• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.9-18
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• 1986

MNDO and STO-3G calculations were performed to determine relative stabilities of rotamers for ${\alpha}$-substituted acetones, $CH_2XCOCH_3$, X = F, Cl, OH, SH, and $NH_2$. It was found that rotamers corresponding to gauche forms are preferred for all the ${\alpha}$-substituents except for X = F and NH$_2$, for which the cis forms were the preferred ones. The stability of gauche form was dictated by the stabilizing two-orbital-two-electron interaction ${\sigma}_{cx}$-${\pi}_{co}^*$, operating uniquely in the gauche form due to the substantial vicinal overlap and energy gap narrowing between ${\sigma}_{cx}$ and ${\pi}_{co}^*$ orbitals. The energy gap narrowing was caused by the lowering of ${\pi}_{co}^*$ level due to the hyperconjugative ${\sigma}_{cx}^*$-${\pi}_{co}^*$ interactions; the red shift in the n-${\pi}^*$ transition was another effect of the relatively large ${\sigma}_{cx}^*$-${\pi}_{co}^*$ splitting. Various ${\sigma}-{\pi}$ interactions in the gauche form were found to be stronger in the third-row hetero atom system, X = Cl and SH. Interactions between nonbonding orbital on N, $n_N$ and vicinal C-C ${\sigma}$ bond were shown to be stronger in the trans than in the cis orientation.

• Journal of the Korean Chemical Society
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• v.26 no.2
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• pp.65-72
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• 1982

STO-3G level computations were performed on n-propylamine, n-propylamine radical and cis-and trans-ethylene diamines in order to investigate structural contributions of (n${\pi}$/m) and (n-${\sigma}^*$) structures to the energy variations accompanying the conformational changes. It was found that (5${\pi}$/5) and (4${\pi}$/4) structures had attractive and repulsive nonbonded interactions, respectively, which were approximately additive. anti(n-${\sigma}^*$) structures had more stabilzing hyperconjugative interactions than syn(n-${\sigma}^*$) structures, but due to the large internuclear repulsion the net effect was destabilizing inthe former in contrast with the net stabilizing contribution in the latter. Moreover it was found that the stabilizing ${\pi}$-nonbond structure, (5${\pi}$/5) was always cooperatively reinforced by the more stabilizing anti(n-${\sigma}^*$) interaction, whereas the destabilizing (4${\pi}$/4) structure was accompanied by the less stabilizing syn(n-${\sigma}^*$) interaction. This type of cooperativity was found general through-bond interaction of the terminal lone pair lobes split the energy levels into two, $n_+ = \frac{1}{\sqrt{2}}(n_1 + n_2)$ and $n_- = \frac{1}{\sqrt{2}}(n_1 - n_2)$, the latter being the lower level, which can be shown using simple overlap patterns of the two lobes with a common vicinal ${\sigma}^*$ orbital.

• Proceedings of the Korean Society of Plant Pathology Conference
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• 2003.10a
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• pp.64.2-64
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• 2003

Twenty-seven monogenic rice lines harboring major resistant gene for blast were screened to analyze their resistance spectrum to Korean blast fungus population using 190 isolates collected from 1985 to 2002. Especially, the monogenic line containing Pi-9 gene was screened using 320 isolates. Based on the monogenic lines-blast isolate interactions, the 27 rice lines were classified into 9 groups. The chinese rice cultivar LTH showed susceptible to all the tested isolates. Those lines IRBLz-Fu, ERBL5-M and IRBL9-W harboring Pi-z, Pi-5, and Pi-9, respectively showed broader spectrum of resistance than those rice lines having Pi-19, Pi-7 etc. Interestingly, the Pi-9 gene(IRBL9-W) showed resistance to most isolates collected before 2000, but it showed susceptible reactions to 5％ and 20％ of blast fungus population in 2001 and 2002, respectively. Population of virulent isolates to Pi-ta, Pi-b, and Pi-7 also were increased in 2002 compared to those before 2000.

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.95-99
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• 2012

Two novel copper(II) complexes, [Cu(dmamhp)$(H_2O)_2(SO_4)]_n$ (1) and [Cu(dmamhp)$(NO_3)_2(H_2O)]{\cdot}H_2O$ (2) [dmamhp = 2-dimethylaminomethyl-3-hydroxypyridine] have been synthesized and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 displays a double one-dimensional chains structure, in which each chain is constituted with the distorted octahedral copper(II) complex bridged through bidentate sulfate ligands resulting in a coordination polymer. The bifurcated hydrogen bonds and $\pi-\pi$ interactions play important roles in the formation of the double chains structure. On the other hand, compound 2 adopts a distorted square pyramidal geometry around copper(II) ion and exists as a discrete monomer. There are intermolecular bifurcated hydrogen bonds and $\pi-\pi$ stacking interactions between the monomeric units. The magnetic properties revealed that the paramagnetic behaviors are dominantly manifested and there are no intermolecular magnetic interactions in both compound 1 and 2.

• Journal of Photoscience
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• v.2 no.2
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• pp.89-93
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• 1995

Solvatochromic effects and hydrogen bonding interactions of 4-hydroxy-4'-nitrostilbene(NSOH) were investigated. Electronic transition energies of NSOH have good correlation with Taft's $\pi$$^*$. The hydrogen bonding interactions can be accounted by analysis with equation of $\Delta$E= $\Delta$E$_0$ + s($\pi$$^*$ + d$\delta$) + a$\alpha$ + b$\beta$. From UV-visible absorption maximum energies, $\Delta$E = 81.2 kcal/mole - 6.66($\pi$$^*$ - 0.20$\delta$) - 0.66$\alpha$ - 1.93$\beta$ (corr.=0.970) was obtained, and from fluorescence intensity maximum energies, $\Delta$E= 70.07 kcal/mole - 21.6($\pi$$^*$ - 0.11d) - 1.74$\alpha$ - 2.73$\beta$ (corr.=0.947) was obtained. The micropolarity estimated at the solubilization sites is close to the polarity of water. The apparent Taft's $\pi$$^*$ values of solubilization sites are close to 1. Howcver, the solubilization sites for the fluorescent NSOH is rather nonpolar. Both NSOH and NSO$^-$ can be solubilized in CTAB and CTAC micelles and NSOH is the only species that can be solubilized in SDS and Brij-35 micelles.

