• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1521-1525
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• 2009

Thermosensitive block copolymers of ethylene oxide and N-isopropylacrylamide (NIPAM) were synthesized. A five armed star shape oligo(ethylene oxide) initiator with a cyclotriphosphazene core was prepared and used for the atom transfer radical polymerization (ATRP) of NIPAM. The lower critical solution temperatures (LCSTs) of the copolymers were 36 to 46 ${^{\circ}C}$, higher than that of PNIPAM (32 ${^{\circ}C}$), depending on their molecular weights. The copolymers were soluble in water below the LCSTs but formed micelles above the LCSTs. The thermosensitive micellization behaviors of the polymers were investigated by fluorescence spectroscopy. With increasing the temperature of an aqueous solution of P2 and pyrene above the LCST, the peak of 333 nm red-shifted to appear around 339 nm and its intensity increased significantly, indicating the micelle formation. The transfer of pyrene into the micelles was also confirmed by a confocal laser scanning microscope. The fluorescence image obtained from P2 in an aqueous pyrene solution exhibited a green emission resulting from the pyrene transferred into the micelles. Salt effects on the solubility of the copolymers in an aqueous solution were investigated. The LCST of P2 decreased sharply as the concentration of sodium chloride increased, while decreased slowly with potassium chloride.

• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.743-749
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• 1997

Local structure refinement of the BaFe1-xSnxO3-y system (x=0.00-0.50) has been carried out with Fe K-edge x-ray absorpion spectroscopic studies. It is found out that the Fe ions are placed in two different symmetric sites such as tetrahedral and octahedral sites in the compounds by comparison with Fe K-edge x-ray absorption near edge structure (XANES) spectrum of the γ-Fe2O3 compound as a reference. Small absorption peaks of dipole-forbiden transitions appear at a pre-edge region of 7111 eV due to the existence of Fe ions in the tetrahedral and octahedral sites. The peak intensity decreases with the substitution amount of Sn ion. Three different absorption peaks of 1s→4p dipole-allowed transition appear on the energy region between 7123 and 7131 eV. The peaks correspond to 1s→4p main transition of Fe ions in tetrahedral and octahedral sites and 1s→4p transition followed by the shakedown process of ligand to metal charge transfer. The bond distances between Fe ions in the tetrahedral site and nearest neighboring oxygen atom (Fe-4O), and those in octahedral site (Fe-6O) are determined with the extended x-ray absorption fine structure (EXAFS) analysis. Two different interatomic distances increase with the substitution amount of Sn ion and also the bond lengths of Fe-4O are shorter than those of Fe-6O in all compounds.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.891-895
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• 2000

Transmission of substituent effects through 5-membered heteroaromaticrings isinvestigated theoretically at the RHF/6-31+G* and B3LYP/6-31+G* levelsusing the deprotonation equilibria of phenol analogues with heteroatoms Y = NH, O, PHand S. The incr ease in the resonance delocalization of the $\pilone-pair$ on the phe-nolic oxygen atom, $n\pi(O)$, accompanied with the deprotonation depends on the heteroatom Y,in the order NH < O < PH < S. This represents the $\pielectron$ accepting ability, or conversely reverse order of the $\pielectron$ donating ability of the $\pilone-pair$ on Y, $n\pi(Y).$ The transmission efficiency of substituenteffects is, however,in the reverse order NH > O > S, which represents the order of delocalizability of $n\pi(Y).$ A better correlation is obtained with ${\sigma}p$ - than with ${\sigma}p$ for the Hammett type plots with the positive slope, $\rho-$ > 0, of the magnitude in the same order as that for the delocalizability of $n\pi(Y).$ Thedeprotonation energy, ΔG = [G(PA) + G(H+)] -G(P), decreases with the increasein the extence delocalization in the order NH > O > PH > S.

