• Bulletin of the Korean Chemical Society
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• 제18권4호
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• pp.415-424
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• 1997

Conformational flexibilities of the GlcNAc(β1,3)Gal(β)OMe are investigated through NMR spectroscopy and molecular modeling. Adiabatic energy map generated with a dielectric constant of 50 contains three local minima. All of the molecular dynamics simulations on three local minimum energy structures show fluctuations between two low energy structures, N2 at φ=80° and ψ=60° and N3 at φ=60° and ψ=-40°. We have presented adequate evidences to state that GlcNAc(β1,3)Gal(β)OMe exists in two conformationally discrete forms. Two state model of N2 and N3 conformers with a population ratio of 40:60 is used to calculate the effective cross relaxation rate and reproduces the experimental NOEs very well. Molecular dynamics simulation in conjunction with two state model proves successfully the dynamic equilibrium existed in GlcNAc(β1,3)Gal(β)OMe and can be considered as a powerful method to analyze the motional properties in the structure of carbohydrate. This observation also cautions against the indiscriminate use of a rigid model to analyze NMR data.

• Bulletin of the Korean Chemical Society
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• 제18권10호
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• pp.1076-1082
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• 1997

The infrared, Raman, and jet-cooled laser-induced fluorescence excitation spectra of 1,2,3,4-tetrahydronaphthalene have been recorded and analyzed. The observed vibrations have been assigned to understand the conformational behaviors in its electronic ground (S0) and excited (S1) states. Ab initio at the HF/6-31G** level and molecular mechanics (MM3) force field calculations have been carried out to generate the complete normal mode frequencies of the molecule in its S0 state. The vibrational frequencies calculated from the ab initio method show a better agreement with the observed infrared and Raman frequencies than those calculated from the MM3 method. In several cases, the normal mode calculations were very helpful to clarify some ambiguities of previous assignments. In addition, the ring inversion process between two twisted conformers of 1,2,3,4-tetrahydronaphthalene has been reexamined utilizing ab initio calculation. The results show that the ring inversion energy is in the range of 3.7-4.3 kcal/mol which is higher than the previously reported AM1 value of 2.1 kcal/mol.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1145-1148
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• 1999

1H NMR spectra of methyl-, ethyl-, propyl-, isopropyl-, butyl-, N-methylethyl-, N-methylpropyl-, and N-methylisopropylamine coordinated to the paramagnetic 11-tungstocobalto(II)silicate anion (SiW11Co) in dimethylsulfoxide-d6 or dimethylformamide-d7 are reported. For these complexes the ligand exchange is slow on the NMR time scale and pure 1H NMR signals have been observed at room temperature. No complex is detected in D2O. From the pseudocontact shifts of the CH2 and CH3 groups in ethylamine the energy of the gauche conformers with respect to the anti conformer is estimated. Two diastereotopic protons in the CH2 group of N-methylethylamine have quite different chemical shifts especially at low temperatures (e.g. 48.5 vs. 19.4 ppm at -10℃). This may be attributed mainly to the different positions of the two protons in the most stable (gauche) conformer.

• Bulletin of the Korean Chemical Society
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• 제10권3호
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• pp.227-230
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• 1989

The lowest excited state of styrylquinoxaline (StQx) has been studied by the SCF-MO-CI P-P-P and MM2 method. Results suggest that the lowest excited state is of a ${\pi},{\pi}^{\ast}(S_1$) nature with the n,${\pi}^{\ast}(S_2)$ state lying slightly above it. On the basis of these calculations the observed electronic spectra are discussed. The calculated absorption spectra are qualitatively similar to experimental ones with their characteristic visible bands. MM2 force field calculation suggested that the postulated conformers are different from each other in energy and planarity and are seperated by a barrier of about 4 Kcal/mole.

• Bulletin of the Korean Chemical Society
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• 제6권5호
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• pp.300-303
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• 1985

To understand the nature of the linkage between chromophore and apoprotein in the photoreceptor of Stentor coeruleus, a conformational analysis has been carried out on the dipeptide amides linked to the chromophore hypericin using an empirical potential function. The conformational energies for the dipeptide amides of Glu (OHyp)-X-NHMe, where X = Leu, Phe, Asp, and Tyr, have been calculated to investigate the influence of peptide residues in stabilizing conformers. It was found that the increase of acidity of hypericin upon photoexcitation may be facilitated by the formation of intramolecular hydrogen bonds between hydroxyl groups of hypericin and carbonyl groups of peptide backbone, and that the stabilities of dipeptide amides do not significantly depend on peptide residues directly linked to chromophore.

• Bulletin of the Korean Chemical Society
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• 제21권3호
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• pp.300-304
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• 2000

The B3LYP method based on the density functional theory(DFT) is shown to be much better than the ab initio MP2 method for structural determination of diphosphadithiatetrazocine systems having transannular S--S bonding. The presence of bonding between the two sulfur atoms across the cyclic ring is theoretically confirmed in the case of the neutral diphosphadithiatetrazocine. The S--S dobding disappears in the ionized species. The planarity of the dicationic heterocyclic ring system turns out to be closely associated with the $\pi-electron$ delocalization over the entire ring as well as the N-S-N bonds, which become stiffened upon ionizaiton. In the case of dianionic species, the chair-boat and chair conformers are nearly degenerate and far more stable than the crown conformer.

