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Effect of cationic gemini surfactants on the hydrolysis of carboxylate and phosphate esters using hydroxamate ions

Colloid and Polymer Science, ISSN: 0303-402X, Vol: 286, Issue: 3, Page: 293-303
2008
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Metrics Details

  • Citations
    23
    • Citation Indexes
      23
  • Captures
    14

Article Description

The kinetics of the hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyl diphenyl phosphate (PNPDPP) by hydroxamate ions mediated by gemini surfactants with quaternary ammonium bromide (16-n-16,2Br, n = 3, 4, 6, 12) and pyridinium chloride (12py-n-py12,2Cl, n = 3, 4) head group have been investigated at 27 °C. The gemini surfactant with the pyridinium head group, 12-py-4-py12,2Cl (tetramethylene-1,4 bis dodecylpyridinium chloride) shows a large rate acceleration effect than that with an ammonium head group, 16-12-16,2Br, relative to those in water. The apparent pK of the hydroxamic acids have been determined in the presence of gemini surfactants. Catalytic system N-phenylbenzohydroxamate/12py-4-py12,2Cl demonstrated over ∼1,590-fold and ∼255-fold rate enhancement in the hydrolysis of PNPA and PNPDPP, respectively, for the identical reaction performed in buffer aqueous media at 27 °C. The second order rate constant and binding constants for reactions were determined employing pseudophase model for micellar catalysis. © Springer-Verlag 2007.

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