Glycan tagging to produce bioactive ligands for a surface plasmon resonance study via immobilization on different surfaces.

Suitable glycan derivatives will find immediate application in the study of their interactions. Here, we present an efficient synthetic strategy to introduce a fluorescent tag functionalized with an amino group into a model disaccharide structure (lactose). This strategy led to the maintenance of bioactivity, checked by the study of the interaction of this bioconjugate with a plant lectin (mistletoe lectin 1) by NMR spectroscopy, computational docking, and surface plasmon resonance (SPR). To demonstrate the versatility of this approach, we immobilized the new glycan derivatives on different surfaces, and a comparative analysis is presented and can be successfully used for biomimetic carbohydrate-protein interaction studies on the SPR biochip.

[1]  M. Martín-Pastor,et al.  Solution conformation and dynamics of a tetrasaccharide related to the LewisX antigen deduced by NMR relaxation measurements , 1997, Journal of biomolecular NMR.

[2]  Zhichao Pei,et al.  Glycosyldisulfides from dynamic combinatorial libraries as O-glycoside mimetics for plant and endogenous lectins: their reactivities in solid-phase and cell assays and conformational analysis by molecular dynamics simulations. , 2006, Bioorganic & medicinal chemistry.

[3]  D. Toomre,et al.  Advances in the use of biotinylated diaminopyridine (BAP) as a versatile fluorescent tag for oligosaccharides. , 1994, Glycobiology.

[4]  F. Cañada,et al.  Bovine Heart Galectin-1 Selects a Unique (Syn) Conformation of C-Lactose, a Flexible Lactose Analogue , 1999 .

[5]  Milan Mrksich,et al.  Carbohydrate arrays for the evaluation of protein binding and enzymatic modification. , 2002, Chemistry & biology.

[6]  A. Tonevitsky,et al.  Mistletoe lectin I forms a double trefoil structure , 1998, FEBS letters.

[7]  J. L. Asensio,et al.  The pattern of distribution of amino groups modulates the structure and dynamics of natural aminoglycosides: implications for RNA recognition. , 2007, Journal of the American Chemical Society.

[8]  H. Gabius,et al.  AB-type lectin (toxin/agglutinin) from mistletoe: differences in affinity of the two galactoside-binding Trp/Tyr-sites and regulation of their functionality by monomer/dimer equilibrium. , 2006, Glycobiology.

[9]  R. Parekh,et al.  Nonselective and efficient fluorescent labeling of glycans using 2-amino benzamide and anthranilic acid. , 1995, Analytical biochemistry.

[10]  F. Cañada,et al.  Conformational Behavior of Aza-C-Glycosides: Experimental Demonstration of the Relative Role of the exo-anomeric Effect and 1,3-Type Interactions in Controlling the Conformation of Regular Glycosides , 1999 .

[11]  B. Meyer,et al.  Group epitope mapping by saturation transfer difference NMR to identify segments of a ligand in direct contact with a protein receptor. , 2001, Journal of the American Chemical Society.

[12]  D. Toomre,et al.  Biotinylated diaminopyridine: an approach to tagging oligosaccharides and exploring their biology. , 1993, Proceedings of the National Academy of Sciences of the United States of America.

[13]  W. C. Still,et al.  Semianalytical treatment of solvation for molecular mechanics and dynamics , 1990 .

[14]  Gabriel Cuevas,et al.  Molecular recognition of saccharides by proteins. Insights on the origin of the carbohydrate-aromatic interactions. , 2005, Journal of the American Chemical Society.

[15]  Jesús Jiménez-Barbero,et al.  New structural insights into carbohydrate-protein interactions from NMR spectroscopy. , 2003, Current opinion in structural biology.

[16]  Dustin J Maly,et al.  Probing Low Affinity and Multivalent Interactions with Surface Plasmon Resonance: Ligands for Concanavalin A , 1998 .

[17]  Lai-Xi Wang,et al.  Neutral, acidic, and basic derivatives of anthranilamide that confer different formal charge to reducing oligosaccharides. , 2004, Carbohydrate research.