• 한국산학기술학회논문지
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• 제19권7호
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• pp.95-104
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• 2018

이성질체의 형태는 수용액 상태에서 종종 안정성과 반응성 등의 기본상태 뿐만 아니라 사슬성장 및 접힘 과정으로 인하여 형태형성에 영향을 주기 때문에 올리고펩티드의 형태를 이해하는 것이 중요하다. 본 논문에서는 L-알라닌(LA), 글리신(G) 5량체 모델의 무수 및 수화물(수화율; h/1) 상태의 구조와 에너지를 4가지 형태이성질체 (베타-확장형;= t-/t+, $PP_{II}$형; g-/t+, $PP_{II}$-유사형; g-/g+ 및 알파-나선형; g-/g-)에 대하여 B3LYP/6-31G(d,p)를 이용하여 양자화학계산(QCC) 방법으로 분석하였다. 구조최적화는 밀도함수 이론(DFT)으로써 B3LYP를 사용하였으며, 기본설정(Basic set)으로는 6-31G(d,p)를 이용하였다. 이미노 양성자(NH)를 갖는 LA와 G에서 베타-확장형, $PP_{II}$-유사형, 알파-나선형의 3가지 형태가 얻어졌으며, 대부분 물 분자가 $PP_{II}$-유사형과 알파-나선형에서는 CO-HN 분자 내 수소결합 사이에 주로 삽입되었고, 베타-확장형은 CO기에 부착되었다. 또한, LA와 G에서 $PP_{II}$-유사형 형태이성질체가 무수 및 수화물 상태에서 가장 안정적이었으며, $PP_{II}$ 형태이성질체는 얻어지지 않았다. LA에 대한 결과는 알라닌 올리고펩티드의 안정적인 형태가 주로 $PP_{II}$라고 보고한 다른 연구의 실험적 및 이론적인 결과와는 상이했다. 올리고펩티드 형태이성질체의 생성패턴과 안정성이 CO-HN의 분자 내 수소결합의 존재 여부 또는 출발 아미노산 내 $NH_2$기의 존재 여부에 강한 영향을 받는 것을 알 수 있었다.

• 대한화학회지
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• 제53권5호
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• pp.521-529
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• 2009

1,3-디메톡시-티아캘릭스[4]크라운-5-에테르 (3)의 다양한 이형체들(cone_oo, cone_oi, pc_oo, pc_io, pc_oi, pc_ii, 13a_oo, 13a_io)에 대한 구조들이 DFT B3LYP/6 - 31 + G(d,p)와 mPW1PW91/6 - 31 + G (d,p) (hybrid HF-DF) 계산 방법들에 의하여 최적화 되었다. 13a_oo (1,3-alternate 이형체에서 두 개의 메 톡시기가 모두 밖으로 향해 있는 구조)가 가장 안정하였으며, 기존에 보고된 실험 결과와 잘 일치하였다. mPW1PW91/6 - 31 + G(d,p) 계산에 의한 상대적인 안정성은 다음과 같았다: 13a_oo (가장 안정) > 13a_io$\sim$ pc_io$\sim$cone_oo > cone_oi$\sim$pc_oo$\sim$pc_oi > pc_ii.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1323-1328
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• 2014

Molecular structures of the various conformational stereoisomers of 2,8,14,20-cyanophenyl pyrogallol[4]arenes 1 were optimized using the mPW1PW91 (hybrid Hartree-Fock density functional) calculation method. The total electronic and Gibbs free energies and the normal vibrational frequencies of the different structures from three major conformations (CHAIR, TABLE, and 1,2-Alternate) of the four stereoisomers [1(rccc), 1(rcct), 1(rctt), and 1(rtct)] were analyzed. The mPW1PW91/6-31G(d,p) calculations suggested that $1(rcct)_{1,2-A}$, 1(rctt)CHAIR, and $1(rtct)_{CHAIR}$ were the more stable conformations of the respective stereoisomers. Hydrogen bonding is the primary factor for the relative stabilities of the various conformational isomers, and maximizing the ${\pi}-{\pi}$ interaction between the cyanophenyl rings is the secondary factor. The calculated IR spectra of the more stable conformers [$1(rctt)_{CHAIR}$, $1(rcct)_{1,2-A}$, $1(rtct)_{CHAIR}$] were compared with the experimental IR spectrum of $1(rtct)_{CHAIR}$.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1187-1194
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• 2011

The hydrogen abstraction reaction of $CF_3CH_2CHO$ + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans- and cis-$CF_3CH_2CHO$, have been located, and there are four distinct OH hydrogen-abstraction channels from t-$CF_3CH_2CHO$ and two channels from c-$CF_3CH_2CHO$. The required potential energy surface information for the kinetic calculation was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants, which were calculated using improved canonical transitionstate theory with small-curvature tunneling correction (ICVT/SCT) were fitted by a four-parameter Arrhenius equation. It is shown that the reaction proceeds predominantly via the H-abstraction from the -CHO group over the temperature range 200-2000 K. The calculated rate constants were in good agreement with the experimental data between 263 and 358 K.