• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.100-104
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• 2011

The structures of the conformers for 1,3-di-t-butyl-2,4-dinitro-tetramethoxysulfonylcalix[4]arene (1) and 1,2-di-t-butyl-3,4-dinitro-tetramethoxysulfonylcalix[4]arene (2) were optimized using DFT BLYP and mPW1PW91/6-31G(d,p) (hybrid HF-DF) calculation methods. We have analyzed the total electronic and Gibbs free energies and the differences between the various conformations (cone, partial-cone (PC), 1,2-alternate, and 1,3-alternate) of 1 and 2. For both compounds, the 1,3-alternate (1,3-A) conformers were calculated to be the most stable, which correlate very well with the experimental results. The orderings of the relative stability of 1 and 2 that resulted from the mPW1PW91/6-31G(d,p) calculations are the following: 1: 1,3-A (syn) > PC (syn) > PC (anti) > 1,2-A (anti) > CONE (syn); 2: 1,3-A (anti) > PC (anti) > PC (syn) > 1,2-A (anti) > 1,2-A (syn) > CONE (syn). The BLYP/6-31G(d) calculated IR spectra of the most stable 1,3-A conformers of 1 and 2 are compared.

• 한국환경과학회지
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• 제16권7호
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• pp.855-863
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• 2007

In order to understand the temporal distribution of pico- and nanoplankton and factors controlling its distribution at a station in Okkye Bay of Masan Bay located in the southern part of Korea, this study was conducted on two weeks interval from April 2005 to April 2006, and several abiotic and biotic factors were measured. During the study, picoplankton consisted of picoflagellates, cyanobacteria and heterotrophic bacteria, and nanoplankton consisted of nanoflagellates excluding dinoflagellates. The concentration of chlorophyll-a (chl-a) was a mean of $4.33\;{\mu}g/L$, and the nanoplanktonic ($<20\;{\mu}m$) chl-a size fraction was a mean of 39.5 % and significantly correlated with water temperature. The abundances of cyanobacteria and photosynthetic flagellates (PF) were means of $24.4{\times}10^{3}\;cells/mL\;and\;2.87{\times}10^{3}\;cells/mL$, respectively. The contribution of picoflagellates to the PF abundance varied among the sampling occasions and was a mean of 29 %, but to the PF carbon biomass was 2.6 % only. The PF abundance had significant relationships with water temperature, and silicate and TIN concentrations, suggesting that the PF abundance seemed to be primarily bottom-up regulated. The abundance of heterotrophic bacteria was a mean of $3.18{\times}10^{6}\;cells/mL$ and unlike other ecosystems it did not have relationships with chl-a and heterotrophic flagellates (HF), suggesting that bacterial abundance did not seem to be bottom-up or top-down regulated. HF mostly consisted of cells less than $5{\mu}m$ and its abundance was a mean of $2.71{\times}10^{3}\;cells/mL$. Of the HF abundance, picoflagellates occupied about 31 %, and occupied about 9 % of the HF carbon biomass. HF grazing activity on heterotrophic bacteria was relatively low and removed about 10 % of bacterial abundance, suggesting that HF might not be major consumers of bacteria and there seems to be other consumers in Okkye Bay. These results suggest that Okkye Bay may have a unique microbial ecosystem.

• 대한전자공학회논문지SD
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• 제48권6호
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• pp.1-6
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• 2011

