Structural Analysis of Heparin-Derived 3-O-Sulfated Tetrasaccharides: Antithrombin Binding Site Variants

J Pharm Sci. 2017 Apr;106(4):973-981. doi: 10.1016/j.xphs.2016.11.023. Epub 2016 Dec 20.

Abstract

Heparin is a polysaccharide that is widely used as an anticoagulant drug. The mechanism for heparin's anticoagulant activity is primarily through its interaction with a serine protease inhibitor, antithrombin III (AT), that enhances its ability to inactivate blood coagulation serine proteases, including thrombin (factor IIa) and factor Xa. The AT-binding site in the heparin is one of the most well-studied carbohydrate-protein binding sites and its structure is the basis for the synthesis of the heparin pentasaccharide drug, fondaparinux. Despite our understanding of the structural requirements for the heparin pentasaccharide AT-binding site, there is a lack of data on the natural variability of these binding sites in heparins extracted from animal tissues. The present work provides a detailed study on the structural variants of the tetrasaccharide fragments of this binding site afforded following treatment of a heparin with heparin lyase II. The 5 most commonly observed tetrasaccharide fragments of the AT-binding site are fully characterized, and a method for their quantification in heparin and low-molecular-weight heparin products is described.

Keywords: anticoagulant activity; antithrombin-binding site; heparin lyase; heparin-derived tetrasaccharides; structure-activity relationship.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Anticoagulants / chemistry*
  • Anticoagulants / metabolism
  • Antithrombin III / chemistry*
  • Antithrombin III / metabolism
  • Binding Sites / physiology
  • Heparin / chemistry*
  • Heparin / metabolism
  • Molecular Structure
  • Polysaccharides / chemistry*
  • Polysaccharides / metabolism
  • Swine

Substances

  • Anticoagulants
  • Polysaccharides
  • Antithrombin III
  • Heparin