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Diphenyl-4-nitrophenylphosphinate(DPNPIN)의 탈인산화반응에 미치는 Alkylbenzimidazole의 친핵적 및 Cetylpyridinium chloride(CPyCl) 미셀 촉매효과 KCI 등재

Nucleophilic Effect of Alkylbenzimidazole and Micellar Effect of Cetylpyridinium chloride(CPyCl) on Dephosphorylation of Diphenyl-4-nitrophenylphosphinate(DPNPIN)

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한국환경과학회지 (Journal of Environmental Science International)
한국환경과학회 (The Korean Environmental Sciences Society)
초록

This study is mainly focused on micellar effect of cetylpyridinium chloride(CPyCl) solution including alkylbenzimidazole( R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). The reactions of DPNPIN with R-BI⊖ are strongly catalyzed by the micelles of CPyCl. Dephosphorylation of DPNPIN is accelerated by BI⊖ ion in 10 -2 M carbonate buffer(pH 10.7) of 4×10 -3 M CPyCl solution up to 100 times as compared with the reaction in carbonate buffer by no BI solution of 4×10 -3 M CPyCl. The value of pseudo first order rate constant(k m BI) of the reaction in CPyCl solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-BI⊖ in micellar solutions are obviously slower than those by BI⊖, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BI⊖ in Stern layer of micellar solution. The surfactant reagent, cetylpyridinium chloride(CPyCl) , strongly catalyzes the reaction of diphenyl-4-nitrophenylphosphinate(DPNPIN) with alkylbenzimidazole (R-BI) and its anion(R-BI⊖) in carbonate buffer(pH 10.7). For example, 4×10 -3 M CPyCl in 1×10 -4 M BI solution increase the rate constant (kψ=1.0×10 -2 sec -1 ) of the dephosphorylation by a factor ca.14, when compared with reaction (kψ=7.3×10 -4 sec -1 ) in 1×10 -4 M BI solution(without CPyCl). And no CPyCl solution, in 1×10 -4 M BI solution increase the rate constant (kψ=7.3×10 -4 sec -1 ) of the dephosphorylation by a factor ca.36, when compared with reaction (kψ=2.0×10 -5 sec -1 ) in water solution(without BI). This predicts that the reactivities of R-BI⊖ in the micellar pseudophase are much smaller than that of BI⊖ . Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CPyCl.

목차
Abstract
 1. 서 론
 2. 재료 및 방법
  2.1. 시약 및 기기
  2.2. Alkylbenzimidazole의 해리상수(Ka )값과 PCyCl과의 결합상수(Ks)의 측정
  2.3. CPyCl 용액속에서 alkylbenzimidazole에 의해 추진되는 DPNPIN의 탈인산화반응의(dephosphorylation)속도상수(kψ)결정
 3. 결과 및 고찰
  3.1. CPyCl 미셀 수용액에서의 alkylbenzimidazole의결합상수(Ks) 값과 Ka 값
  3.2. CPyCl 미셀 유사층 내에서의 R-BI⊖의 농도
  3.3. CPyCl 미셀 용액내에서 R-BI⊖에 의한 탈인산화반응의 유사일차속도상수( ), (sec-1)
  3.4. 탈인산화 반응속도에 미치는 친핵체(R-BI⊖)의 농도의 영향
 4. 결 론
 참 고 문 헌
저자
  • 김정배(계명대학교 환경대학 지구환경학과) | Jeung-Bea Kim (Faculty of Environmental Studies, Keimyung University) Corresponding Author
  • 김학윤(계명대학교 환경대학 지구환경학과) | Hak-Yoon Kim (Faculty of Environmental Studies, Keimyung University)