• Polymer(Korea)
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• v.28 no.2
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• pp.111-120
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• 2004

The interaction between poly(diallyldimethylammonium chloride) (PDADMAC) of positive charge per repeating unit and anionic surfactant, sodium dodecyl sulfate (SDS) has been investigated by light scattering, turbidimetry and fluorescence. Chain behavior of PDADMAC in 0.3 M NaCl aqueous solution seems like neutral polymer chain In good solvent. By adding SDS into PDADMAC solution, strong attractive interaction develops between them, and can be described with two kinds of critical aggregation concentration(CAC). First, at [SDS]/]DADMAC] 0.06, intramolecular critical micellization of SDS occurs inside a single polymer chain. The maximum size of SDS-polymer complex is observed just before intramolecular CAC. Above intramolecular CAC, the size of this complex starts to shrink slowly due to involvement of polymer subchain in micelle. Second, intermolecular CAC is also observed at [SDS]/[DADMAC] 0.5 by means of turbidimetry. Strong aggregation of polymer chains decorated with many micelles occurs after the second CAC, and huge aggregates have formed.

• Journal of the Korean Applied Science and Technology
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• v.31 no.4
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• pp.602-611
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• 2014

The critical micelle concentration (CMC) of the zwitterionic surfactant of dodecyldimethyl(3-sulfopropyl)ammonium hydroxide(LSB, $CH_3(CH_2)_{11}N^+(CH_3)_2(CH_2)_3SO{_3}^-$) and LSB/Tween-20, LSB/Tween-40, LSB/Tween-80 and LSB/DTAB, LSB/TTAB, LSB/CTAB mixed surfactant systems were determined by using the UV/Vis absorbance method from 284 K to 312 K. And the effects of temperature on the micellization have been measured for the thermodynamic study. The results show that the measured values of gibbs free energy are all negative in the whole measured. The values of enthalpy are positive Tween-20, And negative other surfactants. but the values of entropy are positive in the whole measured temperature region. The results show that all of the thermodynamic parameters are dependent on temperature and alkyl-group's length.

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.401-409
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• 1996

The effect of temperature on the cmc of sodium N-lauroyl-N-methyl taurate was examined. The cmc values were found to be decreased initially but increased further with the increase of temperature. From the temperature dependence of cmc, various thermodynamic properties were calculated. The effects of various electrolytes on the cmc of sodium N-lauroyl-N-methyl-taurate were also examined. The free energy of hydrophobic bond formation and the degree of dissociation of the micelles were calculated from log cmc vs. log counter ion concentration plots. The ${\Delta}H_m$ values were decreased with increasing the temperature and changed their signs from plus to minus at $40^{\circ}C{\sim}50^{\circ}C$. The ${\Delta}G_m$ values were decreased with the increase of electrolyte concentration and temperature.

• Polymer(Korea)
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• v.30 no.6
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• pp.453-463
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• 2006

Molecular simulation is an exceptionally useful method for predicting self-assembled structures in various macromolecular systems, enlightening the origins of many interesting molecular events such as protein folding, polymer micellization, and ordering of molten block copolymer. The length scales of those events ranges widely from sub-nanometer scale to micron-scale or to even larger, which is the main obstacle to simulate all the events in an ab initio principle. In order to detour this major obstacle in the molecular simulation approach, a molecular model can be rebuilt by sacrificing some unimportant molecular details, based on two different perspectives with respect to the resolution of model. These two perspectives are generally referred to as 'atomistic' and 'mesoscopit'. This paper reviews various simulation methods for macromolecular self-assembly in both atomistic and mesoscopic perspectives.

• Journal of the Korean Applied Science and Technology
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• v.6 no.1
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• pp.31-40
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• 1989

Five novel amphoteric surfactants of N-acyloxyethylcarboxybetaine series were synthesized via Schotten-Baumman reaction between five acid chlorides containing 10, 12, 14, 16 and 18 carbon atoms in their N-alkyl groups and dimethylaminoethanol to give the intermediate products, 2-dimethylaminoethylalkanoates(2). Quaternization of these products(2) was permitted to from 2-(acyloxyethyldimethylammonic)- acetates(3), whose structures were identified by elemental analysis, IR spectrophotometry and $^1Hnmr$ spectrometry. The yield of the final products was shown in the range of 77-80% based on the intermediate products. The surface tension of the aqueous solution of (3) was measured, and the critical micelle concentrations (cmc) were shown in the range of $2.1\;{\times}\;10^{-3}\;-\;3.3\;{\times}\;10^{-4}mol/l$, and the surface tension at cmc was 28-36 dyne/cm. Cmc was lowered gradually by the increment of the length of N-alkyl ester containing group. The isoelectric point was shown in the range of 4.44-5.20. It showed a tendency to lean toward the acidic site and its range was broadened as increase of the hydrophobic group length. A linear relationship between log cmc and the number of carbon atoms(N) in the hydrophobic alkyl chain was shown in the relative equation of log cmc=-1.75-0.1N, and the contribution rate of N on the standard free energy change in micellization, ${\bigtriangleup}({\bigtriangleup}G^{\circ}m)/{\bigtriangleup}N$, was calculated as -0.23 RT.

