• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.168-170
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• 1987

The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

• Current Applied Physics
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• v.18 no.12
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• pp.1507-1512
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• 2018

The development of an organic-based aqueous redox flow battery (RFB) using quinone as an electroactive material has attracted great attention recently. This is because this battery is inexpensive, produces high energy density, and is environment friendly in stationary electrical energy storage applications. Herein, we investigate the redox potentials and solubilities of indole-5,6-quinone and indole-4,7-quinone derivatives in terms of the substituent effects of functional groups using theoretical calculations. Our results indicate that full-site substituted derivatives of indolequinone are more useful as active materials compared to single-site substituted derivatives. In particular, our calculations reveal that the substitution of $-PO_3H_2$ and $-SO_3H$ functional groups with multiple polar bonds is very effective in increasing the activity of the aqueous RFB. As a strategy to overcome the limitation that the aqueous solubility is intrinsically low because they are organic molecules, we suggest the substitution of functional groups with multiple polar bonds to the backbones of active organic materials. Among 180 indolequinone derivatives, 17 candidates that meet the redox potential standards ($${\leq_-}0.2V$$ or $${\geq_-}0.9V$$) and eight candidates with solubility exceeding 2 mol/L are identified. Three indolequinone derivatives that satisfy both conditions are finally presented as promising electroactive candidates for an aqueous RFB.

• Journal of Electrochemical Science and Technology
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• v.12 no.4
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• pp.440-452
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• 2021

Enhancement of durability and reduction of maintenance cost of concrete, with the implementation of various approaches, has always been a matter of concern to researchers. The integration of pozzolans as a substitute for cement into the concrete is one of the most desirable technique. Silica fume (SF) and colloidal nanosilica (CS) have received a great deal of interest from researchers with their significant performance in improving the durability of concrete. The synergistic role of the micro and nano-silica particles in improving the main characteristics of cemented materials needs to be investigated. This work aims to examine the utility of partial substitution of cement by SF and CS in binary and ternary blends in the improvement of the durability characteristics linked to resistance for electrochemical corrosion using electrical resistivity and half-cell potential analysis and chloride penetration trough rapid chloride penetration test. Furthermore, the effects of this silica mixture on the compressive strength of concrete under normal and aggressive environment have also been investigated. Based on the maximum compression strength of the concrete, the optimal cement substituent ratios have been obtained as 12% SF and 1.5% CS for binary blends. The optimal CS and SF combination mixing ratios has been obtained as 1.0% and 12% respectively for ternary blends. The ternary blends with substitution of cement by optimal percentage of CS and SF exhibited decreased rate for electrochemical corrosion. The strength and durability studies were found in consistence with the microstructural analysis signifying the beneficiary role of CS and SF in upgrading the performance of concrete.

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.28-42
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• 1999

Polysilanes with sterically bulky substituents, -[2-( $R^1R^2$-phenyl)propyl]Si[$R^3$]-, such as poly(2-phenylpropyl)(n-hexyl)silane [$R^1=R^2$=H, $R^3$=n-hexyl] were prepared by Wurtz-type coupling reactions with Na using a sonochemical method. The high-intensity ultrasound provided the formation of high quality Na dispersion in toluene and its active surface which was important for the synthesis of polysilanes in Wurtz-type coupling reaction was freshly and continuously regenerated during the process. The polysilanes products were mixtures of high molecular weight polymers with $\={M}_W$ of ∼$10^6$ and low molecular weight polymers with $\={M}_W$ of ∼$10^3$. It was found that the formation of high molecular weight polymerr was greatly influenced by the substituents $R^3$, directly attached to Si. On the contrary, changes on substituents ($R^1, R^2$) gave no influences at all. Overall yields for polysilanes were 75-99% in general but high molecular weight polysilanes were obtained as a major product when substituent $R^3$ is n-hexyl group and low molecular weight polysilanes were obtained as a major product when substituent $R^3$ is cyclohexyl and 2-phenylethyl groups. Effects of reaction conditions to polysilane yields were investigated.

• Applied Biological Chemistry
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• v.38 no.2
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• pp.163-167
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• 1995

New twenty 2-(n-octyl)-3-(n-propyl)isothiourea derivatives(S) were synthesized which is modified from the insecticidal Buprofezine (Applaud) in the selective insecticidal activities in-vitro against Diamond-Back moth (Plutella Xylostella Linnaeus). The structure activity relationships(SAR) between the insecticidal activity$(pI_{50})$ and a various physicochemical parameters of the substituent(Z) of S were analyzed by the multiple regression technique. The activities would depend largely on the MR, ${\pi}$ and $L_1$ parameters. The SAR was rationalized by parabolic function of MR, ${\pi}$ and $L_1$ constant, where the optimal values of the constants were $L_1=5.22{{\AA}}$, $MR=15.70\;Cm^3/mol$ and ${\pi}=1.60$, respectively. The steric effects play an important role in determining insecticidal activity. The SAR suggest that the S derivatives having a substituents with a small breadth and an appropriate length as Z group showed potent activity. From the results, the iso-propyl group(Z) substituent (5) with three carbon atom was the most effective compound.

• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.641-644
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• 2005

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.400-405
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• 1987

The two dissociation constants of three amino acid, glycine, alanine, and tryptophan were measured by the conductometric method in the temperature from 15 to 35$^{\circ}$C and pressure up to 2,500bar in aqueous solution. The both dissociation constants were increased as the temperature increased but the pressure effect were not same as the temperature effect. The first constants were increased as the pressure increased but second constants were decreased except tryptophan. The characteristic properties of these amino acids were discussed from the thermodynamic properties of the dissociation reaction. The substituted effects of the reaction were deduced from Hammett reaction and substituted constants which were calculated from the dissociation constants.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4185-4190
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}=+30\;cal\;mol^{-1}K^{-1}$ compared to negative value of 1a (${\Delta}S^{\neq}=-45\;cal\;mol^{-1}K^{-1}$) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=27.7\;kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=8.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. The free energy correlations exhibit biphasic concave upwards for substituent X variations in the X-anilines with a break point at X = 3-Me. The deuterium kinetic isotope effects are secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines and primary normal ($k_H/k_D$ > 1) with the weakly basic anilines and rationalized by the TS variation from a dominant backside attack to a dominant frontside attack, respectively. A concerted $S_N2$ mechanism is proposed and the primary normal deuterium kinetic isotope effects are substantiated by a hydrogen bonded, four-center-type TS.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.343-349
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• 1989

The dissociation constants of ${\beta}$-alanine and ${\gamma}$-aminobutyric acid were measured in the temperature range from 20 to $40^{\circ}C$ and pressure up to 2,500 bar by conductometric method. The both dissociation constants of respective amino acid increase with temperature increase but pressure effect is not same as the temperature. The $K_1$ increases as pressure increases but $K_2$ decreases. The properties of these amino acids were discussed in terms of the thermodynamic properties of the dissociation reaction. A relationship between the dissociation constants and the distance between substituted groups of amino acid was discussed. The substituted effects of the reaction were deduced from Hammett reaction and substituted constants which were calculated from the measured dissociation constants.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1579-1582
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• 2009

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.