Ab initio calculations on various sialic acids provide valuable information about sialic acid-specific enzymes

This study presents ab initio calculations on six sialic acid derivatives (N-acetylneuraminic acid, 2-deoxy-2,3-didehydro-Nacetylneuraminic acid, N-acetyl-4-O-acetylneuraminic acid, N-glycolylneuraminic acid, N-glycolyl-4-O-acetylneuraminic acid and N-acetyl-9-O-acetylneuraminic acid). The calculations were carried out using the GAMESS-UK-Program. Since the charge distribution of a ligand has an essential impact on the specific interaction with an enzyme or a receptor, the precise results of ab initio calculations lead to significant information concerning possible roles of the different functional groups occurring on sialic acids. In correlation to this, valuable conclusions about the activities of different sialic acid-specific enzymes, such as sialidases, trans-sialidases, lyases and O-acetyl- or O-methyltransferases can be drawn, since these activities strongly depend on the presence or absence of the various functional groups. q 2004 Published by Elsevier B.V.

[1]  B. Horenstein,et al.  The N-Acetyl Neuraminyl Oxecarbenium Ion Is an Intermediate in the Presence of Anionic Nucleophiles , 1998 .

[2]  A. Frasch,et al.  Structural basis of sialyltransferase activity in trypanosomal sialidases , 2000 .

[3]  E. Tajkhorshid,et al.  Knowledge-based Homology Modeling and Experimental Determination of Amino Acid Side Chain Accessibility by the Laser Photo CIDNP (Chemically Induced Dynamic Nuclear Polarization) Approach in Solution: Lessons from the Small Sialidase of Clostridium perfringens , 1996 .

[4]  J. Vionnet,et al.  Elongation of alternating alpha 2,8/2,9 polysialic acid by the Escherichia coli K92 polysialyltransferase. , 2001, Glycobiology.

[5]  G. Hart,et al.  Carbohydrates in chemistry and biology , 2000 .

[6]  A. M. Wu,et al.  The Molecular Immunology of Complex Carbohydrates , 1988 .

[7]  J. Almlöf,et al.  Principles for a direct SCF approach to LICAO–MOab‐initio calculations , 1982 .

[8]  B. Henrissat,et al.  Structures and mechanisms of glycosyl hydrolases. , 1995, Structure.

[9]  R. Schauer Sialic acids : chemistry, metabolism and function , 1982 .

[10]  Jean-Raymond Abrial,et al.  On B , 1998, B.

[11]  Miss A.O. Penney (b) , 1974, The New Yale Book of Quotations.

[12]  U. Sommer,et al.  The Terminal Enzymes of Sialic Acid Metabolism: Acylneuraminate Pyruvate-Lyases , 1999, Bioscience reports.

[13]  Emad Tajkhorshid,et al.  Barrier to rotation around the Csp2-Csp2 bond of the ketoaldehyde enol ether MeC(o)CH=CH-OEt as determined by 13C NMR and ab initio calculations , 2001 .

[14]  B. Samyn-Petit,et al.  The human sialyltransferase family. , 2001, Biochimie.

[15]  J F Vliegenthart,et al.  Molecular dynamics-derived conformation and intramolecular interaction analysis of the N-acetyl-9-O-acetylneuraminic acid-containing ganglioside GD1a and NMR-based analysis of its binding to a human polyclonal immunoglobulin G fraction with selectivity for O-acetylated sialic acids. , 1996, Glycobiology.

[16]  S Cusack,et al.  Influenza B virus neuraminidase can synthesize its own inhibitor. , 1993, Structure.

[17]  A. Varki,et al.  Diversity in the sialic acids , 1992, Glycobiology.

[18]  G. Hansson,et al.  A novel sialidase which releases 2,7-anhydro-alpha-N-acetylneuraminic acid from sialoglycoconjugates. , 1990, The Journal of biological chemistry.

[19]  Taylor Nr,et al.  Molecular modeling studies on ligand binding to sialidase from influenza virus and the mechanism of catalysis. , 1994 .

