• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2111-2116
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• 2013

This paper reports substituent effects on the conformational changes in polyaniline (PAni) derivatives. PAni, poly-o-toluidine (POT), and poly-o-anisidine (POA) were formed by potentiodynamic electropolymerization in aqueous solution containing (+)-camphorsulfonic acid (CSA) as a dopant. UV-Vis spectroscopy and cyclic voltammetry measurements revealed that the methyl group showed a greater steric hindrance than the methoxy group. Further, the doping level decreased with increasing steric hindrance. The sign pattern of the circular dichroism (CD) bands for POA was opposite to that for PAni. However, no CD bands were observed in POT. The steric hindrance caused helical inversion, but at a high level of steric hindrance, the helical conformation could not be adopted, because of the reduced doping level. The reduced crystallinity was greatly affected by the decreased doping level. The steric effect influenced the polymer conformation and the doping level, thus determining the optical activity, morphology, and crystallinity of the PAni derivatives.

• Journal of the Korean Chemical Society
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• v.46 no.3
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• pp.225-228
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• 2002

Poly-o-toluidine (POT) was chemically and electrochemically synthesized for the study of the electronic and steric effect of methyl substituents. It was found that the steric effect was dominant in POT. The IP 4.95 eV, EA 3.24 eV, Eg 1.71 eV of POT were found by the CV (Cyclic Voltammetry) and CCPSA (Constant Current Potentiometric Stripping Analysis).

• Journal of Pharmaceutical Investigation
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• v.23 no.3
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• pp.119-125
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• 1993

The protein binding of salicylate analogs has been investigated by equilibrium dialysis. A series of binding experiments were performed in order to elucidate the effects of physicochemical properties of salicylate analogs on the binding with bovine serum albumin. Attempts to correlate affinity constants with capacity factor, steric factor and Hammett ${\sigma}$ values suggested hydrophobic forces to be involved in the binding of salicylate analogs. Steric factor contributes to binding process partly, whereas electronic interaction appears to be insignificant.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.163-170
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• 1988

The MNDO calculations were performed on the various rotamers of N-methyl formamide, N,N-dimethyl formamide, N-methyl acetamide, and N,N-dimethylacetamide in order to investigate the contribution of the one-electron and the steric effect on their rotational barriers about the C-N bond. Results show that while the conformational stabilities of formamides depend mainly on the one-electron factor, those of acetamides depend mainly on the steric factor. According to results obtained by calculations on the rotational barriers about C-N bond, for N-monosubstituted amides the steric effect is larger in the rotational ground state than in the transition state and for N,N-disubstituted amides the steric effect is larger in the rotational transition state.

• Bulletin of the Korean Chemical Society
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• v.17 no.8
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• pp.693-695
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• 1996

The steric effect on the first order hyperpolarizability of the β-nitrostyrene derivatives has been investigated by comparing the β values and the dihedral angles between the aryl and nitroalkenyl groups. In general the β value increased with the electron-donating ability of the substituent. The larger β value for 3,4-dimethoxy-β-nitrostyrene than that for p-methoxy-β-nitrostyrene has been attributed to the lower charge transfer energy for the former. The most striking substituent effect was observed in the β-methyl-β-nitrostyrene derivatives. Thus the β values for 3,4-dimethoxy- and p-methoxy derivatives of the latter decreased to near zero, probably because of the large distortion from planarity caused by the steric repulsion between the β-methyl and the aryl groups. The larger β value for p-dimethylamino-β-methyl-β-nitrostyrene has been interpreted with an increased electron-donating ability of the substituent and increased co-planarity.

• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.1081-1084
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• 2004

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.193-196
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• 1987

The gas phase pyrolyses of eight esters have been studied by MNDO-MO method. In the ethylformate pyrolysis, ${\alpha}$-methylation had a steric releasing effect whereas ${\beta}$-methylation had a steric crowding in the transition state; the latter, however, is over-compensated by a greater electronic repulsion resulting in a net steric releasing effect. Considerations of formal charges and geometrical changes involved in the activation led us to propose a pyrolysis mechanism in which a preequilibrium of acidic proton transfer is followed by the rate-limiting bond polarization of $C_{\alpha}$-O bond in a cyclic transition state.

• Journal of the Korean Chemical Society
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• v.47 no.4
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• pp.412-416
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• 2003

• Bulletin of the Korean Chemical Society
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• v.28 no.1
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• pp.133-135
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• 2007

• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1525-1530
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• 2004

Mutagen X (MX) exists in our drinking water as the bi-products of chlorine disinfection. Being one of the most potent mutagen, it attracted much attention from many researchers. MX and its analogs are synthesized and modeled by quantitative structure activity relationship (QSAR) methods. As a result, factors affecting this class of compounds have been found to be steric and electrostatic effects. We tried to collect all the data available from the literature. With both CoMFA and CoMSIA various combinations of physiochemical parameters were systematically studied to produce reasonable 3-dimensional models. The best model for CoMFA gave $q^2$ = 0.90 and $r^2$ = 0.97, while for CoMSIA $q^2$ = 0.85 and $r^2$ = 0.94. So the models seem to be reasonable. Unlike previous result of CoMFA, in our case steric parameter alone gave the best statistics. Although the steric contribution was found to be the most important in both CoMFA and CoMSIA, steric parameter along with electrostatic parameter produced slightly better model in CoMSIA. Overall, steric contribution is clearly the most important single factor. However, when we compare chlorine and bromine substitution, chlorine substitution can be more mutagenic. This indicates that other factors such as electrostatic effect also influence the mutagenicity. From the contour maps, steric contribution seems to be focused on rather small area near C6 substituent of the furanone ring, rather than C3 substituent. Therefore the locality of steric contribution can play a significant role in mutagenicity.