• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3947-3951
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• 2011

The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

• 전기화학회지
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• 제18권2호
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• pp.75-80
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• 2015

방향족 친핵성 치환반응을 이용하여 멀티블록형 sulfonated poly(arylene ether sulfone)(SPAES) 공중합체를 합성하였다. 서로 다른 말단(F- 또는 OH-말단)을 가지는 친수성 및 소수성 올리고머를 합성한 후 이를 이용하여 고분자 전해질 막을 합성하였다. 각기 다른 말단이 블록공중합체의 분자량에 미치는 영향을 분석하였고, 서로 다른 친수성구조가 블록고분자의 특성에 어떠한 영향을 미치는지 분석하였다. 합성된 멀티블록고분자는 70%이상의 습도에서 나피온 막과 비슷하거나 우수한 이온전도도를 나타내었고, 특히 SPAES 9의 경우 전습도 영역에서 SPAES 10보다 높은 이온전도도를 보였는데, 이는 친수성 블록내의 술폰산기의 부분 농도가 높아짐에 따라 친수성-소수성 간의 상분리가 발달되어 이온전도도가 향상된 것으로 보인다.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1907-1911
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• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

• 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.

• BMB Reports
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• 제31권2호
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• pp.149-155
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• 1998

The N199H variant of the EcoRI endonuclease has about twice the catalytic activity of the wild-type. A comparison of their biochemical characteristics, using synthetic oligonucleotides 5'-dAAAACTTAAGAAAAAAAAAAA-3' (KA) and 5'-dTTTTTGAATTCTTTTTTTTTT-3' (KT), helps to define the cleavage reaction pathway of these enzymes. Both EcoRI and EcoRI variant N199H were found to cleave singlestranded KA or KT about three times faster than the double-stranded forms, although the KT oligonucleotide was more susceptible. Using the ssDNA substrate in kinetic analyses, lower $K_m$ values were obtained for the N199H variant than for the wild-type at low (50 mM), as well as high (200 mM), sodium chloride concentrations. This difference between the endonucleases is attributed to a grealter accessibility for tbe substrate by the variant, and also a higher affinity for the DNA backbone. It also appears that the relative activities of the two enzymes, particularly at high ionic strength, are proportional to their populations in the monomeric enzyme form. That is, according to gel filtration data, half of the N199H molecules exist as monomers in 200 mM NaCl, whereas those of the wild-type are mainly dimeric. Consequently, the Asp199 residue of the EcoRI endonuclease may be implicated in the protein-protein interaction leading to dimerization, as well as in coupling to DNA substrates. In summary, it is proposed that active monomeric endonuclease molecules, derived from the dimeric enzyme, recognize and form a complex with a single stranded form of the DNA substrate, which then undergoes nucleophilic substitution and cleavage.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1525-1529
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• 2013

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

• 대한방사성의약품학회지
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• 제6권2호
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• pp.75-91
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• 2020

[^99mTc]Tc-Hexamethylpropylene amine oxime (HMPAO) is currently used as a regional cerebral blood flow imaging agent for single photon emission computed tomography (SPECT). The HMPAO ligand exists in two isomeric forms: d,l and meso showing different properties in vivo. Later studies indicated that brain uptake patterns of ^99mTc-complexes formed from separated enantiomers differed. Separation of enantiomers is difficult by fractional crystallizations method. Usually, the substance is obtained in low chemical yield in a time-consuming procedure. Furthermore, the final product still contains some impurity. So we have developed new efficient route for synthesis of R,R- and S,S-HMPAO enantiomeric compounds in 6-steps. Nucleophilic substitution (S_N2) reactions of 2,2-dimethylpropane-1,3-diamine either with S- (1a) or R-methyl2-chloropropanoate (1b) were performed to produce compounds R,R- (2a) or S,S-isomer (2b) derivatives protected with benzylchloroformate (Cbz), respectively. And then Weinreb amide and methylation reaction using Grignard reagent, oxime formation with ketone group and deprotectiion of Cbz group by hydrogenolysis gave S,S- (7a) or R,R-HMPAO (7b), respectively. Entaniomeric compounds were synthesied with high yield and purity without any undesired product. The 7a or 7b kits containing 10 ㎍ SnCl₂-2H₂O were labeled with ^99mTc with high radiolabeling yield (90%).

