• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.366-371
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• 1994

The kinetics of the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives was investigated by ultraviolet spectrophotometry in $H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron donating groups. Final product of the hydrolysis was 2-(N-acetylaminoethylthio)-acetoacetanilide enol from Judging from the results of the rate equation, general base effect, activation parameters and final products, the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives seemed to be initiated by the neutral $H_2O$ molecule which does not dissociate at pH below 10.0, but proceeded by the hydroxide ion at pH above 11.0, and those two reactions occurred competively at pH 10.0∼11.0 range. On the basis of these findings a plausible mechanism for the hydrolysis of 5,6-dihydro-1,4-thiazine derivative was proposed.

• Textile Coloration and Finishing
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• v.10 no.4
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• pp.24-29
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• 1998

11종류의 cellulose에 고착된 vinylsulfone(VS)계 반응성 염료(F-type)의 알칼리 가수분해 거동과 염료와 섬유의 결합 안정성을 cellophane film을 이용한 film권층법에 의하여 조사하였다. F-type은 알칼리욕에서 분해되어 VS type을 생성하고 VS type은 가수분해에 의해 hydroxyethylsulfone(Hy)을 생성하거나 cellulose와 재결합하여 F-type을 생성하였다. F-type은 알칼리 처리에 의해 cellulose의 수산기의 위치에 기인하는 bimodal 가수분해 거동(fast and slow hydrolysis)을 나타내었다. Orange 7과 Yellow 17는 cellulose와의 반응성이 높고 F-type의 초기 분해속도가 빠르며 일반적으로 fast 가수분해속도가 slow 가수분해 속도보다 약 5배정도 큼을 알 수 있었다. 또한 조사된 대부분의 염료의 경우 slow 가수분해 속도는 거의 유사함을 알 수 있었다.

• Proceedings of the Korean Society for Applied Microbiology Conference
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• 1986.12a
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• pp.508-508
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• 1986

이온성 계면활성제 존재하에서 유기용매에 물을 첨가하면 물이 계면활성제에 약해 둘러싸이면서 유기용매에 용해되어 의사 이상계가 형성된다. 이러한 계를 역미셀 또는 W/O microemulsion이라고 하며 계면활성제로 둘러 쌓인 물분자 집하체를 water pool이라고 한다. 그런데, 10여년 전 water pool에 bipolymer를 용해시킬 수 있다는 사실이 밟혀짐에 따라 이러한 체계를 생체막을 단순화시킨 모형막으로서 막을 통해 일어나는 여러 가지 현상의 규명에 이용하거나 물에 불용성인 기질의 효소 촉매반응의 반응계로 이용하는 연구가 꾸준히 이루어져 있다. 본 강연은 역미셀계에 리파제를 용해시켜 유지의 가수분해를 유도함으로써 지방산을 생산하는 방법에 관한 연구이다. 역미셀계에서 리파제의 특성은 에멀전계와 비교했을 때 큰 차이가 없었으며 물과 계면활성제의 몰 비율(R값)은 효소의 초기반응 속도에 커다란 영향을 끼치는 인자로 나타났다. 올리브유 농도가 5%(v/v), AOT농도가 0.1M, 초기 물 농도가 1.0M의 조건에서 유지의 회분식 가수분해 실험을 행한 결과 이 기질은 거의 완전히 가수분해되었으며, 이 반응계에서 R값과 초기 물 농도는 반응의 평형에 커다란 영향을 끼치는 것으로 나타났는데 초기 물 농도가 증가할수록 평형 가수분해율은 증가하였단 이러한 결과를 반응속도론 측면에서 분석한 결과 역미셀계에서 리파제 반응은 에멀전계에서와는 달리 2차 반응을 따르는 것으로 나타났다. 물 농도가 평형 가수 분해율과 속도 변수에 끼치는 영향을 수학적으로 표시하기 위하여 2차 가역적 반응 속도론에 근거하여 가수분해율, 평형상수, 속도상수 둥을 나타내는 식을 유도하였고 이를 바탕으로 여러 가지 실험 조건 하에서 리파제 반응의 반응 시간에 따른 가수분해율을 예측한 결과는 실제 실험 결과와 잘 일치하였다(편차는 5%). 또한 속도상수와 R값과의 관계식 및 유도한 방정식을 이용하여 추정한 초기속도와 평형 가수분해율을 최대화하는 R값은 각각 10.4 와 11.4 였다.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.919-924
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• 1992

