skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structural Insight into Substrate Selectivity of Erwinia chrysanthemi L-Asparaginase

Journal Article · · Biochemistry
 [1];  [1];  [1]
  1. The Jesse Brown VA Medical Center, Chicago, IL (United States); Univ. of Chicago, IL (United States)

L-Asparaginases of bacterial origin are a mainstay of acute lymphoblastic leukemia treatment. The mechanism of action of these enzyme drugs is associated with their capacity to deplete the amino acid L-asparagine from the blood. However, clinical use of bacterial L-asparaginases is complicated by their dual L-asparaginase and L-glutaminase activities. The latter, even though representing only ~10% of the overall activity, is partially responsible for the observed toxic side effects. Hence, L-asparaginases devoid of L-glutaminase activity hold potential as safer drugs. Understanding the key determinants of L-asparaginase substrate specificity is a prerequisite step toward the development of enzyme variants with reduced toxicity. Here we present crystal structures of the Erwinia chrysanthemi L-asparaginase in complex with L-aspartic acid and with L-glutamic acid. These structures reveal two enzyme conformations—open and closed—corresponding to the inactive and active states, respectively. The binding of ligands induces the positioning of the catalytic Thr15 into its active conformation, which in turn allows for the ordering and closure of the flexible N-terminal loop. Notably, L-aspartic acid is more efficient than L-glutamic acid in inducing the active positioning of Thr15. Structural elements explaining the preference of the enzyme for L-asparagine over L-glutamine are discussed with guidance to the future development of more specific L-asparaginases.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
National Institutes of Health (NIH); US Department of Veterans Affairs (VA)
Grant/Contract Number:
RO1 EB013685; I01BX001919
OSTI ID:
1247365
Journal Information:
Biochemistry, Vol. 55, Issue 8; ISSN 0006-2960
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science

References (30)

Helicobacter pyloril-asparaginase: A promising chemotherapeutic agent journal December 2008
Atomic resolution structure of Erwinia chrysanthemi L -asparaginase journal December 2002
Refinement of Macromolecular Structures by the Maximum-Likelihood Method journal May 1997
Rational engineering of L-asparaginase reveals importance of dual activity for cancer cell toxicity journal February 2011
PHENIX: a comprehensive Python-based system for macromolecular structure solution. text January 2010
Glutaminase-free asparaginase fromvibrio succinogenes: An antilymphoma enzyme lacking hepatotoxicity journal September 1982
Structural Basis for the Activity and Substrate Specificity of Erwinia chrysanthemi l -Asparaginase , journal May 2001
Identification and Structural Analysis of an l-Asparaginase Enzyme from Guinea Pig with Putative Tumor Cell Killing Properties journal October 2014
Structural aspects of L-asparaginases, their friends and relations. journal December 2006
Glutaminase activity determines cytotoxicity of l-asparaginases on most leukemia cell lines journal July 2015
Pharmacological and clinical evaluation of l-asparaginase in the treatment of leukemia journal March 2007
Structures of two highly homologous bacterial L -asparaginases: a case of enantiomorphic space groups journal March 2001
A left-handed crossover involved in amidohydrolase catalysis: Crystal structure of journal August 1993
Integration, scaling, space-group assignment and post-refinement journal January 2010
Role of Glutamine Depletion in Directing Tissue-specific Nutrient Stress Responses to L-Asparaginase journal August 2006
Purification and characterization of glutaminase-free l-asparaginase from Pectobacterium carotovorum MTCC 1428 journal January 2011
Ion Binding Induces Closed Conformation in Pseudomonas 7A Glutaminase-Asparaginase (PGA):  Crystal Structure of the PGA-SO 4 2- -NH 4 + Complex at 1.7 Å Resolution , journal January 1997
Reduced antithrombin III levels during L-asparaginase therapy journal January 1980
Crystal structure of Escherichia coli L-asparaginase, an enzyme used in cancer therapy. journal February 1993
Evidence that the L-Asparaginase of Guinea pig Serum is Responsible for its Antilymphoma Effects journal July 1963
States and Functions of Tyrosine Residues in Escherichia coli Asparaginase II journal September 1994
Features and development of Coot journal March 2010
Kinetic properties and inhibition of Acinetobacter glutaminase-asparaginase journal March 1983
PHENIX: a comprehensive Python-based system for macromolecular structure solution journal January 2010
Engineering the substrate specificity of Escherichia coli asparaginase II. Selective reduction of glutaminase activity by amino acid replacements at position 248 journal January 2000
L-asparaginase for treatment of childhood acute lymphoblastic leukemia: What have we learned? (Commentary on Schrey et al., page 378) journal April 2011
In silico Engineering of L-Asparaginase to Have Reduced Glutaminase Side Activity for Effective Treatment of Acute Lymphoblastic Leukemia journal January 2011
MOLREP an Automated Program for Molecular Replacement journal December 1997
Dynamics of a mobile loop at the active site of Escherichia coli asparaginase journal September 2000
Purification and properties of a highly potent antitumor glutaminase-asparaginase from Pseudomonas 7Z. journal April 1976

Cited By (7)

Glutamine Metabolism in Cancer book January 2018
Development of L-Asparaginase Biobetters: Current Research Status and Review of the Desirable Quality Profiles journal January 2019
The differential ability of asparagine and glutamine in promoting the closed/active enzyme conformation rationalizes the Wolinella succinogenes L-asparaginase substrate specificity journal January 2017
Design and Characterization of Erwinia Chrysanthemi l-Asparaginase Variants with Diminished l-Glutaminase Activity journal June 2016
Engineering Cell‐Free Protein Synthesis for High‐Yield Production and Human Serum Activity Assessment of Asparaginase: Toward On‐Demand Treatment of Acute Lymphoblastic Leukemia journal April 2020
L-Asparaginase from E. chrysanthemi expressed in glycoswitch ® : effect of His-Tag fusion on the extracellular expression journal April 2019
Structure and function of the thermostable L -asparaginase from Thermococcus kodakarensis journal October 2017

Similar Records

Crystallization and preliminary crystallographic analysis of l-asparaginase from Erwinia carotovora
Journal Article · Fri Apr 01 00:00:00 EST 2005 · Acta Crystallographica. Section F · OSTI ID:1247365

Expression, purification and crystallization of Helicobacter pyloril-asparaginase
Journal Article · Fri Aug 01 00:00:00 EDT 2008 · Acta Crystallographica. Section F · OSTI ID:1247365

Three-dimensional structure of Erwinia carotovora L-asparaginase
Journal Article · Sun Oct 15 00:00:00 EDT 2006 · Crystallography Reports · OSTI ID:1247365