• Proceeding of EDISON Challenge
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• 2017.03a
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• pp.165-171
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• 2017

Diels-Alder 반응은 고리형 탄소화합물을 만드는 유기 합성 과정에서 매우 중요한 반응이다. 이 반응은 중간생성물 없이 오직 1 step으로 진행되는데, diene이나 dienophile에 결합한 치환기의 electron donating 및 electron withdrawing 성질에 따라 반응성이 달라진다고 알려져 있다. 이 때 반응물인 diene과 dienophile의 분자 오비탈 및 전이 상태의 에너지 변화를 계산화학을 통해 분석한다면 Diels-Alder 반응을 보다 심도 있게 이해할 수 있다. 이에 따라 본 연구에서는 DFT 계산을 통하여 치환기에 따른 활성화 에너지의 크기와 diene의 nucleophilicity 및 dienophile의 electrophilicity를 비교하였다. 이를 통해 electron withdrawing group의 경우 분자의 electrophilicity를 증가시키고, electron donating group의 경우 nucleophilicity를 증가시킨다는 것을 확인할 수 있었다. 그 결과, Diels-Alder 반응이 일어날 때 dienophile의 경우 치환된 electron withdrawing group에 의해 electrophilicity가 증가함에 따라 활성화 에너지가 낮아져 반응이 잘 일어나고, 반대로 diene의 경우 electron donating group이 치환되어 있을 때 nucleophilicity의 증가에 따라 반응이 잘 일어난다는 것을 알 수 있었다.

• Journal of Photoscience
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• v.11 no.1
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• pp.7-9
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• 2004

The synthesized macrocycle L was found to be a smart fluorescent receptor which distinguishable efficiently from various neutral molecules with the functional groups such as the electron donating (X =$CH_3$, N($CH_3$)$_2$ and O$CH_3$) and electron withdrawing groups (X =F and Cl), respectively. In the case of guest molecules containing electron donating groups, the fluorescence of macrocycle L was enhanced in the presence of the guest molecules. On the contrary, in the case of guest molecules containing electron withdrawing groups, it was almost quenched in the presence of those.

• Macromolecular Research
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• v.15 no.3
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• pp.216-220
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• 2007

A new polyfluorene-based copolymer having 2-ethylhexyloxy-5-methoxy-l,4-phenylene as an electron donating group and 2,5-diphenyl-oxadiazole as an electron withdrawing group was synthesized by the Suzuki coupling reaction. The obtained copolymer was characterized by $^1H-NMR,\;^{13}C-NMR$, and IR-spectroscopy. The weight average molecular weight ($M_w$) of the obtained polymer was 18,600 with a polydispersity index of 1.5. The maximum photoluminescence of the solution and film of the polymer was observed at 453 nm and 456 nm, respectively. A double-layer device with the configuration, ITO/PEDOT/copolymer/Al, emitted blue light at 460 nm.

• Journal of the Korean Chemical Society
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• v.67 no.3
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• pp.175-180
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• 2023

Tetra-aryl substituted A4-type porphyrins (TP, TD, TA) and trans-A2B2 porphyrins (DDP1, AAP1) with electron-donating or withdrawing groups were synthesized. The band gap energy of those porphyrins was calculated from their UV-Vis spectra and CV data. With an electron-withdrawing group, the band gap energy of porphyrin TA increased via the LUMO energy up. Meanwhile, the introduction of an electron-donating group decreased the band gap of porphyrin by HOMO level up as as in the case of porphyrin TD. The band gap (2.19-2.28 eV) of metalloporphyrin PP-Ni was greater than those (1.81-2.06 eV) of non-metalloporphyrins PP due to the LUMO level up.