[18]  M. Martín-Pastor,et al.  The use of CVFF and CFF91 force fields in conformational analysis of carbohydrate molecules. Comparison with AMBER molecular mechanics and dynamics calculations for methyl alpha-lactoside. , 1995, International journal of biological macromolecules.

[19]  H. Gabius,et al.  Introduction of extended LEC14‐type branching into core‐fucosylated biantennary N‐glycan , 2005, The FEBS journal.

[20]  S. Peyrottes,et al.  Biolabile constructs for pronucleotide design , 2005 .

[21]  M. Monsigny,et al.  Carbohydrate-lectin interactions assessed by surface plasmon resonance. , 2003, Biochimie.

[22]  Norman L. Allinger,et al.  Molecular mechanics. The MM3 force field for hydrocarbons. 1 , 1989 .

[23]  A. Tonevitsky,et al.  Crystal structure at 3 A of mistletoe lectin I, a dimeric type-II ribosome-inactivating protein, complexed with galactose. , 2003, European journal of biochemistry.

[24]  H. Gabius,et al.  Lactose-containing starburst dendrimers: influence of dendrimer generation and binding-site orientation of receptors (plant/animal lectins and immunoglobulins) on binding properties. , 1999, Glycobiology.

[25]  H. Hashimoto,et al.  Synthesis of 2-[(2-pyridyl)amino]ethyl beta-D-lactosaminide and evaluation of its acceptor ability for sialyltransferase: a comparison with 4-methylumbelliferyl and dansyl beta-D-lactosaminide. , 2004, Carbohydrate research.

[26]  W. Willats,et al.  Solid-phase chemical tools for glycobiology. , 2006, Carbohydrate research.

[27]  R. Kiss,et al.  Evidence for Stimulation of Tumor Proliferation in Cell Lines and Histotypic Cultures by Clinically Relevant Low Doses of the Galactoside-Binding Mistletoe Lectin, A Component of Proprietary Extracts , 2001, Cancer investigation.

[28]  L. M. Likhosherstov,et al.  A New Simple Synthesis of Amino Sugar β-D-Glycosylamines. , 1986 .

[29]  M. Gallop,et al.  Strategies for the synthesis and screening of glycoconjugates. 1. A library of glycosylamines. , 1995, Bioconjugate chemistry.

[30]  B. Imperiali,et al.  Improving glycopeptide synthesis: a convenient protocol for the preparation of beta-glycosylamines and the synthesis of glycopeptides. , 2005, The Journal of organic chemistry.

[31]  G. Magnusson,et al.  2-Bromoethyl glycosides: synthesis and characterisation , 1983 .

[32]  B. Xia,et al.  Versatile fluorescent derivatization of glycans for glycomic analysis , 2005, Nature Methods.

[33]  Johannis P Kamerling,et al.  Identification of carbohydrates binding to lectins by using surface plasmon resonance in combination with HPLC profiling. , 2004, Glycobiology.

[34]  H. Gabius.  Influence of type of linkage and spacer on the interaction of beta-galactoside-binding proteins with immobilized affinity ligands. , 1990, Analytical biochemistry.

[35]  David S. Goodsell,et al.  Automated docking using a Lamarckian genetic algorithm and an empirical binding free energy function , 1998, J. Comput. Chem..

[36]  H. Gabius,et al.  Monomer/dimer equilibrium of the AB-type lectin from mistletoe enables combination of toxin/agglutinin activities in one protein: analysis of native and citraconylated proteins by ultracentrifugation/gel filtration and cell biological consequences of dimer destabilization. , 2005, Glycobiology.

[37]  J. Jiménez-Barbero,et al.  NMR investigations of protein-carbohydrate interactions: insights into the topology of the bound conformation of a lactose isomer and beta-galactosyl xyloses to mistletoe lectin and galectin-1. , 2001, Biochimica et biophysica acta.

[38]  P. Seeberger,et al.  Carbohydrate arrays as tools for glycomics. , 2002, Angewandte Chemie.

[39]  L. Anderson,et al.  Efficient preparation of allyl 2,3,6,2',3',6'-hexa-O-benzyl-beta-lactoside and its use as a glycosyl acceptor for chain extension at O-4'. , 1994, Carbohydrate research.