• Bulletin of the Korean Chemical Society
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• 제22권4호
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• pp.383-387
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• 2001

The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• 제16권3호
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• pp.277-281
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• 1995

The relationship between the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$ and validity of the reactivity-selectivity principle (RSP) has been derived: RSP is valid when W = ${\rho}i(0){\cdot}{\rho}j(0)/{\rho}ij$ is negative. The analysis of 100 reaction series indicated that for normal SN2 reactions involving variations of substituents in the nucleophile (X) and in the substrate (Y) RSP is valid only for a dissociative type for which ${\rho}Y(0)$ is negative, whereas for the acyl transfer reactions with rate-limiting breakdown of the tetrahedral intermediate RSP is valid in general for all substituent changes, X, Y and/or Z (substituent on the leaving group). The trends in the validity of RSP for certain types of reaction can be useful in supplementing the mechanistic criteria based on the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$.

• 한국응용과학기술학회지
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• 제13권3호
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• pp.127-136
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• 1996

Thermograms of methylene blue(MB) in $L-{\alpha}-lecithin$ vesicle and incorporated purple membrane vesicle(InPM) systems have been studied by photochemical reaction differential scanning calorimetry at $25{\sim}55^{\circ}C$. Phase transition temperatures of lecithin vesicle, purple membrane(PM), and InPM were found to be independent of illumination of light(436nm) at $39{\sim}40^{\circ}C$, but endothermic phase transition was found in InPM vesicle. In MB-InPM system, endothermic phase transition was found on unillumination of light at $40{\sim}42^{\circ}C$, but exothermic phase transition was found on steady illumination of light at $48{\sim}52^{\circ}C$. It was estimated that the light energy absorbed from MB on vesicular surface was transferred to PM, and the transferred energy was redistributed to hydrophobic site of membrane. Therefore, the exothermic phase transition was measured at high temperature because of the increased hydrophobicity of acyl chain.

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.473-477
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• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.669-672
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.673-677
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.

• 생명과학회지
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• 제12권1호
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• pp.32-42
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• 2002

합성된 hexanoylthiocholine을 기질로 하여 butyrylcholinesterase와의 반응을 연구하였다. 기질의 농도 변화에 따른 초기반응속도 관찰을 통해 아실기의 탄소수가 증가함에 따라 반응성은 감소하나 $K_{m}$ 값은 0.140(mM)으로 더 강한 ES 복합체를 형성함을 알 수 있었다. Hexanoylthio-choline의 촉매화된 acetylcholinesterase 가수분해에 대한 pH-V/K profile에서 p $K_{a}$ 값 4.974$\pm$0.02을 얻었다. 이는 최근 문헌의 보고와 상통하는 것으로 p $K_{a}$ =6.2~6.4를 갖는 잔류물의 기본형에 활성이 의존하는 것으로부터 하나의 잔류물 또는 p $K_{a}$ =4.7~5.0을 갖는 잔류물들의 촉매작용으로 계통적인 자리밀림을 보여준다. 이는 촉매화된 BChE의 활성영역 esteratic site 주변에 긴 사슬 아실기의 가수분해에 관여하는 새로운 활성영역이 존재함을 밝히는 증거이다. 분자 조형은 기질의 아실기의 탄소수에 따라 acetylcholinesterase에 의해 표현되어지는 반응과정의 변화의 합리성을 제공한다. 본 연구에서는 한국과학기술원 도핑컨트롤센터와 연계하여 acetylcholinesterase와 기질인 acylthiocholine과의 입체적으로 둘러싸인 acyl-binding site를 분자 조형하고자 노력 중에 있다.

• Bulletin of the Korean Chemical Society
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• 제29권3호
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• pp.580-584
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• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3) in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (b lg) changes from 0.97 to 0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brnsted curvature) is 4.8, which is practically identical to the pKa of the conjugate acid of N3 ion (4.73). Hammett plots correlated with s o and s constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with r = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brnsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.

• 생명과학회지
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• 제20권1호
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• pp.97-102
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• 2010

식품단백질의 물성과 기능성을 개선시켜 산업적인 가치가 매우 높은 TGase를 생산하는 S. platensis YK-2의 분자 유전학적인 연구를 위해 형질전환방법을 확립하였으며 본 연구를 위해 도입된 방법은 대장균을 plasmid DNA의 공여체로, S. platensis의 포자를 수용체로 사용하는 접합전달법이다. S. platensis를 위한 최적 접합전달조건은 50 mM의 $MgCl_2$를 첨가한 MS배지에 열처리를 하지 않은 포자와 $5{\times}10^7$의 plasmid DNA 공여체인 E. coli를 사용하는 것이다. 또 본 연구를 통해 얻어진 접합전달체의 attB site에 대한 분석을 통해 S. platensis chromosome의 pirin 상동체를 코드하는 ORF내에 attB site가 단일위치로 존재하고 있으며 이미 밝혀진 다른 방선균유래 attB site의 염기서열에 대해 77.8%~96.3%의 상동성을 나타냈다.

• 대한화학회지
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• 제67권3호
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• pp.191-198
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• 2023

본 연구에서는 2,4-dinitrophenyl-5-substituted-2-furoates (1a-d)와 R₂NH/R₂NH₂⁺-20 mol%DMSO(aq)의 아실 이동 반응을 반응속도론적으로 연구하였다. 이 반응은 이차반응이고, pK_a⁰ = 9.5, β₁= 0.23-0.35 및 β₂ = 0.88-0.99의 결과와 함께 아래 방향으로 굽은 Brönsted plots이 관측되었다. k₁값은 5-furyl 치환기의 전자끄는 능력이 증가하고 친핵체의 친핵성도가 커질수록 증가하였다. 반면, k₂/k_-1 값 비율은 5-furyl 치환기에 관계없이 거의 일정하였다. 실험결과로 부터 반응은 속도결정단계가 변하는 단계반응 메커니즘으로 진행됨을 제안하였다.