• Current Applied Physics
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• 제18권12호
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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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• 제12권4호
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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.

• 대한화학회지
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• 제43권1호
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• pp.28-42
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• 1999

크기가 큰 치환기의 폴리실란-[2-($R^1R^2$-phenyl)propyl]Si[$R^3$]-[예:$R^1=R^2$=H, $R^3$=n-hexyl; 폴리(2-페닐프로필)(n-헥실)실란]을 초음파 화학적 방법을 사용하여 Wurtz 축합반응에 의해 합성하였다. 초음파는 톨루엔 용매 중 금속 나트륨을 분산시켜 작은 크기와 높은 표면 활성의 나트륨을 형성하였으며 이에 의해 Wurtz 축합반응이 진행되었고 또한 초음파는 부 생성물인 염화나트륨이 나트륨 표면에 침착되는 것을 방지하여 표면활성이 지속적으로 유지되도록 하여 효율적인 반응이 기대되었다. 폴리실란 생성물은 저분자량의 중합체(분자량~$10^3$)와 고분자량의 중합체(분자량~$10^6$)의 혼합물로 얻어 졌다. 전체 수득률은 75-99% 이었으나 $R^3$가 n-hexyl기인 경우에는 혼합비율은 고분자량 중합체가 주 생성물로, cyclohexyl 또는 2-phenylethyl기인 경우에는 저분자량 중합체가 주 생성물로 얻어져 폴리실란의 치환기 종류에 영향을 받는 것으로 나타났으나 $R^1, R^2$의 변화는 영향을 나타내지 않았다.

• Applied Biological Chemistry
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• 제38권2호
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• pp.163-167
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• 1995

살충성Buprofezine분자의 구조를 변형한 20종의 새로운 isothiourea유도체(S)를 합성하고 N-치환(Z)amino기의 변화에 따르는 6종의 해충에 대한 살충활성을 검토한 바, 배추 좀나방(Plutella Xylostella Linnaeus)에 대하여 현저하게 선택적인 살충성을 나타내었다. N-치환(Z) amino기의 치환기(Z)가 변화함에 따른 물리-화학적 파라미터와 배추 좀나방에 대한 살충활성값 (Obs. $pI_{50}$)과의 구조-활성 관계(SAR)식으로부터 살충활성에 미치는 물리-화학적 파라미터의 영향은 MR>${\pi}$>$L_1$의 순이었으며, 이들 파라미터의 적정값(optimal value)은 각각 $L_1=5.22{{\AA}}$, $MR=15.70(Cm^3/mol)$ 및 ${\pi}=1.60$이었다. 이 값을 만족하는 치환기(Z)로는 탄소 원자수가 3개로 구성된 iso-propyl 치환체(5)로써 가장 큰 살충성(Obs. $pI_{50}=3.00$)을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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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.

• 대한화학회지
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• 제31권5호
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• pp.400-405
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• 1987

세가지 아미노산 즉 글리신, 알라닌 및 트립토판의 두가지 해리상수를 전도도법을 이용하여 온도(15 ~ 35$^{\circ}$C)와 압력(1~2,500bar)을 변화시키면서 측정하였다. 두가지 해리상수는 온도가 높아지면 모두 증가했으나 압력이 높아지면 첫째 해리상수는 증가하고 둘째 해리상수는 트립토판을 제외하면 감소하였다. 이와같은 현상은 반응의 열역학적 성질을 이용하여 설명하였으며 나아가서 반응의 특성을 알아보기 위해서 Hammett의 법칙을 적용하고 반응의 치환기 상수와 압력에 따른 반응상수를 계산하였다. 아미노산의 해리상수의 특성을 치환 효과로 설명하였고 반응의 유형을 반응상수로서 알아보았다.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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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.

• 대한화학회지
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• 제33권4호
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• pp.343-349
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• 1989

${\omega}$-아미노산인 ${\beta}$-alanine과 ${\gamma}$-aminobutyric acid의 해리상수를 전도도법을 이용하여 온도($20{\sim}40^{\circ}C$)와 압력($1{\sim}2500$ bar)을 변화시키면서 측정하였다. 각각 아미노산의 두 가지 해리상수는 온도가 증가하면 증가하지만 압력이 증가하면 $K_1$은 증가하지만 $K_2$는 감소하였다. 해리상수를 이용하여 여러 가지 열역학적 성질들을 계산하고 이들로부터 해리반응의 특성을 알아보았다. ${\omega}$-아미노산의 해리상수를 해리기와 치환기간의 거리의 상관관계로 알아보았다. 반응특성을 알아보기 위해 Hammett 법칙을 적용하여 반응의 치환기 상수와 압력에 따른 반응상수를 계산하였다. ${\omega}$-아미노산의 특성을 치환기 효과로 설명하고 반응유형을 반응상수로서 알아보았다.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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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.

• 대한화학회지
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• 제29권3호
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• pp.277-282
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• 1985

N-benzylideneaniline 유도체의 C-phenyl group 파라위치에 치환기가 변화함에 따라 imidoyl양성자의 화학적 이동 (H${\alpha}$-SCS)에 미치는 자유에너지 직선관계(LFER)를 검토하기 위하여 치환기별 H$_{\alpha}$-SCS와 ${\sigma}$,${\sigma}^+$, ${\sigma}_I$,${\sigma}_R$, F 및 R등의 여러가지 자유에너지 관계 파라미터를 Hammett, Okamoto-Brown식과 그리고 Taft, Swain-Lupton의 DSP식에 적용한 바, 2.8∼3.2의 섞임계수(blending coefficient values, ${\lambda}$)값을 얻음으로써 공명효과(R)가 유발효과(I)나 장효과(F)보다 H_${\sigma}$-SCS에 크게 영향을 미친다는 사실을 알 수 있었으며 Swain-Lupton의 식으로 구한 %R = 66.6 and %F = 33.4의 값으로 부터 H$_{\sigma}$-SCS에 미치는 공명효과(R)와 장효과(F)의 비가 2:1이라는 정량적인 관계를 알았다.