• Bulletin of the Korean Chemical Society
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• 제4권4호
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• pp.189-191
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• 1983

• Bulletin of the Korean Chemical Society
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• 제27권5호
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• pp.718-724
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• 2006

The heterogeneous association behaviour of various concentration binary mixtures of mono alkyl ethers of ethylene glycol with ethyl alcohol were investigated by dielectric measurement in benzene solutions over the entire concentration range at 25 ${^{\circ}C}$. The values of static dielectric constant $\epsilon_0$ of the mixtures were measured at 1 MHz using a four terminal dielectric liquid test fixture and precision LCR meter. The high frequency limiting dielectric constant $\epsilon_\infty$ values were determined by measurement of refractive index $n_D$ ($\epsilon_\infty\;=\;n_D\;^2$). The measured values of $\epsilon_0$ and $\epsilon_\infty$ were used to evaluate the values of excess dielectric constant $\epsilon^E$, effective Kirkwood correlation factor $g^{eff}$ and corrective correlation factor $g_f$ of the binary polar mixtures to obtain qualitative and quantitative information about the H-bond complex formation. The non-linear behaviour of the observed $\epsilon_0$ values of the polar molecules and their mixtures in benzene solvent confirms the variation in the associated structures with change in polar mixture constituents concentration and also by dilution in non-polar solvents. Appearance of the maximum in $\epsilon^E$ values at different concentration of the polar mixtures suggest the formation of stable adduct complex, which depends on the molecular size of the mono alkyl ethers of ethylene glycol. Further, the observed $\epsilon^E$ < 0 also confirms the heterogeneous H-bond complex formation reduces the effective number of dipoles in these polar binary mixtures. In benzene solutions these polar molecules shows the maximum reduce in effective number of dipoles at 50 percent dilutions. But ethyl alcohol rich binary polar mixtures in benzene solvent show the maximum reduce in effective number of dipoles in benzene rich solutions.

• Bulletin of the Korean Chemical Society
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• 제25권6호
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• pp.838-842
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• 2004

Amyloid peptide (A${\beta}$) is the major component of senile plaques found in the brain of patient of Alzheimer's disease. ${\beta}$-amyloid peptide (25-35) (A${\beta}$25-35) is biologically active fragment of A${\beta}$. The three-dimensional structure of A${\beta}$25-35 in aqueous solution with 50% (vol/vol) TFE determined by NMR spectroscopy previously adopts an ${\alpha}$-helical conformation from $Ala^{30}$ to $Met^{35}$. It has been proposed that A${\beta}$(25-35) exhibits pH- and concentration-dependent ${\alpha}-helix{\leftrightarrow}{\beta}$sheet transition. This conformational transition with concomitant peptide aggregation is a possible mechanism of plaque formation. Here, in order to gain more insight into the mechanism of ${\alpha}$-helix formation of A${\beta}$25-35 peptide by TFE, which particularly stabilizes ${\alpha}$-helical conformation, we studied the secondary-structural elements of A${\beta}$25-35 peptide by molecular dynamics simulations. Secondary structural elements determined from NMR spectroscopy in aqueous TFE solution are preserved during the MD simulation. TFE/water mixed solvent has reduced capacity for forming hydrogen bond to the peptide compared to pure water solvent. TFE allows A${\beta}$25-35 to form bifurcated hydrogen bonds to TFE as well as to residues in peptide itself. MD simulation in this study supports the notion that TFE can act as an ${\alpha}$-helical structure forming solvent.

• Bulletin of the Korean Chemical Society
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• 제4권5호
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• pp.223-227
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• 1983

A molecular dynamic computer experiment was performed on a system of 108 particles composed of a single polymer chain and solvent molecules. The state considered was in the immediate neighborhood of the triple point of the system. The polymer itself is an analog of a freely jointed chain. The Lennard-Jones potential was used to represent the interactions between all particles except for that between the chain elements forming a bond in the polymer chain, for which the interaction was expressed by a harmonic potential. The self-diffusion coefficient and velocity autocorrelation function (VACF) of a polymer were calculated at various chain lengths $N_p$, and various interaction strengths between solvent molecules and a polymer chain element. For self-diffusion coefficients D, the Einstein relation holds good; as chain length $N_p$ increases the D value decreases, and D also decreases as ${\varepsilon}_{cs}$ (the interaction parameter between the chain element and solvent molecules) increases. The relaxation time of velocity autocorrelation decreases as ${\varepsilon}_{cs}$ increases, and it is constant for various chain lengths. The diffusion coefficients in various conditions reveal that our systems are in a free draining limit as is well known from the behavior of low molecular weight polymers, this also agrees with the Kirkwood-Riesman theory.

• Restorative Dentistry and Endodontics
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• 제34권1호
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• pp.42-50
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• 2009