투명 산화물 반도체 (Transparent Oxide-TFT)를 활성층과 소스/드레인, 게이트 전극층으로 동시에 사용한 비결정 indium zinc oxide (a-IZO), 절연층으로 co-sputtered $HfO_2-Al_2O_3$ (HfAIO)을 적용하여 실온에서 RF-magnetron 스퍼터 공정에 의해 제작하였다. TFT의 게이트 절연막으로써 $HfO_2$ 는 그 높은 유전상수( > 20)에도 불구하고 미세결정구조와 작은 에너지 밴드갭 (5.31eV) 으로 부터 기인한 거친계면특성, 높은 누설전류의 단점을 가지고 있다. 본 연구에서는, 어떠한 추가적인 열처리 공정 없이 co-sputtering에 의해 $HfO_2$와 $Al_2O_3$를 동시에 증착함으로써 구조적, 전기적 특성이 TFT 의 절연막으로 더욱 적합하게 향상되어진 $HfO_2$ 박막의 변화를 x-ray diffraction (XRD), atomic force microscopy (AFM) and spectroscopic ellipsometer (SE)를 통해 분석하였다. XRD 분석은 기존 $HfO_2$ 의 미세결정 구조가 $Al_2O_3$와의 co-sputter에 의해 비결정 구조로 변한 것을 확인 시켜 주었고, AFM 분석을 통해 $HfO_2$ 의 표면 거칠기를 비교할 수 있는 RMS 값이 2.979 nm 인 것에 반해 HfAIO의 경우 0.490 nm로 향상된 것을 확인하였다. 또한 SE 분석을 통해 $HfO_2$ 의 에너지 밴드 갭 5.17 eV 이 HfAIO 의 에너지 밴드 갭 5.42 eV 로 향상 되어진 것을 알 수 있었다. 자유 전자 농도와 그에 따른 비저항도를 적절하게 조절한 활성층/전극층 으로써의 IZO 물질과 게이트 절연층으로써 co-sputtered HfAIO를 적용하여 제작한 Oxide-TFT 의 전기적 특성은 이동도 $10cm^2/V{\cdot}s$이상, 문턱전압 2 V 이하, 전류점멸비 $10^5$ 이상, 최대 전류량 2 mA 이상을 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3247-3251
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• 2010

Molecular structures of the various conformers for the four stereoisomers of tetra-t-butyl-tetra-O-methylsulfinylcalix[4]arene (1) were optimized using DFT BLYP and mPW1PW91/6-31G(d,p) (hybrid HF-DF) calculation methods. We have analyzed the total electronic and Gibbs free energies and normal vibrational frequencies of 16 different structures from four major conformations (cone (CONE), partial cone (PC), 1,2-alternate (1,2-A), 1,3-alternate (1,3-A)) of the four stereoisomers [1(rccc), 1(rcct), 1(rctt), 1(rtct)]. The mPW1PW91/6-31G(d,p) calculations suggested that the $1(rccc)_{CONE}$, $1(rcct)_{PC}$, $1(rctt)_{PC}$, and $1(rtct)_{1,3-A}$ were the most stable conformations of the respective stereoisomers. These outcomes are in accordance with the experimental structures obtained from X-ray crystallography. The electrostatic repulsion between the sulfinyl and methoxy groups is a primary factor for the relative stabilities of the four different conformations. The IR spectra of the most stable conformers [$1(rccc)_{CONE}$, $1(rcct)_{PC}$, $1(rctt)_{PC}$, $1(rtct)_{1,3-A}$] of each stereoisomer were compared to each other.

• 대한약학회:학술대회논문집
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• 대한약학회 2003년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2-2
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• pp.158.1-158.1
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• 2003

We report here the results on N-acetyl-N"-methylamide of oxazolidine (Ac-Oxa-NHMe) calculated using the ab initio molecular orbital method with the self-consistent reaction field (SCRF) theory at the HF level of theory with the 6-31 +G(d) basis set. The displacement of the $\gamma$-$CH_2$ group in proline ring by oxygen atom has affected the structure of proline, cis-trans equilibrium, and rotational barrier. The up-puckered structure is found to be prevalent for the trans conformers of the Oxa amide. (omitted)

• 대한화학회지
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• 제53권6호
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• pp.640-652
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• 2009

