• Journal of the Korean Chemical Society
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• v.59 no.5
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• pp.379-386
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• 2015

The solubilization of p-chlorobenzoic acid in aqueous solutions of pure cationic, nonionic, amphoteric, and their mixed surfactant systems have been measured by the UV-Vis spectrophotometric method. The effects of hydrophobic tail-group with different chain length and the hydrophilic head-group on the solubilization of p-chlorobenzoic acid have been studied and also thermodynamic parameters have been calculated from the dependence of K_s values on the temperature. The results show that the values of ΔG^o for the solubilization by all surfactant systems are negative and the values of ΔH^o and ΔS^o are all positive.

• Polymer(Korea)
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• v.30 no.6
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• pp.464-470
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• 2006

Diblock copolymers consisting of methoxy Poly (ethylene glycol) (MPEG) and poly (${\epsilon}-ca$ prolactone) (PCL), poly(${\delta}-valerolactone$) (PVL), poly(L-lactide) (PLLA), or poly(L-lactide-co-glycolide) (PLGA) were prepared to compare the characterization of diblock copolymers as a drug carrier. MPEG-PCL, MPEG-PVL, MPEG-PLLA, and MPEG-PLGA diblock copolymers were synthesized by the ring-opening polymerization of ${\epsilon}$-caprolactone or ${\delta}$-valerolactone in the presence of $HCl{\cdot}Et_2O$ as a monomer activator at room temperature and by the ring-opening polymerization of L-lactide or a mixture of L-lactide and glycolide in the presence of stannous octoate at $130^{\circ}C$, respectively. The synthesized diblock copolymers were characterized with $^1H-NMR$, GPC, DSC, and XRD. The micellar characterization of MPEG-polyester diblock copolymers in an aqueous phase was carried out by using NMR, dynamic light scattering, AFM, and fluorescence techniques. Most micelles exhibited a spherical shape in AFM. Thus, ore confirmed that the micelles formed with MPEG-polyester diblock copolymers have possibility as a potential hydrophobic drug delivery vehicle because a hydrophobic drug could be preferentially distributed in the micelle core.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.522-532
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• 1985

The reactions of p-nitrophenyldiphenylphosphate (p-NPDPP) with anions of benzimidazole (BI) and its 2-alkyl derivatives (R-BI) are strongly catalyzed by the micelles of cetyltrimethyl ammonium bromide (CTABr). On the other hand, the first order rate constants $(k'_{R-BI^-})$ and the second order rate constants $(k_{m(R-BI^-)})$ of the reactions mediated by R-$BI^-$in the micellar pseudophase are much smaller than those mediated by $BI^-$. In order to explain the slower rates of the micellar reactions mediated by R-$BI^-$, we compared the concentration-ratios ([R-$BI^-$]/[$BI^-$]) with the first order rate constant-ratios $(k'_{R-BI^-}/k'_{BI^-})$ and the second order constant-ratios $(k_{m(R-BI^-)}/k_{m(BI^-)})$ for the reactions taking place in the micellar pseudophase. The rate constant-ratios were much smaller than the concentration-ratios. For example in a 5 ${\times}10^{-4}$M butyl-BI solution, the two ratios were 0.089 and 0.430 (for the first order) respectively, and in a $10^{-4}$M butyl-BI solution the former was 0.100 (for the second order). This predicts that the reactivities of R-$BI^-$ in the micellar pseudophase are much smaller than that of $BI^-$. Based on the values of several kinetic parameters measured for dephosphorylation of p-NPDPP mediated by R-$BI^-$, a schemetic model is proposed. Due to the hydrophobicity and the steric effect of the alkyl substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long cetyl groups of CTABr. Consequently, the movements of R-$BI^-$ bound to the micelle should be restricted, leading to decreased collison frequencies between the nucleophiles and p-NPDPP. We refer this as an "anchor effect". This effect became more predominent when a larger alky group in R-BI was employed and when a greater concentration of R-BI was used.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.112-117
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• 1999

The pulsed field gradient NMR method has been used to determine self-diffusion coefficients in ternary N-alkyl-N, N-dimethylamine oxide/hydrocarbon/$D_2O$ system. For n = 12, 14, 16 and n' = 8, 10, 12, 14, 16, in the micellar phase, diffusion is chiefly governed by the hydrodynamic transport of micelles, supplemented by an exchange of solubilized hydrocarbon upon micellar collisions. This investgation is performed by variations in both the surfactant alkyl chain length and in the size of the hydrocarbon molecules. In cubic phases, the solvent still exhibits values of the diffusion coefficients which are typical for motion in a continuous water phase, with the microemulsion droplets acting as obstacle. Mobilities of the surfactant in the gel state were low and have been determined only for the surfactant($C_{12}DMAO$) with the shortest alkyl chain length. Exchange of hydrocarbon between micellar entities in the gel was found to be occured by a hopping process, the associated rate decreased with alkyl chain length of the surfactant.

