Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV

The ReAV enzyme from <i>Rhizobium etli</i>, a representative of Class 3 L-asparaginases, is sequentially and structurally different from other known L-asparaginases. This distinctiveness makes ReAV a candidate for novel antileukemic therapies. ReAV is a homodimeric protein, with each sub...

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Main Authors: Kinga Pokrywka, Marta Grzechowiak, Joanna Sliwiak, Paulina Worsztynowicz, Joanna I. Loch, Milosz Ruszkowski, Miroslaw Gilski, Mariusz Jaskolski
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Biomolecules
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Online Access:https://www.mdpi.com/2218-273X/15/7/944
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author Kinga Pokrywka
Marta Grzechowiak
Joanna Sliwiak
Paulina Worsztynowicz
Joanna I. Loch
Milosz Ruszkowski
Miroslaw Gilski
Mariusz Jaskolski
author_facet Kinga Pokrywka
Marta Grzechowiak
Joanna Sliwiak
Paulina Worsztynowicz
Joanna I. Loch
Milosz Ruszkowski
Miroslaw Gilski
Mariusz Jaskolski
author_sort Kinga Pokrywka
collection DOAJ
description The ReAV enzyme from <i>Rhizobium etli</i>, a representative of Class 3 L-asparaginases, is sequentially and structurally different from other known L-asparaginases. This distinctiveness makes ReAV a candidate for novel antileukemic therapies. ReAV is a homodimeric protein, with each subunit containing a highly specific zinc-binding site created by two cysteines, a lysine, and a water molecule. Two Ser-Lys tandems (Ser48-Lys51, Ser80-Lys263) are located in the close proximity of the metal binding site, with Ser48 hypothesized to be the catalytic nucleophile. To further investigate the catalytic process of ReAV, site-directed mutagenesis was employed to introduce alanine substitutions at residues from the Ser-Lys tandems and at Arg47, located near the Ser48-Lys51 tandem. These mutational studies, along with enzymatic assays and X-ray structure determinations, demonstrated that substitution of each of these highly conserved residues abolished the catalytic activity, confirming their essential role in enzyme mechanism.
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spelling doaj-art-a873a0ef5c2c4c868d8a225ffae8dc322025-08-20T02:45:45ZengMDPI AGBiomolecules2218-273X2025-06-0115794410.3390/biom15070944Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAVKinga Pokrywka0Marta Grzechowiak1Joanna Sliwiak2Paulina Worsztynowicz3Joanna I. Loch4Milosz Ruszkowski5Miroslaw Gilski6Mariusz Jaskolski7Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandInstitute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandInstitute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandInstitute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandDepartment of Crystal Chemistry and Crystal Physics, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, PolandInstitute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandInstitute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandInstitute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznan, PolandThe ReAV enzyme from <i>Rhizobium etli</i>, a representative of Class 3 L-asparaginases, is sequentially and structurally different from other known L-asparaginases. This distinctiveness makes ReAV a candidate for novel antileukemic therapies. ReAV is a homodimeric protein, with each subunit containing a highly specific zinc-binding site created by two cysteines, a lysine, and a water molecule. Two Ser-Lys tandems (Ser48-Lys51, Ser80-Lys263) are located in the close proximity of the metal binding site, with Ser48 hypothesized to be the catalytic nucleophile. To further investigate the catalytic process of ReAV, site-directed mutagenesis was employed to introduce alanine substitutions at residues from the Ser-Lys tandems and at Arg47, located near the Ser48-Lys51 tandem. These mutational studies, along with enzymatic assays and X-ray structure determinations, demonstrated that substitution of each of these highly conserved residues abolished the catalytic activity, confirming their essential role in enzyme mechanism.https://www.mdpi.com/2218-273X/15/7/944hydrolaseamidohydrolaseL-asparaginaseleukemiametalloproteinsite-directed mutagenesis
spellingShingle Kinga Pokrywka
Marta Grzechowiak
Joanna Sliwiak
Paulina Worsztynowicz
Joanna I. Loch
Milosz Ruszkowski
Miroslaw Gilski
Mariusz Jaskolski
Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV
Biomolecules
hydrolase
amidohydrolase
L-asparaginase
leukemia
metalloprotein
site-directed mutagenesis
title Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV
title_full Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV
title_fullStr Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV
title_full_unstemmed Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV
title_short Probing the Active Site of Class 3 L-Asparaginase by Mutagenesis: Mutations of the Ser-Lys Tandems of ReAV
title_sort probing the active site of class 3 l asparaginase by mutagenesis mutations of the ser lys tandems of reav
topic hydrolase
amidohydrolase
L-asparaginase
leukemia
metalloprotein
site-directed mutagenesis
url https://www.mdpi.com/2218-273X/15/7/944
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