This study is mainly focused on micellar effect of tetradecyltrimethyl ammonium bromide(TTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). Dephosphorylation of DPNPIN is accelerated by BI⊖ ion in 10-2 M Carbonate buffer(pH 10.7) of 4×10-4 M TTABr solution up to 80 times as compared with the reaction in Carbonate buffer by no benzimidazole(BI) solution of TTABr. The value of pseudo first order rate constant(kψ) of the reaction in TTABr solution reached a maximum rate constant increasing micelle concentration. 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, TTABr, strongly catalyzes the reaction of DPNPIN with R-BI and its anion(R-BI⊖) in Carbonate buffer(pH 10.7). For example, 4×10-4 M TTABr in 1×10-4 M BI solution increase the rate constant(kψ=99.7×10-4 1/sec) of the dephosphorylation by a factor ca. 28, when compared with reaction(kψ=3.5×10-4 1/sec) in BI solution(without TTABr). And no TTABr solution, in BI solution increase the rate constant(kψ=3.5×10-4 1/sec) of the dephosphorylation by a factor ca. 39, when compared with reaction (kψ=1.0×10-5 1/sec) in water solution(without BI).

This study is mainly focused on micellar effect of cetyltrimethyl ammonium bromide(CTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of isopropyl-4-nitrophenylphosphinate(IPNPIN) in carbonate buffer(pH 10.7). The reactions of IPNPIN with R-BI⊖ are strongly catalyzed by the micelles of CTABr. Dephosphorylation of IPNPIN is accelerated by BI⊖ ion in 10-2 M carbonate buffer(pH 10.7) of 4×10-3 M CTABr solution up to 89 times as compared with the reaction in carbonate buffer by no benzimidazole(BI) solution of 4×10-3 M CTABr. The value of pseudo first order rate constant(kψ) of the reaction in CTABr 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, CTABr, strongly catalyzes the reaction of IPNPIN with R-BI and its anion(R-BI⊖) in carbonate buffer(pH 10.7). For example, 4×10-3 M CTABr in 1×10-4 M BI solution increase the rate constant(kψ=98.5×10-3 sec-1) of the dephosphorylation by a factor ca.25, when compared with reaction(kψ=3.9×10-4 sec-1) in 1×10-4 M BI solution(without CTABr). And no CTABr solution, in 1×10-4 M BI solution increase the rate constant(kψ=3.9×10-4 sec-1) of the dephosphorylation by a factor ca.39, when compared with reaction (kψ=1.0×10-5 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 CTABr.

New functional surfactant, N,N-dimethyl-N-dodecyl-N-(2-methyl benzimidazoyl) ammonium chloride(DDBAC) having benzimidazole(BI) functional group have been synthesized and the critical micellar concentration of DDBAC measured by surface tentiometry and electric conductivity method was 8.9×10-4M. Micellar effects in DDBAC functional surfactant solution on the hydrolysis of p-nitrophenylacetate(p-NPA), p-nitrophenylpropionate(p-NPP) and p-nitrophenylvalerate(p-NPV) were observed with change of various pH (Tris-buffer). The pseudo first rate constants of hydrolysis of p-NPA, p-NPP and p-NPV in optimum concentration of DDBAC solution increase to about 160, 280 and 600 times, respectively, as compared with those of aqueous solution at pH 8.00(Tris-buffer). It is considered that benzimidazole functional moiety accelerates the reaction rates of hydrolysis because they act as nucleophile or general base. In optimum concentration of DDBAC solution, the rate constants of hydrolysis of p-NPP and p-NPV increase to about 1.5 and 3.0 times, respectively, as compared with that of p-NPA. It means that the more the carbon numbers of alkyl group of substrates, the larger the binding constants between DDBAC micelle and substrates are. To know the hydrolysis mechanism of p-NPCE(p-NPA, p-NPP and p-NPV), the deuterium kinetic isotope effects were measured in D2O solutions. Consequently the pseudo first order rate constant ratios in H2O and D2O solution, kH2O/kD2O, were about 2.8～3.0 range. It means that the mechanism of hydrolysis were proceeded by nucleophile and general base attack in approximately same value.