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

• 생명과학회지
• /
• 제12권6호
• /
• pp.682-687
• /
• 2002

다양한 금속이온의 첨가에 따른 CPase Taq의 효소활성의 개선에 관한 연구를 행하였다. 1 mA의 코발트이온의 첨가에 의해 효소활성이 4배 이상 증가했고, 1 mA의 칼슘이온의 첨가에 의해서는 효소활성이 거의 3배 정도로 증가했다. 하지만 활성중심에 존재하는 아연이온은 효소활성에 영향을 주지 않았다. 활성중심의 금속 이온이 효소활성에 영향을 주는지를 알아보기 위해 활성중심을 차지하고 있는 아연이온을 본 효소를 효과적으로 활성화시키는 코발트이온으로 치환하였다. 그 결과, 코발트이온으로의 치환이 CPase Taq의 효소활성에 영향을 주지 않으므로, 코발트이온은 본 효소의 활성중심의 금속이온인 아연이온을 대신하여 CPase Taq가 효소활성을 가지는데 있어서 동일한 역할을 할 수 있는 금속이온이라 사료된다.

• Bulletin of the Korean Chemical Society
• /
• 제31권2호
• /
• pp.303-308
• /
• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• 한국정밀공학회:학술대회논문집
• /
• 한국정밀공학회 2009년도 춘계학술대회 논문집
• /
• pp.363-364
• /
• 2009

• 한국진공학회지
• /
• 제7권3호
• /
• pp.221-228
• /
• 1998

금속과 고분자 사이에 접착력을 향상시키기 위하여 이온 보조 반응법을 이용하여 고분자의 표면을 친수성으로 처리하였다. 이온 보조 반응법은 기존의 이온빔을 이용한 고분 자 개질 방법과는 달리 이온조사시 시료 표면에 반응성 가스를 흘려줌으로써 반응성 가스와 고분자 표면에 반응이 일어나게 하여 새로운 기능성 그룹을 형성하는 방법이다. 이온보조 반응법에서는 이온의 양은 $5\times 10^{14}$에서 $1\times 10^{17}\textrm{ions/cm}^2$까지 변화시켰고 반응성 가스의 양은 0에서 8sccm까지 변화시켰으며 이온의 에너지는 0.3keV에서 1.2keV까지 변화시켰다. 이온 보조 반응법을 이용하여 처리한 고분자의 경우 접촉각은 단순히 Ar+이온만을 이용하여 처 리한 경우 $40^{\circ}$근처의 값을 나타내었다. 그러나, 반응성 가스인 산소를 표면에 주입하여 주 었을 경우 접촉각은 20도 미만의 값을 나타내었다. 그리고 이때의 표면에너지는 ~ 70dyne/cm2까지 증가하였다. 그러나 테프론(polytetraflouroethylene: PTFE)의 경우 이온의 양이 증가하면 원래의 접촉각 보다도 큰 값을 나타내었다. 이렇게 처리된 고분자 위에 금속 을 증착 시켰을 때 금속과 고분자사이에 접착력을 조사하여 본 결과 처리하지 않은 시료의 경우 증착한 박막이 벗겨져 나가는데 반하여 이온 보조 반응법에 의하여 처리된 고분자 표 면에 증착된 금속막은 떨어져 나가지 않음을 관찰 할 수 있었다.

• 한국섬유공학회:학술대회논문집
• /
• 한국섬유공학회 2001년도 가을 학술발표회 논문집
• /
• pp.219-222
• /
• 2001

Membranes which selectively transport specific metals on an industrial scale is much useful in a number of applications, such as aqueous stream purification, catalyst and recycling of the reactants, the applications in metal ion sensing and so forth. Numerous studies have been already made to use liquid, supported liquid and, emulsion liquid membranes (LM) for selective carriers for metal ion transport. (omitted)

• Bulletin of the Korean Chemical Society
• /
• 제15권8호
• /
• pp.654-658
• /
• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.

• 한국진공학회지
• /
• 제6권S1호
• /
• pp.110-114
• /
• 1997

Development of metal ion source growth of high quality Cu metal film formation of non-stoichiometric $SnO_2$ films of Si(100), and modification fo polymer surface by low enregy ion beam have been carried out at KIST Ion Beam Lab. A new metal ion source with high ion beam flux has been developed by a hybrid ion beam (HIB) deposition and non-stoichiometric $SnO_2$ films are controlled by supplying energy. The ion assisted reaction (IAR) in which keV ion beam is irradiated in reactive gas environment has been deveolped for modifying the polymers and enhancing adhesion to other materials and advantages of the IAR have been reviewed.

• Bulletin of the Korean Chemical Society
• /
• 제22권1호
• /
• pp.53-58
• /
• 2001

Sulfonated poly(phenylene sulfide) (SPPS) polymers were prepared by sulfonation of poly[methyl[4-(phenylthio) phenyl]sulfonium trifluoromethanesulfonate] (PPST) with fumic sulfonic acid (10% $SO_3-H_2SO_4$) and demethylation with aqueous NaOH solution. The equilibrium constants of ion exchange reactions between alkali metal cations ($Li^+,\;Na^+,\;and\;K^+$) and SPPS ion exchanger in organic solvents such as tetrahydrofuran (THF) and dioxane were measured. The equilibrium constants of ion exchange reactions increased as the polarity of the solvent increased, and the reaction temperature decreased. The equilibrium constants of the ion exchange reaction ($K_{eq}$) also increased in the order of $Li^+,\;Na^+,\;and\;K^+$. To elucidate the spontaneity of the exchange reaction in organic solvents, the enthalpy, entropy, and Gibbs free energy were calculated. The enthalpy of reaction ranged from -0.88 to -1.33 kcal/mol, entropy ranged from 1.42 to 4.41 cal/Kmol, and Gibbs free energy ranged from -1.03 to -2.55 kcal/mol. Therefore, the exchange reactions were spontaneous because the Gibbs free energies were negative. The SPPS ion exchanger and alkali metal ion bounding each other produced good ion exchange capability in organic solvents.

• 한국재료학회:학술대회논문집
• /
• 한국재료학회 1993년도 추계 학술발표 강연 및 논문 개요집
• /
• pp.83-83
• /
• 1993