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.824-832
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• 2008

micellar solution which is comprised of surfactant monomers, monodisperse micelles, and solvent(water) is studied from a statistical-mechanical point of view. The model examined in this article is for the ideal mixture of monomers, micelles, and solvent with the dielectric constant identical to that of solvent, which is an assumption common to continuum models. The model also reflects interactions between monomer and solvent molecule, and also between micelle and solvent molecule. The statistical-mechanical model under consideration yields ln $X_{CMC}=A+BT+C/T+D{\ln}T$ with $X_{CMC}$ being critical mcielle concentration (in mole fraction), being temperature, and A, B, C, D being constants which depend on the properties of the surfactant molecules. The statistical-mechanical model discussed in this article provides a theoretical basis on the thermal dependence of critical micelle concentration

• Journal of the Korean Chemical Society
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• v.40 no.6
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• pp.420-426
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• 1996

The critical micelle concentration(CMC) and the counterion binding $constant(\beta)$ at the CMC of the mixtures of Sodium dodecylsulfate(SDS) with Sodium dodecylbenzenesulfonate(DBS) in aqueous solutions have been determined from the concentration dependence of electrical conductance at several temperatures from $15^{\circ}C$ to $35^{\circ}C.$ Thermodynamic parameters(${\Delta}C_p,\;{\Delta}G_m^{\circ},\;{\Delta}H_m^{\circ}$ 및 ${\Delta}S_m^{\circ}$ and ${\Delta}C_p$), associated with the micelle formation of SDS/DBS mixtures, have been estimated from the temperature dependence of CMC and $\beta$ values. The measured values of ${\Delta}G_m^{\circ}\;and\;{\Delta}C_p$ are negative but the values of ${\Delta}S_m/^{\circ}$ are positive in the whole measured temperature region. The significance of these thermodynamic parameters and their relation to the theory of the micelle formation of SDS/DBS mixtures have been also considered.

• Macromolecular Research
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• v.15 no.5
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• pp.437-442
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• 2007

Poly(ethylene glycol) methyl ether (PEG)-poly(${\beta}$-amino ester) (PAE) block copolymers were synthesized using a Michael-type step polymerization, and the construction of pH-sensitive polymeric micelles (PM) investigated. The ${\beta}$-amino ester block of the block copolymers functioned as a pH-sensitive moiety as well as a hydrophobic block in relation to the ionization of PAE, while PEG acted as a hydrophilic block, regardless of ionization. The synthesized polymers were characterized using $^1H-NMR$, with their molecular weights measured using gel permeation chromatography. The $pK_b$ values of the pH-sensitive polymers were measured using a titration method. The pH-sensitivity and critical micelle concentration (CMC) of the block copolymers in PBS solution were estimated using fluorescence spectroscopy. The pH dependent micellization behaviors with various bisacrylate esters varied within a narrow pH range. The critical micelle concentration at pH 7.4 decreased from 0.032 to 0.004 mg/mL on increasing the number of methyl group in the bisacrylate from 4 to 10. Also, the particle size of the block copolymer micelles was determined using dynamic light scattering (DLS). The DLS results revealed the micelles had an average size below 100 nm. These pH-sensitive polymeric micelles may be good carriers for the delivery of an anticancer drug.

• Journal of the Korean Applied Science and Technology
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• v.8 no.2
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• pp.115-122
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• 1991

Four novel amphoteric surfactants of N-(2-alkylamidoethyl)-N, N-dimethyl ammonioacetates were synthesized. The each reaction between four saturated fatty acids containing 10, 12, 14 and 16 carbon atoms and N, N-dimethylethylene diamine permitted to give the intermediate products, N-(2-alkylamidoethyl)-N, N-dimethylamines. Quaterinzation of these intermediates was permitted to form N-(2-alkylamidoethyl)-N, N-dimethyl, ammonioacetates, whose sturctures were identified by CC, TLC, elemental analysis, IR pectrophotometry and $^1$HNMR spectrometry. The products yielded from 48% to 58%. The isoelectric points were shown in the range of $4.30{\sim}6.64$. It showed a tendency to learn to the acidic site and its range was broadened as increase of the hydrophobic group length. Surface tensions of the aqueous solution in the $10^{-6}{\sim}10^{-1}$mol/l of amidobetaines were measured. and the critical micell concentration(cmc) were shown in the range of $8.37{\times}10^{-6}{\sim}8.96{\times}10^{-2}$mol/l, and ${\Gamma}_{cmc}$ were reduced to 32.3~38.2 dyne/cm. A linear relationship between log cmc and the number of carbon in the hydrophobic alkyl chain was presented by the formula of log cmc=2.38-0.5n, and the contribution-rate of n on the standard free energy change in micellization ${\partial}({\Delta}G^0$$_m)/{\partial}n$, was calulated as -0.5RT.

• Applied Chemistry for Engineering
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• v.9 no.7
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• pp.968-973
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• 1998

The critical micelle concentrations($CMC^*$) of the mixed surfactant systems of cationic surfactant cetylpyridinium chloride(CPC) and nonionic surfactant Triton X-100(TX-100) in aqueous solutions of salts(KCl and $Na_2CO_3$) and isomeric butanols(tert-butanol, iso-butanol and n-butanol) were determined by UV spectroscopy method. The various thermodynamic values in aqueous solutions of salts and isomeric butanols were compared with the values in pure water, calculated by means of the equation derived from the pseudo-phase separation model. Thermodynamic parameters($X_1$, $\beta$, ${\gamma}i$, $ai^M$, $C_i$ and ${\Delta}H_{mix}$) were found to have great effects of salts and isomeric butanols on the mixed micellization of CPC/TX-100 mixtures, and also in good agreements with the nonideal mixed micelle model. They showed all negative deviations from the ideal mixed micellar behavior.