• Macromolecular Research
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• v.12 no.3
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• pp.251-257
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• 2004

The nature of the nematic liquid crystal (LC) alignment induced by the rubbed polyimide (PI) alignment layers (ALs) and the electro-optical (EO) properties of the LC cells are expected to depend on the chemical and physical features of the PI. By employing five pyromellitic dianhydride (PMDA)-type PIs having different functionalities, we have studied the effects of the PI's structure and chemistry on the alignment characteristics and the cell's EO properties. Increasing the flexibility of the PI increases the pretilt angle and tends to improve the alignment stability. On the other hand, the rigid, fluorinated PI displays poor stability for LCs and induces a less stable/uniform LC alignment and, subsequently, a small pre tilt angle. It also transpired that fluorination of the PI deteriorated the voltage-transmittance characteristics and the voltage holding ratio; increasing the flexibility of the PI structure improves these EO properties. The finding that the qualitative trends for the PI's functionalities are similar for both the alignment and EO properties suggests that the EO properties are closely related to the alignment characteristics, which are determined by short-range interactions between LC and PI molecules.

• BMB Reports
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• v.49 no.7
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• pp.355-356
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• 2016

The THO/TREX complex consists of several conserved subunits and is required for mRNA export. In metazoans, THO/TREX binds a subset of mRNAs during RNA splicing, and facilitates their nuclear export. How THO/TREX selects RNA targets is, however, incompletely understood. In our recent study, we reported that THO is loaded onto Piwi-interacting RNA (piRNA) precursor transcripts independent of splicing, and facilitates convergent transcription in Drosophila ovary. The precursors are later processed into mature piRNAs, small noncoding RNAs that silence transposable elements (TEs). We observed that piRNAs originating from dual-strand clusters, where precursors are transcribed from both strands, were specifically affected by THO mutation. Analysis of THO-bound RNAs showed enrichment of dual-strand cluster transcripts. Interestingly, THO loading onto piRNA precursors was dependent on Cutoff (Cuff), which comprises the Rhino-Deadlock-Cutoff (RDC) complex that is recruited to dual-strand clusters by recognizing H3K9me3 and licenses convergent transcription from he cluster. We also found that THO mutation affected transcription from dual-strand clusters. Therefore, we concluded that THO/TREX is recruited to dual-strand piRNA clusters, independent of splicing events, via multi-protein interactions with chromatin structure. Then, it facilitates transcription likely by suppressing premature termination to ensure adequate expression of piRNA precursors.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2148-2154
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• 2013

Three push-pull organic semiconductors, TPA-$Th_3$-MMN (1), TPA-ThTT-MMN (2), and TPA-ThDTT-MMN (3), comprising a triphenylamine donor and a methylene malononitrile acceptor linked by various ${\pi}$-conjugated thiophene units were synthesized, and the effects of the ${\pi}$-conjugated bridging unit on the photovoltaic characteristics of solution-processed small-molecule organic solar cells based on these semiconductors were investigated. Planar bridging units with extended ${\pi}$-conjugation effectively facilitated intermolecular ${\pi}-{\pi}$ packing interactions in the solid state, resulting in enhanced $J_{sc}$ values of the SMOSCs fabricated with bulk heterojunction films.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.101-107
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• 1980

Composite ${\pi}$-structure analysis has been proposed for predicting relative isomer stabilities based on nonbonded effects: all the possible crowded ${\pi}$-structures are identified for each isomer, and the systems are represented by abbreviated notation of $(n{\pi}/m)$ : then using simple rules and additivity of the nonbonded effects, the order of stability can be determined. A number of examples are given in support of this analytical procedure.

• BMB Reports
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• v.47 no.7
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• pp.361-368
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• 2014

Lipid components in biological membranes are essential for maintaining cellular function. Phosphoinositides, the phosphorylated derivatives of phosphatidylinositol (PI), regulate many critical cell processes involving membrane signaling, trafficking, and reorganization. Multiple metabolic pathways including phosphoinositide kinases and phosphatases and phospholipases tightly control spatio-temporal concentration of membrane phosphoinositides. Metabolizing enzymes responsible for PI 4,5-bisphosphate (PI(4,5)P2) production or degradation play a regulatory role in Toll-like receptor (TLR) signaling and trafficking. These enzymes include PI 4-phosphate 5-kinase, phosphatase and tensin homolog, PI 3-kinase, and phospholipase C. PI(4,5)P2 mediates the interaction with target cytosolic proteins to induce their membrane translocation, regulate vesicular trafficking, and serve as a precursor for other signaling lipids. TLR activation is important for the innate immune response and is implicated in diverse pathophysiological disorders. TLR signaling is controlled by specific interactions with distinct signaling and sorting adaptors. Importantly, TLR signaling machinery is differentially formed depending on a specific membrane compartment during signaling cascades. Although detailed mechanisms remain to be fully clarified, phosphoinositide metabolism is promising for a better understanding of such spatio-temporal regulation of TLR signaling and trafficking.