The kinetics of the hydrolysis of N-benzylidenebenzenesulfonamide derivatives have been investigated by ultraviolet spectrophotometry in $H_2O$ at $25^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effect on the hydrolysis of N-benzylidenebenzenesulfonamide derivatives were studied and rate of hydrolysis is known to be accelerated by electron withdrowing group. Final product of the hydrolysis was benzenesulfonamide and benzaldehyde. Base on the rate equation, substituent effect, general base effect and final products, hydrolysis of N-benzylidenebenzenesulfonamide derivatives seemed to be initiated by the hydronium ion at the pH 0.2${\sim}$2.5 and proceeded by the neutral $H_2O$ molecule at pH 3.0${\sim}$8.0 but proceeded by the hydroxide ion at above pH 8.5.

• KSBB Journal
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• v.6 no.2
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• pp.167-174
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• 1991

Enzymatic cellulose hydrolysis depends on the several factors such as the structural features (CrI, particle size and surface area, etc.), the nature of cellulase enzyme system, the inhibitory effects of products, and enzyme deactivation. At the presence of products on the initial hydro- lysis rate of cellulose, cellobiose has more severe inhibitory effect than glucose. Othewise, the inhibition effect of products for adsorbed enzyme is related to the glucose and cellobiose conentration hyperbolically. Enzyme deactivation of FPA and ${\beta}-glucosidase$ were expressed by exponential decay profile.

• Journal of the Korean Chemical Society
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• v.27 no.2
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• pp.133-141
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• 1983

The kinetics of the acid-catalyzed hydrolysis of a series of 1-aryl-2-pyrrylideneaniline (3) have been studied in 20% MeOH solution using UV spectrophotometer. Substituents in 3 showed a relatively small effect, with hydrolysis facilitated by electron withdrawing group. By obtaing linear plots of $log k_{obs}$ against Hammett ${\sigma}$ constants, it was able to show that substituents had a considerable contribution to the aromaticity of pyrrole compounds. The small positive ${\rho}$ values were consistent with the rate-determining addition of water to the protonated schiff base in the buffer solution of pH 4 to 8, whereas the addition of water to the free imine seemed to be the rate-determining in the solution of acidities greater than pH 8.

• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.429-434
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• 2000

The rate constants for the hydrolysis of styryldiphossphine oxide(SDPO) were deter-mined by ultraviolet visible spectrophotometric method and rate equation which can be applied over wide pH ranges was obtained. On the basis of pH-rate profile, hydrolysis product analysis, general base catalysis and substituent effect, a plausible hydrolysis mechanism is proposed : Below pH 4.5, the hydrolysis reaction is pro-ceeded by the attack of water to carbocation after protonaticentration of hydroxide ion.

• Textile Coloration and Finishing
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• v.6 no.4
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• pp.9-16
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• 1994

알칼리 수용액 중에서의 Vinylsulfone(VS)계 반응성염료의 혼합상태의 가수분해 반응을 정량적으로 조사하였다. 혼합이량체의 생성 및 분해반응 속도상수를 각각의 염료의 가수분해반응에서 구한 속도상수를 이용하여 계산하였다. 단독이량체를 생성하는 염료들을 조합하였을 경우에는 혼합이량체가 생성되었다. C.I.Reactive Blue 19가 다른 VS계 염료들과 혼합되었을 경우에는 일반적으로 혼합이량체가 생성되었다. Blue 19와 Orange 16의 조합의 경우에는 낮은 염료농도에서만 혼합이량체가 생성되었으며, Red 22의 경우에는 단독 및 혼합이량체가 생성되지 않았다. 단독이량체가 생성되지않는 Orange 7는 다른 VS계 염료들과의 조합에서 혼합이량체를 생성함을 확인하였다. Yellow 17의 혼합이량체의 분해속도 상수값이 가장 큼을 알 수 있었다.

• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.150-157
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• 1978

The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.584-588
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• 1992

The rate constants of hydrolysis of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by UV spectrophotometry at 25$^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the hydrolysis products obtained and from general base and substituent effects, plausible mechanisms of hydrolysis in various pH range have been proposed. Below pH 4.5, the hydrolysis was initiated by the protonation and followed by the addition of water to ${\alpha}$-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide ion to ${\alpha}$-carbon. In the range of pH4.5∼10.0, the addition of water to nitrone is rate controlling step.