Hydrophobic Mutagenesis and Semi-rational Engineering of Arginine Deiminase for Markedly Enhanced Stability and Catalytic Efficiency

Appl Biochem Biotechnol. 2015 Jul;176(5):1335-50. doi: 10.1007/s12010-015-1649-4. Epub 2015 Jun 4.

Abstract

Due to its systemic arginine degradation, arginine deiminase (ADI) has attracted attentions as an anti-tumor drug. Its low activity at physiological conditions among other limitations has necessitated its engineering for improved properties. The present study describes the hydrophobic mutagenesis and semi-rational engineering of ADI from Pseudomonas plecoglossicida (PpADI). Using an improved ADI variant M13 (D38H/A128T/E296K/H404R/I410L) as parent, site saturation mutagenesis at position 162 resulted in an over 20 % increase in protein solubility. Compared with M13 (15.23 U/mg), mutants M13-2 (M13+S245D) and M13-5 (M13+R243L) exhibited enhanced specific activity of 21.19 and 31.20 U/mg at physiological conditions. M13-5 displayed enhanced substrate specificity with a dramatic reduction in its K m value (from 0.52 to 0.16 mM). It is speculated that the improvements in M13-5 could mainly be attributed to the enhanced structural stability due to an R243L substitution. The hydrophobic contribution of Leu 243 was supported by mutant M13-9 (M13+A276W) generated based on the hydrophobic mutagenesis concept. M13-9 showed a specific activity of 18.68 U/mg, as well as remarkable thermal and pH stability. It retained over 90 % activity over pH range from 4.5 to 8.5. At 60 °C, the half-life of M13-9 was enhanced from 4 to 17.5 min in comparison with M13, and its specific activity at 62 °C (93.0 U/mg) was approximately fivefold of that determined at 37 °C. Our results suggest that the increased hydrophobicity around the active regions of PpADI might be crucial in improving its structural stability and ultimately catalytic efficiency.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Biocatalysis*
  • Electrophoresis, Polyacrylamide Gel
  • Enzyme Stability
  • Hydrogen Bonding
  • Hydrogen-Ion Concentration
  • Hydrolases / chemistry
  • Hydrolases / metabolism*
  • Hydrophobic and Hydrophilic Interactions*
  • Kinetics
  • Models, Molecular
  • Molecular Sequence Data
  • Mutagenesis*
  • Mutant Proteins / chemistry
  • Mutant Proteins / metabolism
  • Protein Engineering / methods*
  • Pseudomonas / enzymology
  • Rotation*
  • Sequence Alignment
  • Solubility
  • Temperature

Substances

  • Mutant Proteins
  • Hydrolases
  • arginine deiminase