• 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.

• 공업화학
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• 제19권1호
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• pp.51-58
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• 2008

내마모제로 사용하기 위하여 mercaptobenzothiazole 및 디알킬렌디티오카바메이트 그룹을 함유하는 환경친화적인 올레인산 에스테르를 디알킬아민과 이황화탄소의 치환반응, 디클로로아세톤과의 치환반응, $NaBH_4$을 사용한 환원반응 및 올레인산과의 축합반응 등의 과정을 행하여 90% 이상의 수율로 합성하였다. 중간 생성물 및 내마모제의 구조적 특성은 FT-IR, $^1H$-NMR 스펙트럼 및 원소분석으로 분석하였으며 광유계 오일(100 N) 및 식물유에서의 용해성을 1 중량%에서 평가한 결과 잘 용해되었다. 또한, 합성한 내마모제의 열 안정성을 TGA로 분석하였으며 초기 5 wt% 분해온도가 구조에 따라 $192^{\circ}C$에서 $217^{\circ}C$의 안정성을 나타내었다. CEC L-33-A-93 방법으로 생분해도를 평가한 결과 89%에서 99%의 생분해도를 나타내어 환경친화적인 내마모제임을 확인하였다. 내마모제의 윤활특성을 100 N 윤활기유 및 식물유에 첨가하여 4구 마모시험기를 사용하여 평가한 결과, 100 N BO에서 4-ball 마모흔의 직경은 Bz-thia-OE < C4-DTC-OE < Pyrro-DTC-OE < C8-DTC-OE의 순으로 큰 값을 나타내어 내마모성능이 나쁘게 나타났다. 한편, 식용유에서는 4-ball 마모흔의 직경이 0.8260 mm에서 0.9637 mm를 나타내어 내마모제의 첨가효과가 나타나지 않았다.

• Korean Chemical Engineering Research
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• 제53권3호
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• pp.282-288
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• 2015

에틸렌-비닐아세테이트(EVA)와 아지드화 폴리부타디엔(Az-PBD)를 블렌드 함으로써 새로운 에너지함유 열가소성탄성체를 제조하고, 이들의 미세구조 및 제반물성을 SEM, DSC, DMA, 인장실험 및 연소시험으로부터 조사하였다. Az-PBD는 1,2-비닐기를 갖는 폴리부타디엔(PBD)을 첨가반응에 의해 비닐기를 브롬화시킨 후, $NaN_3$를 이용하여 브롬기를 아지드기($-N_3$)로 치환시킴으로써 제조하였다. EVA/Az-PBD 블렌드는 EVA/Az-PBD 비율이 무게비로 각각 90/10, 80/20, 70/30이 되도록 용액 블렌딩으로 제조하였다. SEM, DSC, DMA 분석 결과 이들 블렌드는 부분적으로 상용성이며, EVA가 연속상을 이루고 Az-PBD가 분산상을 이루는 미세구조를 갖는 것을 알 수 있었다. 인장실험으로부터 Az-PBD 함량이 증가될수록 인장모듈러스 및 영구신장변형율이 증가되고 파단신율이 감소되는 경향을 보였으나, 제조된 모든 블렌드들은 700% 이상의 파단신율과 5% 이하의 영구인장변형율을 나타내어, 일반적인 탄성고무소재와 같은 특성을 나타내었다. 또한, 연소 시 Az-PBD 함량 증가함에 따라 더 큰 불꽂이 발생되어 연소 시 더 높은 에너지를 발생시킬 수 있음을 확인할 수 있었다.