• 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 Chemical Society
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• v.47 no.6
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• pp.569-577
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• 2003

Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.516-521
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• 1985

Ethylenediamine-triacetatocobalt (III) complexes with an ammine, an ethylene-diamine, and a trimethylenediamine as the unidentate ligand were prepared, and were isolated as only one isomer for each case by the Dowex 50W-X8, cation exchange resin in $H^+$ form. The geometrical isomer of these complexes have been assigned cis-equatorial form in the three possible geometrical isomers from the elemental analysis, pH titration, IR, NMR, and electronic absorption spectrum. It was found that $[CoN_3O_3]$ system of the meridional form with multidentate ligand have the first absorption band of the largely splitting pattern, and that the diamines (ethylenediamine, trimethylenediamine) have coordinated to the central cobalt (III) ion as a unidentate ligand.

• Polymer(Korea)
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• v.35 no.6
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• pp.593-598
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• 2011

The IPA-co-HDO-co-(TPA/MA) copolymers for all-vanadium redox flow battery were synthesized by melt condensation polymerization using isophthalic acid(IPA), 1,6-hexandiol (HDO), terephthalic acid(TPA) and maleic anhydride(MA). The amination of chloromethylated IPA-co- HDO-co-(TPA/MA)(CIHTM) copolymer was carried out using trimethylamine, and the anion exchange membrane was also prepared by UV crosslinking reaction. The structure and thermal stability of IHTM copolymers were confirmed by FTIR, $^1H$ NMR, and TGA analysis. The anion membrane properties such as water uptake, ion exchange capacity, electric resistance and electrical conductivity, were measured by gravimetry, titration and LCR meter. The efficiency of the all-vanadium redox flow battery was analyzed. The ion exchange capacity, electric resistance and electrical conductivity were 1.10 meq/g, $1.98{\Omega}{\cdot}cm^2$, and 0.009 S/cm, respectively. The efficiency of charge-discharge, voltage, and energy for the allvanadium redox flow battery were 96.5, 74.6, 70.0%, respectively.

• Polymer(Korea)
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• v.34 no.3
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• pp.202-209
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• 2010

Aromatic copolyamides were prepared and their applicability to proton exchange membrane wasstudied. The copolymer contains thermally stable and mechanically strong poly(m-phenylene isophthalamide) segments, and easily processable and good film forming polysulfone segments. For the copolymer, amineterminated sulfonated ether sulfone monomer, m-phenylene diamine, and isophthaloyl chloride were reacted, and the obtained copolymer was transformed into crosslinkable prepolymer by the reaction with acryloyl chloride. The prepolymer was thermally cured and converted into proton exchange membranes for fuel cell application. Each reaction step and the molecular characteristics of precursor copolymers were monitored and confirmed by $^1H$ NMR, FTIR, and titration. The performance of the membranes was measured in terms of water uptake, proton conductivity, and thermal stability. The water uptake, ion exchange capacity (IEC), and proton conductivity of the membranes increased with the increase of sulfonated ether sulfone segment content. Membrane containing 30 mol% sulfonic acid sulfone segment showed 1.57 meq/g IEC value. Water uptake was limited less than 44 wt% and the highest proton conductivity up to $3.93{\times}10^{-2}S/cm$ ($25^{\circ}C$, RH= 100%) was observed.

• Polymer(Korea)
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• v.35 no.2
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• pp.106-112
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• 2011

Aromatic copolyamides were prepared and their applicability to proton exchange membrane was studied. The copolymers contain two segments; thermally stable and mechanically strong poly (p-phenylene terephthalamide) (PPTA), and easily processable and good film-forming polysulfone. For the copolymers, different ratios of amine-terminated sulfonated ether sulfone monomer, terephthaloyl chloride, and p-phenylene diamine were sequentially reacted. The obtained copolymers were mixed with trimethylolpropane triglycidyl ether (TMPTGE), thermally cured, and converted into proton exchange membranes for fuel cell application. The reactions at each step and the molecular characteristics of precursor copolymers were confirmed by $^1H$ NMR, FTIR, and titration. The performance of the membranes was measured in terms of water uptake and proton conductivity. The water uptake, ion exchange capacity (IEC), and proton conductivity of the membranes increased with the increase of sulfonated ether sulfone segment content. Membrane containing 60 mol% sulfonic acid sulfone segment showed 1.88 meq/g IEC value. Water uptake was limited less than 110 wt% and the highest proton conductivity was up to $7.4{\times}10^{-2}$ S/cm ($25^{\circ}C$, RH=100%).

• Journal of Soil and Groundwater Environment
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• v.9 no.4
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• pp.42-51
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• 2004

Peat humin(p-Humin), humic acid(p-HA) and fulvic acid(p-FA) were isolated from Canadian Sphagnum peat moss by dissolution in 0.1M NaOH followed by acid precipitation. After purification cycles, they are characterized for their elemental compositions and, acid/base properties. Functionalities and carbon structures of the humic fractions were also characterized using FT-IR and solid state $^{13}C$-NMR spectroscopy. Those results are compared with one another and with soil humic substances from literatures. Main purpose of this study was to present a chemical and spectroscopic characterization data of humic substance from peat moss needed to evaluate its environmental applicability. The relative proportions of the p-Humin, p-HA and p-FA in the peat moss was $76\%,\;18\%,\;and\;3\%$, respectively, based on the total organic matter content ($957{\pm}32\;g/kg$). Elemental composition of p-Humin were found to be $C_{1.00}H_{1.52}O_{0.79}N_{0.01}$ and had higher H/C and (N+O)/C ratio compared to those of p-HA($C_{1.00}H_{1.09}O_{0.51}N_{0.02}$) and p-FA($C_{1.00}H_{1.08}O_{0.65}N_{0.01}$). Based on the analysis of pH titration data, there are two different types of acidic functional groups in the peat moss and its humic fractions and their proton exchange capacities(PEC, meq/g) were in the order p-FA(4.91) >p-HA(4.09) >p-Humin(2.38). IR spectroscopic results showed that the functionalities of the peat moss humic molecules are similar to those of soil humic substances, and carboxylic acid(-COOH) is main function group providing metal binding sites for Cd(II) sorption. Spectral features obtained from $^{13}C$-NMR indicated that peat moss humic molecules have rather lower degree of humification, and that important structural differences exist between p-Humin and soluble humic fractions(p-HA and p-FA).