장기적인 상아질 접착의 내구성 악화는 접착층과 혼성충의 친수성 부위에서의 가수분해에 의해 일어나는 것으로 보고 되고 있다. 본 연구의 가설은 콜라겐 망상체를 유기용매로 프라이밍하면 콜라겐 조직을 붕괴시키지 않고 수분을 밀어내고 소수성 단량체와 유기용매로 이루어진 접착제가 침투하여 접착강도를 얻을 수 있다는 것이다. 두 소수성 단량체인 Bisphenol-A-glycidylmethacrylate (Bis-GMA)와 triethyleneglycol dimethacrylate (TEGDMA)를 아세톤, 에탄올 또는 메탄올에 용해시켜 세 가지의 실험용 접착제를 준비하였다. 산 부식과 수세과정 후에, 접착제를 습윤 상아질 표면(습윤 접착)이나 동일한 용매로 프라이밍 된 상아질 표면(용매 프라이밍 접착)에 적용하였다. 48시간 후와 1개월 후, 및 10,000회의 열순환 후에 미세인장결합강도를 측정하였다. 접착계면은 주사전자현미경을 이용하여 관찰하였다. 접착 방법에 무관하게 대부분의 시편의 접착계면에서 잘 발달된 혼성층을 관찰할 수 있었고, 가장 높은 평균 미세인장결합강도는 에탄올을 포함하는 접착제의 48시간 후 시편에서 관찰되었다. 용매를 이용하여 프라이밍하는 접착 방법에서는 에탄올이나 메탄올을 포함하는 접착제에서 열순환 후에 미세인장접착강도가 증가하는 경향을 보였다. 그러나, 습윤 접착의 경우에는 시효처리 후 미세인장결합강도의 증가가 관찰되지 않았다. 본 연구에서 에탄올을 이용한 상아질 프라이밍으로 우수한 접착력을 얻을 수 있었고, 열순환 후 접착력 이 더욱 증가하였다.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2976-2980
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• 2012

Nitrile-forming eliminations from (E)-2,4-$(NO_2)_2C_6H_2CH=NOC_6H_4-2-X-4-NO_2$ (1a-e) promoted by $R_3N$ in MeCN have been studied kinetically. The reactions are second-order and exhibit Br$\ddot{o}$nsted ${\beta}$ = 0.83-1.0 and ${\mid}{\beta}_{lg}{\mid}$ = 0.41-0.46. The results have been interpreted in terms of highly E1cb-like transition state with extensive $C_{\beta}$-H bond cleavage and limited $N_{\alpha}$-OAr bond cleavage. Comparison with existing data reveals that the structure of the transition state changes from E2-central to highly E1cb-like either by the change of the ${\beta}$-aryl group from Ph to 2,4-dinitrophenyl under the same condition or by the base-solvent system variation from $EtO^-$-EtOH to $Et_3N$-MeCN for a given substrate (1a-e).

• 대한화학회지
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• 제21권4호
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• pp.262-269
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• 1977

1-염화 및 2-염화나프탈렌술포닐의 가용매 분해반응을 아세톤-물혼합용매속에서 전기전도도법으로 실시하여 여러가지 용매 파라미터 및 활성화파라미터와 관련지워 용매효과와 반응 메카니즘을 논의하였다. 반응은 $S_N2$ 메카니즘으로 진행되나 물함량이 크면 bond-breaking이 약간 증가한다. 또한 바닥상태 안정화효과와 천이상태에서의 peri-hydrogen효과 때문에 2-나프탈렌 화합물의 반응속도가 1-나프탈렌 화합물의 반응속도보다 빨랐으며 이 효과는 에탄올-물 혼합용매속에서와 비슷하였다.

• Bulletin of the Korean Chemical Society
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• 제9권1호
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• pp.1-4
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• 1988

Rates of solvolysis of trans-[Co$(N-eten)_2Cl_2$]$^+$ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ${\Delta}V^{\neq}$ obtained from pressure effect on the rate constants were 2.55∼ 5.83 $cm^3mol^{-1}$. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant ($Ds^{-1}$). The gradient, m of Grunwald-Winstein plot for the trans-[Co$(N-eten)_2Cl_2$]$^+$ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.

• 대한화학회지
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• 제19권4호
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• pp.233-239
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• 1975

세개의 二重結合에 衣하여 conjugate된 비대칭화합물 cis-2-bitenedialdioxime의 두 oxime group의 configuration을 溶媒, 溫度 및 濃度의 影響에 대한 NMR 硏究로서 決定하였다. 溶液狀態에서의 이 化合物은 $-35^{circ}$∼$-95^{\circ}C$의 溫度條件下에서는 항상 "syn-syn" configuration으로 存在함을 알았다. 또한 이 化合物의 oxime group과 溶媒사이의 水素結合의 相對的强度와 溫度 및 濃度에 의 피리딘의 考察하고 몇가지 水素結合의 모델을 提示하였다. 特히 피리딘溶媒 속에서는 水素結合은 한 영향을 窒素가 갖고 있는 非共有電子雙에 衣해서 일어나지 않고, oxime 의 hydroxyl proton과 피리딘의 $\pi$軌道函數 사이에 形成되는 $\pi$-착물의 結果임을 알았다.

• 대한화학회지
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• 제41권2호
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• pp.63-68
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• 1997

등유전성 용매내에서 분자간 상호작용과 액체구조에 대한 정보를 얻기 위하여 양성자성 용매(protic solvent)인 ROH(R=Me, Et)와 양극성 비양성자성 용매(dipolar aprotic solvent)인 MeCN,$Me_2CO,\;MeNO_2(or EtNO_2)$간의 이성분 혼합물에서 각 성분의 분몰 용해엔탈피를 열량계법으로 측정하고 이를 이용하여 mixing과정에 대한 잉여엔탈피를 결정하였다. 이로부터 두 성분간의 수소결합 세기는$ROH-ROH>ROH-Me_2CO>ROH-MeCN>ROH-MeNO_2(or EtNO_2)$순으로 감소하며, ROH의 수소결합주게 산도(hydrogen bond donor acidity)는 MeOH>EtOH의 순으로 감소하며 이로부터 이성분 액체혼합물이 형성될 때의 에너지론(energetics)에 미치는 가장 강한 상호작용이 특별한 수소결합에 기인됨을 알 수 있었다.