Kinetic mechanism of the endogenous lactate dehydrogenase activity of duck epsilon-crystallin

Arch Biochem Biophys. 1991 Feb 1;284(2):285-91. doi: 10.1016/0003-9861(91)90297-v.

Abstract

Initial velocity, product inhibition, and substrate inhibition studies suggest that the endogenous lactate dehydrogenase activity of duck epsilon-crystallin follows an order Bi-Bi sequential mechanism. In the forward reaction (pyruvate reduction), substrate inhibition by pyruvate was uncompetitive with inhibition constant of 6.7 +/- 1.7 mM. In the reverse reaction (lactate oxidation), substrate inhibition by L-lactate was uncompetitive with inhibition constant of 158 +/- 25 mM. The cause of these inhibitions may be due to epsilon-crystallin-NAD(+)-pyruvate and epsilon-crystallin-NADH-L-lactate abortive ternary complex formation as suggested by the multiple inhibition studies. Pyruvate binds to free enzyme very poorly, with a very large dissociation constant. Bromopyruvate, fluoropyruvate, pyruvate methyl ester, and pyruvate ethyl ester are alternative substrates for pyruvate. 3-Acetylpyridine adenine dinucleotide, nicotinamide 1,N6-ethenoadenine dinucleotide, and nicotinamide hypoxanthine dinucleotide serve as alternative coenzymes for epsilon-crystallin. All the above alternative substrates or coenzymes showed an intersecting initial-velocity pattern conforming to the order Bi--Bi kinetic mechanism. Nicotinic acid adenine dinucleotide, thionicotinamide adenine dinucleotide, and 3-aminopyridine adenine dinucleotide acted as inhibitors for this enzymatic crystallin. The inhibitors were competitive versus NAD+ and noncompetitive versus L-lactate. alpha-NAD+ was a noncompetitive inhibitor with respect to the usual beta-NAD+. D-Lactate, tartronate, and oxamate were strong dead-end inhibitors for the lactate dehydrogenase activity of epsilon-crystallin. Both D-lactate and tartronate were competitive inhibitors versus L-lactate while oxamate was a competitive inhibitor versus pyruvate. We conclude that the structural requirements for the substrate and coenzyme of epsilon-crystallin are similar to those of other dehydrogenases and that the carboxamide carbonyl group of the nicotinamide moiety is important for the coenzyme activity.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Binding, Competitive
  • Coenzymes / metabolism
  • Crystallins / chemistry*
  • Ducks
  • Heart / drug effects
  • Kinetics
  • L-Lactate Dehydrogenase / metabolism*
  • Lactates / pharmacology
  • Lactic Acid
  • Myocardium / enzymology*
  • NAD / metabolism
  • Oxamic Acid / pharmacology
  • Pyruvates / metabolism
  • Pyruvic Acid
  • Substrate Specificity / drug effects
  • Tartronates / pharmacology

Substances

  • Coenzymes
  • Crystallins
  • Lactates
  • Pyruvates
  • Tartronates
  • NAD
  • Lactic Acid
  • Pyruvic Acid
  • L-Lactate Dehydrogenase
  • Oxamic Acid