• Bulletin of the Korean Chemical Society
• /
• v.25 no.4
• /
• pp.553-556
• /
• 2004

In this study we have performed ab initio computer simulations to investigate the conformational characteristics of the tetraethyl (1) and triethyl ester (2) of p-tert-butylcalix[4]arene. The structures of different conformational isomers for each compound have been optimized using ab initio RHF/6-31G methods. After optimization, B3LYP/6-31+G(d,p) single point calculations of the final structures are done to include the effect of electron correlation and the basis set with diffuse function and polarization function. Relative stability of tetraethyl ester (1) of p-tert-butylcalix[4]arene is in following order: cone (most stable) > partial cone > 1,3- alternate > 1,2-alternate isomer. Relative stability of triethyl ester (2) of p-tert-butylcalix[4]arene is in following order: cone (most stable) > 2-partial cone > 1-partial cone > 3-partial cone ~ 1,3-alternate ~ 1,2- alternate isomer.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.4
• /
• pp.555-562
• /
• 2002

Isomers based on the RS and EZ geometrical isomerism of the neutral, deprotonated species of HMPAO and their complexes with zinc(Ⅱ) ion have been investigated by semiempirical AM1 optimization method. The Hartree-Fock energies on AM1 geometries o f HMPAO species were calculated with HF/6-31G* methods. Twenty-two isomers of the neutral and twenty isomers of the deprotonated species of HMPAO have been found. The presence of four EE-series isomers of both zinc(Ⅱ) complexes with the neutral and deprotonated HMPAO have been expected and the SREE typical isomer of both types of complexes is the most stable isomer. Energies of complexation of zinc(Ⅱ)/HMPAO isomers with AM1 geometries were calculated by HF/ 6-31G*method. Due to the complexations with zinc(Ⅱ), the structural reorganizations of some isomers of the neutral HMPAO have been occurred. The optimized geometrical parameters of the related conformations have been discussed in terms of their stabilities and existences.

• BMB Reports
• /
• v.36 no.2
• /
• pp.167-172
• /
• 2003

The kinetics of thermal inactivation of copper-containing amine oxidase from lentil seedlings were studied in a 100 mM potassium phosphate buffer, pH 7, using putrescine as the substrate. The temperature range was between $47-60^{\circ}C$. The thermal inactivation curves were not linear at 52 and $57^{\circ}C$; three linear phases were shown. The first phase gave some information about the number of dimeric forms of the enzyme that were induced by the higher temperatures using the "conformational lock" pertaining theory to oligomeric enzyme. The "conformational lock" caused two additional dimeric forms of the enzyme when the temperature increased to $57^{\circ}C$. The second and third phases were interpreted according to a dissociative thermal inactivation model. These phases showed that lentil amine oxidase was reversibly-dissociated before the irreversible thermal inactivation. Although lentil amine oxidase is not a thermostable enzyme, its dimeric structure can form "conformational lock," conferring a structural tolerance to the enzyme against heat stress.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.8
• /
• pp.1229-1234
• /
• 2005

The conformational, configurtational behavior and the structure of N-2-(1,4-Dioxane)-N'-(4-methylbenzenesulfonyl)-O-(4-methylphenoxy) isourea 1 has been studied using DFT method. Calculations predict the imidoyl amino group of the dioxane ring prefers axial conformation and that the tosyl and tolyl groups about the C=N bond retain E configuration. The anomeric effect controls the population of dioxane ring conformers, and anomers. Intramolecular hydrogen bonds contribute to the stability of E isomers. The computational analysis of 1 complements the X-ray findings.

• Bulletin of the Korean Chemical Society
• /
• v.4 no.4
• /
• pp.157-161
• /
• 1983

Ab initio calculations were performed on systems containing various basic ${\pi}$ fragments and glycines to generalize the ${\pi}$-nonbonded interaction (${\pi}$-NBI) method of determining relative conformational and configurational stability of organic molecules. It was found that the relative stability of conformational isomers can be determined in general by the simple application of the ${\pi}$-NBI method, but the method is not applicable to the geometrical isomerism in which stronger structural factors are involved. The ${\pi}$-NBI effect of a crowded ${\pi}$-structure ($n{\pi}/m$) is maximum for the system in which n is equal to m. In crowded structures containing heteroatoms, ${P^{\pi}}_{ij}$ values of 4N+1 system may become negative, but this sign reversal does not invalidate the predictions based on the ${\pi}$-NBI method.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.1323-1328
• /
• 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
• /
• v.33 no.9
• /
• pp.3111-3114
• /
• 2012

• Bulletin of the Korean Chemical Society
• /
• v.13 no.3
• /
• pp.296-306
• /
• 1992

$^{13}C$ spin-lattice relaxation times were measured for n-alkanes of moderate chain length, ranging from n-octane to n-dodecane, under the condition of proton broad-band decoupling within the temperature range of 248-318 K in order to gain some insight into basic features of segmental motions occurring in long chain ploymeric molecules. The NOE data showed that except for methyl carbon-13 dipole-dipole interactions between $^{13}C$ and directly bonded $^1H$ provide the major relaxation pathway, and we have analyzed the observed $T_1data$ on the basis of the internal rotational diffusion theory by Wallach and the conformational jump theory by London and Avitabile. The results show that the internal rotational diffusion constants about C-C bonds in the alkane backbone are all within the range of $10^9\;-10^10\;sec^{-1}$ in magnitude while the mean lifetimes for rotational isomers are all of the order of $10^{-11}\;-10^{-10}$ sec. Analysis by the L-A theory predicts that activation energies for conformational interconversion between gauche and trans form gradually increase as we move from the chain end toward the central C-C bond and they are within the range of 2-4 kcal/mol for all the compounds investigated.

• Journal of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.500-505
• /
• 1991

The stereoselectivity on the electron-transfer reaction between optical active ${\bigwedge}$-[CO(EDDS)]- and conformationally restricted complex $[Co({\pm}chxn)_3]^{2+}$ has been examined in aqueous solution. The products are four conformational isomers $(lel_3,\;lel_2ob,\;lelob_2,\;and\;ob_3)$ of ${\bigwedge}$-[Co(chxn)$_3]^{3+}$ with optical purities of 22% e.e, 25% e.e, 11% e.e, and 10% e.e, respectively. The reaction between ${\bigwedge}$-[CO(EDDS)]- and $[Co({\pm}chxn)_3]^{2+}$ in DMSO produced lel3-${\Delta}$ and lel2ob-${\Delta}$-[Co(chxn)$_3]^{3+}$ whose optical purities are 100% e.e, and 75% e.e, respectively.

• Textile Coloration and Finishing
• /
• v.2 no.4
• /
• pp.245-250
• /
• 1990

Copolyspiroacetals were synthesized by interfacial polycondensation from 3, 9-bis(4-hydroxyphenyl)-2, 4, 8, 10-tetraoxaspiroundecane(SAB) and 4, 4'-biphenol(BP) with sebacoyl chloride. These copolymers were soluble in polar solvent such as phenol/tetrachloroethane and sulfuric acid, and exibited good thermal stability. But they did not exhibit thermotropic mesophases. The structures of spiroacetal moiety were observed by computer-aided-modeling that had two types of conformational isomers and not linear and/or not planar conformations.