• Bulletin of the Korean Chemical Society
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• 제34권7호
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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 Pharmaceutical Investigation
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• 제23권3호
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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.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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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.

• Bulletin of the Korean Chemical Society
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• 제28권1호
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• pp.133-135
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• 2007

• Macromolecular Research
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• 제10권3호
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• pp.140-144
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• 2002

Dispersion polymerization of acrylamide was carried out in the media of methyl alcohol/$H_2O$ mixtures using hydroxypropyl cellulose and ammonium persulfate as steric stabilizer and initiator, respectively. The effects of concentrations of initiator and steric stabilizer, amount of monomer, polymerization temperature, methyl alcohol/$H_2O$ ratio, and purification of monomer and nitrogen purge on the particle size of the latices and molecular weight of the polymers were investigated. The average particle diameter increased with increasing concentration of initiator, water content in methyl alcohol/$H_2O$ media, and polymerization temperature, but decreased with monomer and stabilizer concentrations. The viscosity average molecular weight increased with increasing concentrations of monomer, steric stabilizer, and water content in dispersion media, but decreased with initiator concentration and polymerization temperature. The PAM polymers prepared with the purified monomer and the nitrogen purging before the reaction showed the highest molecular weight.

• Bulletin of the Korean Chemical Society
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• 제19권11호
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• pp.1145-1147
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• 1998

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3274-3278
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• 2012

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $60.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are huge secondary inverse ($k_H/k_D$ = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the $k_H/k_D$ values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4403-4407
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• 2011

The nucleophilic substitution reactions of dipropyl chlorothiophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.11-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of various substrates are discussed.

• Archives of Pharmacal Research
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• 제23권4호
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• pp.324-328
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• 2000

Three dimensional QSAR studies for antihistamine and antibradykinin effects of new piperazine derivatives were conducted using the comparative molecular field analysis. Electrostatic and steric factors, but not hydrophobic factor, of the synthesized compounds were correlated with the antagonistic effect.

• Environmental Analysis Health and Toxicology
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• 제23권2호
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• pp.67-77
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• 2008

It has been observed that the linear relationship between the logarithm of bioconcentration factor (log BCF) of highly hydrophobic chemicals and their log $K_{ow}$ breaks when log $K_{ow}$ becomes greater than 6.0. Consequently, super hydrophobic chemicals were not thought to cause baseline toxicity as a single compound. Researchers often call this phenomenon as "hydrophobicity cutoff" meaning that bioconcentration or corresponding baseline toxicity has a certain cutoff at high log $K_{ow}$ value of hydrophobic organic pollutants. The underlying assumption is that the increased molecular size with increasing hydrophobicity prohibits highly hydrophobic compounds from crossing biological membranes. However, there are debates among scientists about mechanisms and at which log $K_{ow}$ this phenomenon occurs. This paper reviews three hypotheses to explain observed "cutoff": steric effects, kinetic or physiological limitations, and chemical activity cutoff. Although the critical molecular size that makes biological membranes not permeable to hydrophobic organic chemicals is uncertain, size effects in combination with kinetic limitation would explain observed non-linearity between log BCF and log $K_{ow}$. Chemical activity of hydrophobic chemicals generally decreases with increasing melting point at their aqueous solubility. Thus, there may be a chemical activity cutoff of baseline toxicity if there is a critical chemical activity over which baseline effects can be observed.