• Nuclear Engineering and Technology
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• v.55 no.2
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• pp.555-565
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• 2023

Despite many advantages as structural materials, austenitic stainless steels (SSs) have been avoided in many next generation nuclear systems due to poor void swelling resistance. In this paper, we report the results of heavy ion irradiation to the recently developed advanced radiation resistant austenitic SS (ARES-6P) with nanosized NbC precipitates. Heavy ion irradiation was performed at high temperatures (500 ℃ and 575 ℃) to the damage level of ~200 displacement per atom (dpa). The measured void swelling of ARES-6P was 2-3%, which was considerably less compared to commercial 316 SS and comparable to ferritic martensitic steels. In addition, increment of hardness measured by nano-indentation was much smaller for ARES-6P compared to 316 SS. Though some nanosized NbC precipitates were dissociated under relatively high dose rate (~5.0 × 10^-4 dpa/s), sufficient number of NbC precipitates remained to act as sink sites for the point defects, resulting in such superior radiation resistance.

• Polymer(Korea)
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• v.31 no.6
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• pp.550-554
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• 2007

Atom transfer radical polymerization (ATRP) has been widely used in bioconjugation as it is an efficient and facile method to prepare polymers with pre-designed structures. Quite often, bioconjugation with proteins employs primary amines in proteins as a functional group to attach an initiator. When 2-bromoisobutryl bromide, the most widely used precursor for ATRP initiator, is used, ${\alpha}-halo$ amide initiating groups are formed in the proteins, which are known to exhibit slow initiation behavior in the ATRP process. Here we studied the ATRP of [poly(ethylene glycol)methyl ether] methacrylate (PEGMA) using amide-based initiator. PEGMA differs for both the nature and size of the polymer side branches and shows good solubility in water and a property that made it an ideal candidate for biomaterials. While normal ATRP produced ill-defined p(PEGMA) with amide based initiators, the halogen exchange method and the external additional of deactivator effectively improved the control of ATRP of PEGMA.

• Journal of the Korean Magnetics Society
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• v.14 no.3
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• pp.94-98
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• 2004

The electronic structures and magnetism of MgCCo$_3$(001) surface terminated by the plane with the MgCo-Term (Mg, Co terminated) and the CCo-Term (C, Co terminated) were investigated using the all-electron full-potential linearized augmented Plane-wave method. For the MgCo-Term, the magnetic moment of Co atom of the surface is strongly enhanced to 1.00$\mu$$_{B}$, while the magnetic moment of Co atom of the subsurface is similar to that of the center layers. For the CCo-Term, the magnetic moments of Co atoms are enhanced to 0.75 and 0.80$\mu$$_{B}$ for the surface and subsurface layers, respectively. The magnetic moments of C and Mg atoms are coupled antiferromagnetically to that of the neighbour Co atoms. From the calculated density of states, we see that the enhancements of magnetic moments of Co atoms are closely related to localization of the Co-3d states.

• Journal of Integrative Natural Science
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• v.3 no.4
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• pp.226-230
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• 2010

Calculation of partial charge is important in chemistry. However, because there are many methods developed, it is of considerable interest to know how to calculate and apply properly to address various chemical problems. For basis set, usually double zeta quality is acceptable, and double zeta polarization function would be enough for most cases. To describe electronic state more accurately, Many electron configurations would be necessary to describe highly strained or anionic species. The NPA population introduced new concept about amide bonds, i.e., the planar geometry of nitrogen atom may not come from resonance, but from the lowering of p-orbital energy by electronegative carbonyl carbon atom. The issues for hypervalent atomic charges was also addressed by various charge derivation scheme. When the charge schemes were applied to organolithium compounds, the ionic nature of boding was revealed. This comes from the fact that previous Mulliken partial atomic charges overemphasized the covalent character, wihout much justification. The other partial charge derivation schemes such as NPA(natural population analysis), IPP (Integrated Projected Population) showed that much more ionic picture. ESP potential derived charges are generally believed to be suitable to describe intermolecular interactions, therefore they are used for molecular dynamics simulations and CoMFA (comparative molecular field analysis). The charge derivation schemes using multipole polarization was mainly applied to reproduce experimental infrared spectroscopy. In some reports these schemes are also suitable for intermecular electrostatic interactions. Charges derived from electron density gradient have shown the some bonds are not straight, but actually bent. The proper choice of charge-calculation method along with suitable level of theory and basis set are briefly discussed.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.857-862
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• 2011