[20]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[21]  Jan Kroon,et al.  Structure of α-D-N-acetyl-1-O-methylneuraminic acid methyl ester , 1990 .

[22]  H. Gabius,et al.  Sialic acids structure-analysis-metabolism-occurrence-recognition. , 1996, Biological chemistry Hoppe-Seyler.

[23]  A. Rosenberg Biology of the Sialic Acids , 1995, Springer US.

[24]  R. Schauer,et al.  The biosynthesis of 8-O-methylated sialic acids in the starfish Asterias rubens--isolation and characterisation of S-adenosyl-L-methionine:sialate-8-O-methyltransferase. , 1998, European journal of biochemistry.

[25]  J. Kamerling,et al.  Migration of O-acetyl groups in N,O-acetylneuraminic acids. , 1987, European journal of biochemistry.

[26]  J. Tiralongo,et al.  Two Trans-sialidase Forms with Different Sialic Acid Transfer and Sialidase Activities from Trypanosoma congolense* , 2003, Journal of Biological Chemistry.

[27]  S. Withers,et al.  Mechanisms of enzymatic glycoside hydrolysis. , 1994, Current opinion in structural biology.

[28]  R. Gerardy-Schahn,et al.  Polysialic acid: three-dimensional structure, biosynthesis and function. , 1998, Current opinion in structural biology.

[29]  Pedro M Alzari,et al.  The crystal structure and mode of action of trans-sialidase, a key enzyme in Trypanosoma cruzi pathogenesis. , 2002, Molecular cell.

[30]  R. Schauer Chemistry, metabolism, and biological functions of sialic acids. , 1982, Advances in carbohydrate chemistry and biochemistry.

[31]  R. Schauer,et al.  The biosynthesis of N-glycoloylneuraminic acid occurs by hydroxylation of the CMP-glycoside of N-acetylneuraminic acid. , 1988, Biological chemistry Hoppe-Seyler.

[32]  C. W. von der Lieth,et al.  Solution conformations of GM3 gangliosides containing different sialic acid residues as revealed by NOE-based distance mapping, molecular mechanics, and molecular dynamics calculations. , 1992, Biochemistry.

[33]  J. Tiralongo,et al.  Characterization of the Sialate-7(9)-O-Acetyltransferase from the Microsomes of Human Colonic Mucosa , 2002, Biological chemistry.

[34]  Y. Li,et al.  The 1.8 A structures of leech intramolecular trans-sialidase complexes: evidence of its enzymatic mechanism. , 1999, Journal of molecular biology.

[35]  S. Kitazume,et al.  Identification of polysialic acid-containing glycoprotein in the jelly coat of sea urchin eggs. Occurrence of a novel type of polysialic acid structure. , 1994, The Journal of biological chemistry.

[36]  R. Schauer,et al.  Structure, function and metabolism of sialic acids , 1998, Cellular and Molecular Life Sciences CMLS.

[37]  R. Schauer,et al.  Characterization and mutagenesis of the recombinant N-acetylneuraminate lyase from Clostridium perfringens: insights into the reaction mechanism. , 2001, European journal of biochemistry.

[38]  W. R. Jackson,et al.  Active site modulation in the N-acetylneuraminate lyase sub-family as revealed by the structure of the inhibitor-complexed Haemophilus influenzae enzyme. , 2000, Journal of molecular biology.

[39]  R. Schauer,et al.  Characterization of the enzymatic 7-O-acetylation of sialic acids and evidence for enzymatic O-acetyl migration from C-7 to C-9 in bovine submandibular gland. , 1998, Journal of biochemistry.

[40]  M. Field,et al.  Is There a Covalent Intermediate in the Viral Neuraminidase Reaction? A Hybrid Potential Free-Energy Study , 1999 .

[41]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[42]  Anthony J. Stone,et al.  Distributed multipole analysis, or how to describe a molecular charge distribution , 1981 .