The effect of the hydrophobic environment on the retro-aldol reaction: comparison to a computationally-designed enzyme.

نویسندگان

  • Joshua Schmidt
  • Clayton Ehasz
  • Michael Epperson
  • Kimberly Klas
  • Justin Wyatt
  • Mirko Hennig
  • Marcello Forconi
چکیده

Recent work on a computationally-designed retroaldolase RA-61 suggested that most of the rate-acceleration brought about by this enzyme was due to non-specific interactions with the aromatic substrate. To provide a benchmark for the role of non-specific interactions in this system, we measured the second-order rate constant for the amine-catalysed retro-aldol reaction of methodol in the presence of non-specific hydrophobic pockets such as micelles. We found that a simple micellar system, that consists of a positively-charged surfactant and a long-chain amine, can accelerate the retro-aldol reaction of methodol by 9500-fold. This effect rivals the 10(5)-fold rate acceleration of RA-61. Similar results were obtained with BSA used as the catalyst, implying that the retro-aldol reaction of methodol can be greatly accelerated by non-specific hydrophobic pockets that contain an amino group.

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عنوان ژورنال:
  • Organic & biomolecular chemistry

دوره 11 48  شماره 

صفحات  -

تاریخ انتشار 2013