Kinetic studies of the reactions of N-methyl-Y-${\alpha}$-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at $25.0^{\circ}C$. The Hammett plots for substituent X variations in the nucleophiles (log $k_N$ vs ${\sigma}_X$) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log $k_N$ vs $pK_a$) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log $k_N$ vs ${\sigma}_Y$) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant $\rho_{XY}$ values are all negative: $\rho_{XY}$ = -0.32 for X = Y = electron-donating; -0.22 for X = electron-withdrawing and Y = electron-donating; -1.80 for X = electron-donating and Y = electronwithdrawing; -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal ($k_H/k_D$ > 1) for Y = electron-donating, while secondary inverse ($k_H/k_D$ < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-${\alpha}$-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the ${\alpha}$-carbon for Y = electronwithdrawing substituents.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1469-1473
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• 2010

Influences of alrylamino (R) substituents on the herbicidal activity ($pI_{50}$) of 1-(4-chloro-2-fluoro-5-propargyloxypheny)-3-(R)-thiourea analogues (1 ~ 35) against the barnyard grass (Echinochloa crusgalli) in the pre-emergence step were discussed quantitatively using comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) as the three dimensional quantitative structure-activity relationship (3D-QSAR) method. The statistically most satisfactory CoMFA models for the herbicidal activity against the barnyard grass had the better predictability ($r^2{_{cv.}}$) and correlativity ($r^2{_{ncv.}}$) than those of CoMSIA models. The optimized CoMFA model 1($r^2{_{cv.}}$ = 0.531 & $r^2{_{ncv.}}$ = 0.931) with the sensitivity to the perturbation (${d_q}^{2'}{dr^2}_{yy'}$ = 1.081) and the prediction ($q^2$ = 0.475) produced by a progressive scrambling analyses were not dependent on chance correlation. And statistical qualities with the atom based fit alignment (AF) were slightly higher than those of the field fit alignment (FF). According to the optimized CoMFA model 1, the contribution ratio (%) of the steric field (76.9%) on the herbicidal activity of the Thioureas was three-fold higher than that of the electrostatic field (20.1%) and the hydrophobic field (3.0%) had the least influence. A steric favor group is on the vicinity of the nitrogen atom in alrylamino (R) substituent, and a steric disfavor group is on the outer side of alrylamino (R) substituent. Thus, as the size of alrylamino (R) substituent increases, so does the herbicidal activity of the substituent.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.1958-1962
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• 2007

The title complex, Ir(H)(CO)(PEt3)2(η 2-C60) (2), has been prepared by the reaction of excess C60 (4 equiv) with a tetrairidium complex Ir4(CO)8(PEt3)4 (1) in refluxing chlorobenzene in 40% yield as green crystals. Compound 2 has been characterized by cyclic voltammetry (CV), spectroscopic methods (mass, IR, 1H and 31P NMR), and a single crystal X-ray diffraction study. The molecular structure reveals that the iridium atom of 2 is coordinated by two axial ligands of a hydrogen atom and a carbonyl group, and three equatorial ligands of two phosphorus atoms and an η 2-C60 moiety. The CV study exhibits three reversible one-electron redox waves for the successive reductions of 2, together with additional four redox waves due to free C60 reductions, which was formed by decomposition of 2 in the reduced states. The three reversible redox waves of 2 are shifted to more negative potentials by ca. 270 mV compared to free C60, reflecting both metal-to-C60 π-back-donation and the electron-donating nature of the two phosphorus ligands.