• Macromolecular Research
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• 제10권2호
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• pp.91-96
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• 2002

To explore the effects of intramolecular interactions within the copolymer on the phase separation behavior of polymer blends, copolymers having two different types of intramolecular interactions, i.e., intramolecular repulsion and intramolecular attraction were prepared . In this study, poly(styrene-co-methylmethacrylate) (P(S-MMA)) having intramolecular repulsion caused by positive interaction between styrene and MMA and poly(styrene-co-ethyl-methacrylate) (P(S-EMA)) and poly(styrene-co-cyclohexylmethacrylate) (P(S-CHMA)) having intramolecular attraction caused by negative interaction between styrene and methacrylate were blended with tetramethyl poly-carbonate (TMPC). The phase behavior of blends was examined as a function of copolymer composition and blend composition. TMPC formed miscible blends with styrenic copolymers containing less than certain amount of methacrylate. The phase separation temperature of TMPC blends with copolymer such as P(S-MMA) and P(S-EMA), first increases with methacrylate content, goes through a maximum and then decreases just prior to the limiting content of methacrylate for miscibility, while that of TMPC blends with P(S-CHMA) always decreases. The calculated interaction energy for TMPC-P(S-EMA) pair is negative and monotonically increases with EMA content of the copolymer. Such behavior contradicted the general notion that systems with more favorable energetic interactions have higher LCST, The detailed inspection of the lattice-fluid theory related to the phase behavior was performed to explain such behavior.

• Bulletin of the Korean Chemical Society
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• 제6권1호
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• pp.23-29
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• 1985

The charge-transfer complexing properties of 1-methyl nicotinamide (MNA), an acceptor, and adenine, a donor, were investigated in water and SDS micellar solutions in relation to the intramolecular interaction in nicotinamide adenine dinucleotide ($NAD^+$). The spectral and thermodynamic parameters of MNA-indole and methyl viologen-adenine complex formations were determined, and the data were utilized to evaluate the charge-transfer abilities of MNA and adenine. The electron affinity of nicotinamide was estimated to be 0.28 eV from charge-transfer energy $of{\sim}300$ nm for MNA-indole. The large enhancement of MNA-indole complexation in SDS solutions by entropy effect was attributed to hydrophobic nature of indole. The complex between adenine and methyl viologen showed an absorption band peaked near 360 nm. The ionization potential of adenine was evaluated to be 8.28 eV from this. The much smaller enhancement of charge-transfer interaction involving adenine than that of indole in SDS solutions was attributed to weaker hydrophobic nature of the donor. The charge-transfer energy of 4.41 eV (280 nm) was estimated for nicotinamide-adenine complex. The spectral behaviors of $NAD^+$ were accounted to the presence of intramolecular interaction in $NAD^+$, which is only slightly enhanced in SDS solutions. The replacement of nicotinamide-adenine interaction in $NAD^+$ by intermolecular nicotinamide-indole interaction in enzyme bound $NAD^+$, and guiding role of adenine moiety in $NAD^+$ were discussed.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4195-4198
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• 2011

Intramolecular ${\pi}-{\pi}$ and ${\sigma}-{\pi}$ interactions are omnipresent for numerous energetic and structural phenomena in nature, and the exact description of these nonbonding interactions plays an important role in the accurate prediction of the three-dimensional structures for numerous interesting molecular systems such as protein folding and polymer shaping. We have selected two prototype molecular systems for benchmarking calculations of intramolecular ${\pi}-{\pi}$ and ${\sigma}-{\pi}$ interactions. Accurately describing conformational energy of such systems requires highly elaborate but very expensive ab initio methods such as coupled cluster singles, doubles, and (triples) (CCSD(T)). Our calculations reveal a double hybrid density functional incorporating dispersion correction (B2PLYP-D) that agrees excellently with the CCSD(T) results, indicating that B2PLYP-D can serve as a practical method of choice.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2527-2530
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• 2010

The stereoselectivity of the intramolecular Diels-Alder reactions of 1 and its derivatives were investigated by ab initio calculations. The stereoselectivity mainly originates from the steric repulsion and the orbital interactions. The additional s-cis and s-trans conformations by introducing the carbonyl group at the neighbor of diene or dienophile may change the stereoselectivity, hence this kind of substitution can be utilized for stereoselectivive asymmetric synthesis.

• 한국염색가공학회지
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• 제20권4호
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• pp.21-30
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• 2008

To understand the complex hydrogen bonding structure, several phenolic derivatives and benzoxazine model compounds are synthesized and characterized by Fourier transform infrared spectroscopy (FT-IR). The estimation of molar extinction coefficients for various types of hydrogen bonding species is systematically carried out by the curve-resolving of FT-IR spectra. The distribution of hydrogen bonding species in benzoxazine model dimers is quantitatively analyzed. It is revealed that benzoxazine dimers and BA-a polybenzoxazine are mainly composed of intramolecular interaction rather than intermolecular interaction.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1631-1633
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• 2009

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1326-1330
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• 2010

Evidences have proved the versatile role of sulfur atom in supramolecular chemistry. $^1$Presence of S atom in the molecule usually results in the specific structural properties of molecules. In the present study, $S{\cdots}arene$, $N{\cdots}arene$, $CH{\cdots}{\pi}$, $CH{\cdots}S$ and $CH{\cdots}N$ type of weak interactions stabilize the conformation and self assembly of symmetrical as well as dissymmetrical molecules.

• Bulletin of the Korean Chemical Society
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• 제17권1호
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• pp.93-95
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• 1996

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2719-2723
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• 2012

A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).

• 폴리머
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• 제28권2호
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• pp.111-120
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• 2004

반복 단위마다 양전하를 띄고 있는 폴리(디알릴디메틸암모늄 클로라이드) (PDADMAC)와 음이온 계면활성제인 도데실 황산 소듐 (SDS)와의 상호작용을 광산란법, 탁도법 및 형광법을 이용하여 조사하였다. 0.3 M NaCl 수용액에서의 PDADMAC는 마치 좋은 용매에서 팽창되어 있는 중성 고분자처럼 존재하나, SDS를 첨가함에 따라 이들 사이의 상호작용은 두 개의 임계 응집 농도로써 기술할 수 있었다. 첫 번째, 사슬 내 임계 응집 농도에서는 하나의 고분자 사슬 내에서 SDS의 마이셀화 과정으로써 [SDS]/[DADMAC] 0.06 정도에서 일어나며, 이 복합체 크기는 오히려 마이셀 형성되기 직전에 최대 값을 나타내고, 마이셀이 형성된 후부터는 일부 고분자 사슬도 마이셀 형성에 참여하기 때문에 SDS 첨가에 따라 점차로 수축되기 시작하였다. 두 번째, 사슬간 임계 응집 농도는 탁도 법에 의해 [SDS]/[DADMAC] 0.5에서 측정되었고, 이 두 번째 임계 응집농도 이상에서는 많은 마이셀들로 장식된 고분자 사슬들 사이의 응집화에 의한 거대한 응집체가 형성된다.