캘릭스[n]아렌 (1-4)의 다양한 이형체들에 대한 구조들이 DFT B3LYP/6-31+G(d,p) 와 mPW1PW91/ 6-31+G(d,p) (hybrid HF-DF) 계산 방법들에 의하여 최적화 되었다. 모든 캘릭스[n]아렌 (1-4)의 다양한 이형체들 중에서, 수소결합들의 영향으로, cone 이형체가 가장 안정하였다. 그러나, 이형체들의 상대적인 안정성은 다음과 같이 서로 달랐다. 1. t-부틸캘릭스[4]아렌(1): cone > partial-cone > 1,2-alternate > 1,3-alternate. 2. t-부틸캘릭스[5]아렌(2): cone > 1,2-alternate > partial-cone > 1,3-alternate. 3. 탈부틸화된 캘릭스[6]아렌(3): cone(pinched) > partial-cone > cone(winged) ~ 1,2-alternate - 1,2,3-alternate > 1,4-alternate > 1,3-alternate > 1,3,5-alternate. 4. t-부틸캘릭스[6]아렌(4): cone(pinched) > 1,2-alternate > cone(winged) > 1,4-alternate - partial-cone > 1,2,3-alternate > 1,3,5-alternate > 1,3-alternate. 분자 내부의 수소결합의 개수와 강도들이 캘릭스[n]아렌의 다양한 이형체들의 상대적인 안정성에 가장 영향을 많이 미치는 인자들이었다. 두 가지 서로 다른 계산방법들 (B3LYP과 mPW1PW91)에 대한 여러 가지 이형체들에서의 수소결합 길이들이 비교되었다.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• Bulletin of the Korean Chemical Society
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• 제25권5호
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• pp.704-710
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• 2004

A poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) (PHDP) was prepared and its luminescence in tetrahydrofuran (THF) was studied. When PHDP is excited by UV light, it produces very strong blue luminescence. The quantum yield of PHDP (Q = 36.9%) is much greater than that of the monomer, 1-hexyl-3,4-dimethylpyrrole (HDP) with Q = 0.61%. The principal luminescence of PHDP has a single decay component with ca. 1 ns, whereas the decay of HDP is complicated. The molecular structure and conformational behavior of HDP and the oligomers up to trimer have been also determined by ab initio Hartree-Fock (HF/6-31$G^{**}$), density functional theory (DFT-B3LYP/6-31$G^{**}$), and semiempirical (ZINDO) methods. According to the results of calculations, it is proposed that the enhanced quantum yield of the polymer PHDP results mostly from the ${\pi}$-conjugation between neighboring pyrrole rings.

• Bulletin of the Korean Chemical Society
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• 제23권6호
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• pp.891-896
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• 2002

The structures and energies of p-tert-butylcalix[4]crown-6-ether(1) in various conformers and their alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. We have tried to obtain the relative affinity of partial-cone and 1,3-alternate conformers of 1 for alkyl ammonium guests by comparison with its cone-shaped analogue. We have also calculated the relative complexation efficiency of these host-guest complexes focusing on the binding sites of $crown-\sigma-enther$ moiety or benzene-rings pocket of the host molecule 1. These calculations revealed that the crown moiey has better complexation efficiency than upper rim part of calyx[4]arene that is in similar trend to the cone-shaped complexes.

• Bulletin of the Korean Chemical Society
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• 제35권4호
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• pp.989-993
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• 2014

The molecular structures of 2,6-diaza-1,3,5,7-tetraoxaspiro[3,3]heptane (1) and its dinitro derivative, 2,6-dinitro-2,6-diaza-1,3,5,7-tetraoxaspiro[3,3]heptane (2), were fully optimized without symmetry constraints at $HF/6-31G^*$ level of theory. A bisected conformation with respect to the ring is preferred with a $C_2$ symmetric structure. The density of each molecule in the crystalline state was estimated to 1.12 and 2.36 $g/cm^3$ using PM3/VSTO-3G calculations from the molecular volume. The heat of formation was calculated for two compounds at the CBS-4M level of theory. The detonation parameters were computed using the EXPLO5 software: D = 6282 m/s, $P_{C-J}$ = 127 kbar for compound 1, D = 7871 m/s, $P_{C-J}$ = 307 kbar for compound 2, and D = 6975 m/s, $P_{C-J}$ = 170 kbar for 60% compound 2 with 40% TNT. Specific impulse of compound 1 in aluminized formulation when used as monopropellants was very similar to that of the conventional ammonium perchlorate in the same formulation of aluminum.