• Polymer(Korea)
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• v.34 no.3
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• pp.274-281
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• 2010

In this study, PEG-PLA(or PLGA) amphiphilic di-block copolymers were synthesized by ring opening polymerization of D,L-lactide(or glycolide) and applied to polymeric micelle system for solubilization of a rosiglitazone as diabetes drug. The drug could be efficiently loaded into the polymer micelle by solid dispersion technique, and the drug-loaded micelles were characterized and evaluated as a drug delivery carrier by fluorescence spectrometer, DSC, and DLS measurements. The colloidal stability of drug loaded micelles in aqueous media could be enhanced by addition of 2-hydroxy-N-picolylnitinamide as a hydrotropic agent. The polymer micelles also showed biocompatible and nontoxic properties in vitro cell viability using MTT assay, and the drug loaded micelles were observed to be more effective than free drug for decreasing glucose in blood of rats.

• Applied Chemistry for Engineering
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• v.9 no.1
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• pp.149-154
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• 1998

The characteristics of drag reduction and rheological behaviors were investigated using cationic surfactants, whose microstructures are known to change when concentration of the surfactant exceeds CMC. The firstly formed spherical micelles change to rodlike or disklike micelles because of packing between surfactants micells, and of thermodynamic perference. The drag reduction becomes significant when the concentration increases over this micellar transient point. Drag reductions were measured as a function of concentration, and rheological characteristics of the surfactant were further investigated to understand the correlation between their rheological properties and drag reduction. Micelles show the non-Newtonian behavior, and shear thickening behaviors were observed due to the structural development. In addition, structural developments were determined by adding the counter-ion in case of DOBON-G.

• 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.

• Applied Chemistry for Engineering
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• v.22 no.5
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• pp.473-478
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• 2011

The interaction of para-halogenated benzoic acid isomers with the micellar system of tetradecyltrimethylammonium bromide was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of benzoic acid isomers into the micellar system of TTAB and the critical micelle concentration (CMC) of TTAB have been measured with the change of temperature. Various thermodynamic parameters have been calculated and analyzed from those measurement. The results show that the values of ${\Delta}G^{\circ}{_s}$ for the solubilization of all isomers are negative and the values of ${\Delta}H^{\circ}{_s}$ and ${\Delta}S^{\circ}{_s}$ are all positive within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of benzoic acid isomers have been also measured. There was a great decrease on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate that the solubilization sites of each isomers in the TTAB micellar system are the surface or the palisade region of the micelle.

• Journal of the Korean Applied Science and Technology
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• v.38 no.4
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• pp.994-1002
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• 2021

The solubilization constants (K_s) of 4-halogenated aniline derivatives by cationic surfactants (DTAB, TTAB, and CTAB) were measured by the UV-Vis method. As a result, the K_s values decreased as the temperature increased for all the aniline derivatives and showed a tendency to increase as the radius of the halogen substituent and the hydrophobic length of surfactant increased. The calculated values of ΔG^o and ΔH^o for these solubilizations all showed negative values within the measured range, but all the ΔS^o values showed positive values. For all the 4-halogenated anilines, the ΔG^o values all tended to decrease as the temperature increased, but both values of ΔH^o and ΔS^o showed a tendency to increase. In addition, as the radius of the halogen substituent increased, the values of ΔH^o and ΔS^o tended to decrease in general. However, when the hydrophobic group length of the surfactant was increased, the values of these thermodynamic functions showed a tendency to increase in general, although it differed depending on the type of aniline derivative. From the changes of such functions, it was possible to estimate the type and strength of interactions between 4-halogenated aniline and micelle, and the location at which they were solubilized in the micelle.

• Applied Chemistry for Engineering
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• v.35 no.2
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• pp.115-121
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• 2024

This study analyzed the influence of process variables affecting the thermodynamic equilibrium and fluid dynamics of interfaces such as reverse micelle, salt concentration, interfacial tension, and viscosity of fluids to optimize the microencapsulation process using the W1/O/W2 double emulsion method. The process variable with the greatest impact on encapsulation efficiency was found to be the difference in osmotic pressure between the W1 and W2 phases. It was observed that increasing the salt concentration in the W2 phase or decreasing the ascorbic acid concentration in the W1 phase resulted in higher encapsulation efficiency. Additionally, a larger difference in osmotic pressure led to increased damage to the surface of the microparticles, as confirmed by SEM images. The introduction of reverse micelles, which was anticipated to increase encapsulation efficiency, either had a low contribution or even decreased encapsulation efficiency. The yield of microcapsules was expressed as a universal function, applicable to all process conditions or solution compositions. According to this universal function, no further increase in yield was observed beyond the Ca (capillary number) of approximately 20.