micellar partition. The other purpose of this study is to investigate methylene selectivity of alkyl homologous series through correlation between retention and the number of carbons. The correlation between hydrophobicity parameters in MLC and 1-octanol-water partition data was also observed when n-propanol was as a modifier in the mobile phase.

• Polymer(Korea)
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• v.30 no.2
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• pp.146-151
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• 2006

Linear and branched copolymers consisting of poly(ethylene glycol) (PEG) and $Poly({\varepsilon}-caprolactone)$ (PCL) were prepared to compare the characterization of star-shaped copolymers with various molecular architecture. Linear and branched PEG-PCL (1-arm, 2-arm, 4-arm, and 8-arm) copolymers were synthesized by the ring-opening polymerization of ${\varepsilon}-caprolactone$ in the presence of HCl $Et_2O$ as a monomer activator at room temperature. The synthesized copolymers were characterized with $^1H-NMR$, GPC, DSC, and XRD. As a result of the DSC and XRD, each copolymers showed different thermal properties and crystallinity according to the number of ms. The micellar characterization of linear and branched copolymers in an aqueous phase was carried out by using NMR, dynamic light scattering, AM, and fluorescence techniques. The critical micelle concentration (CMC) and diameters of micelles depended on the number of arms. Most micelles exhibited a spherical shape in AFM. In this study, we characterized star-shaped PEG-PCL copolymers and investigated their molecular architecture effect on the various properties. Furthermore, we confirmed that the micelles termed with linear and branched PEG-PCL copolymers have possibility as a potential hydrophobic drug delivery vehicle.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.629-636
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• 1990

Dephosphorylation of p-nitrophenyldiphenylphosphate(p-NPDPP) mediated by anions of sodium 2-alkylbenzimidazole-5-sulfonate(R-BI-SO$_3$Na) in CTABr micellar solutions are obviously slower than that by anion of sodium benzimidazole-5-sulfonate(BI-SO$_3$Na), and the reation rates were decreased with increase of lengths of alkyl groups. This presents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups of R-BI$^-$SO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(△H$^\neq$/TEX>, △G$^\neq$/TEX> and △S$^\neq$/TEX>) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole moiety of R-BI$^-$SO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) are micellized for themseleves, and increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr.

• KSBB Journal
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• v.9 no.3
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• pp.325-331
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• 1994

PGA is formed in a route of CO2 fixation of RuBP catalyzed by RuBPCase, followed by reduction of the PGA by NADH to GAP This reduction is enhanced in an anionic micellar solution(SDS), in which NADH is distributed in the aqueous and the micellar pseudophases in a given ratio. This micellar bounded NADH reacts to PGA, and in higher micellar concentration than $1.25{\times}10^{-2}M$, most of NADH is oxidized to NAD+ by PGA. On the other hand, in the solutions of the positive ionic(CTABr), zwitter ionic(Chaps) and nonionic (Brij and Triton X-100) micelles, the reactions are also enhanced and the concentrations of NADH reach minima with micellar concentrations. Such minima are typical of micellar catalyzed bimolecular reactions, and the fall in concentrations of the reductant followed by a gradual increase is charataristic of reactions of hydrophobic substrates: that is, the reductions of PGA by NADH are sharply enhanced in a range of the lower micellar concentrations, and NADH amounts in ca. $1.25-2.50{\times}10^{-3}M$ micellar solutions are reached to minima, followed by gradual increases of the reductant concentration.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.753-762
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• 1994

Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.97-105
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• 1989

This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

• Bulletin of Food Technology
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• v.8 no.1
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• pp.101-110
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• 1995

• The Korean Publising Journal, Monthly
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• s.157
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• pp.16-17
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• 1994

• Analytical Science and Technology
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• v.6 no.3
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• pp.267-274
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• 1993

The iterative regression optimization strategy using two parameters is described and applied to the separation of amino acids and peptides by means of micellar liquid chromatography. The parameters examined are concentration of surfactant and 2-propanol. This approach results in a efficient optimization using a small number of initial experiments.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10b
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• pp.243-244
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• 2003

계면활성제는 모터오일, 제약, 비누, 세제 등의 용도가 다양한 화학 제품 중 하나이다. 계면활성제는 비극성의 긴 탄화수소 체인으로 이루어진 꼬리(tail)부분과 보통은 이온으로 이루어진 극성을 띄는 머리(head)부분으로 구성되어있다. 보통 계면활성제를 나타낼 때는 fig. 1의 성냥개비와 같은 모형으로 표시하는 경우가 많다. 머리부분이 친수기를 나타내고, 꼬리부분이 친유기를 나타낸다. (1-2) 물과 같은 극성용매에서, 친수성과 친유성의 두 가지의 특징을 동시에 가지고 있는 계면활성제는 미셀(micelle)이라고 알려진 정리된 분자 화합이 일어난다.[3] (중략)