Acidic derivatives of homocysteine thiolactone: utility as anionic linkers

Bioconjug Chem. 1992 Nov-Dec;3(6):514-8. doi: 10.1021/bc00018a009.

Abstract

Homocysteine thiolactone (2) derivatives in which the nitrogen is acylated with groups containing acidic functionalities have been synthesized. These include the succinyl (3), the carboxymethylglutaryl (4), the 3-phosphonopropionyl (7), and the 3-sulfopropionyl (8) derivatives. These thiolactones can be used to introduce a thiol functionality into proteins such as the outer membrane protein complex of Neisseria meningitidis (OMPC) allowing conjugation with electrophilic ligands. This chemistry is the same as with N-acetylhomocysteine thiolactone (1), but their pKa values are such that at pH 7 concomitant negative charge is introduced into the conjugate. Such negative charge should neutralize some excess positive charge introduced when arginine- and lysine-rich peptides are bonded as ligands. In the case of OMPC, introduction of such positive charge appears to effect irreversible precipitation. The system has been studied using the maleimidopropionyl and bromoacetyltriarginine (9 and 10) derivatives as models. In select instances anionic spacers reduce the degree of precipitation relative to N-acetyl-homocysteine thiolactone derivatives.

MeSH terms

  • Amino Acids / chemistry
  • Anions
  • Bacterial Outer Membrane Proteins / chemistry
  • Chemical Precipitation
  • Homocysteine / analogs & derivatives*
  • Homocysteine / chemical synthesis
  • Homocysteine / chemistry
  • Hydrogen-Ion Concentration
  • Neisseria meningitidis / chemistry

Substances

  • Amino Acids
  • Anions
  • Bacterial Outer Membrane Proteins
  • Homocysteine
  • homocysteine thiolactone