• Bulletin of the Korean Chemical Society
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• v.16 no.12
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• pp.1203-1208
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• 1995

Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

• Polymer(Korea)
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• v.38 no.5
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• pp.650-655
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• 2014

The degradation characteristics of perfluoropolyether (PFPE) derivatives currently being used as computer hard disk lubricants have been investigated. Especially, we considered the effects of end group on degradation behavior of PFPE derivatives. It was found that the degradation of PFPE derivatives in the presence of $Al_2O_3$ involves two degradation mechanisms such as thermal degradation and Lewis acid disproportionation by $AlF_3$ which was mainly formed by oxide-to-halide reaction between $Al_2O_3$ and the degraded PFPE. The end groups were strongly related to Lewis acid disproportionation of PFPE derivatives, and it is due to the difference of electron donating ability in the each end groups. Even if PFPE derivatives have same repeating unit in the main chain, Lewis acid disproportionation was prohibited by higher electron donating ability by the end group which caused the high electron density at the acetal group in the repeating unit.

• Applied Biological Chemistry
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• v.1
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• pp.48-54
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• 1960

Studing the binding of the 5-Iodopyrimdines by human serum albumin we obtained the following conclusions; 1. The more strong electron donating groups in the molecule of 5-Iodopyrimidines, the larger the binding force with human serum albumin. This trend seems to be attributed by increase of polarization of the electron donating groups in 5-Iodopyrimidines molecule. 2. The binding force of 5-Iodopyrimidines by human serum albumin is increased with the pH increasing could be occurred the configurational changes of human albumin molecule, and this new binding sites of human serum albumin molecule would form the intermolecular complex with 5-Iodopyrimidines molecule more strongly.

• Journal of the Korean Chemical Society
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• v.8 no.4
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• pp.153-157
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• 1964

The syntheses of substituted tert.-butyl ${\beta}$-(o-tolyl)- perpropionates via intermediates obtained by chloromethylation, malonic syntheses and decarboxylation is described. The intermediates substituted with a group possessing moderate substituent effect such as bromo, chloro, and methyl group were obtained in good yields. The nitro-substituted intermediat was obtained in poor yield. The chloromethylation of toluenes containing electron donating groups resulted in polymerization.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.252-256
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• 1995

Semiempirical MO calculations using the PM3 method are performed on the reactions of acetate esters with substituted phenolate anions. The mechanistic change from rate-limiting formation to breakdown of the anionic intermediate is shown to occur in the gas-phase, especially for meta-nitrophenyl acetate. However the mechanistic change-over takes place at a lower basicity ($pK_0$) of the anion nucleophile than found for the corresponding formate. This lowering of $pK_0$ has been ascribed to the electron donating effect of the methyl group in the acetate. For the reactions involving rate-limiting breakdown of the intermediate, the large Bronsted coefficients, ${\beta}_X({\beta}_{nuc})$, are expected in general, but the magnitude increases to a larger value and the pK0 is lowered accordingly, when an electron-donating nonleaving group, like $CH_3$, is present. This type of nonleaving group effect provides a necessary condition for the carbonyl addition-elimination mechanism with rate-limiting breakdown of the intermediate.

• Macromolecular Research
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• v.15 no.6
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• pp.533-540
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• 2007

We designed and successfully synthesized UV curable, functional acrylate monomers having a polarizing group, i.e., an electron-withdrawing and/or electron-donating group for the optical materials of high refractive index. Optical polymer films made from the functional methacrylate monomers were achieved with photo crosslinking under UV illumination. A monomer having amino and cyano groups (Dimer-CN) exhibited the highest refractive index ($n_{TE}$=1.595 at 850nm) among the studied methacrylate derivatives, due to the large polarizability of the dipolar monomer structures with electron-donating and withdrawing groups. By controlling the compositions of the functional acrylate monomer of copolymers, the refractive indices of the polymers were readily adjusted within a wide range of 1.498-1.595. The copolymers showed a high glass transition temperature $(T_g)$ and good thermal stability, which are desirable for optical applications. $T_g$ and $T_{10%}$ (10%-weight loss occurred) of the copolymers ranged from $120-140^{\circ}C$ and from $329-387^{\circ}C$, respectively.