Novel D- glucose Based Glycomonomers Synthesis and Characterization
In the last decade, carbohydrates have attracted great
attention as renewable resources for the chemical industry.
Carbohydrates are abundantly found in nature in the form of
monomers, oligomers and polymers, or as components of
biopolymers and other naturally occurring substances. As natural
products, they play important roles in conferring certain physical,
chemical, and biological properties to their carrier molecules.The
synthesis of this particular carbohydrate glycomonomer is part of our
work to obtain biodegradable polymers. Our current paper describes
the synthesis and characterization of a novel carbohydrate
glycomonomer starting from D-glucose, in several synthesis steps,
that involve the protection/deprotection of the D-glucose ring via
acetylation, tritylation, then selective deprotection of the aromaticaliphatic
protective group, in order to obtain 1,2,3,4-tetra-O-acetyl-
6-O-allyl-β-D-glucopyranose. The glycomonomer was then obtained
by the allylation in drastic conditions of 1,2,3,4-tetra-O-acetyl-6-Oallyl-
β-D-glucopyranose with allylic alcohol in the presence of
stannic chloride, in methylene chloride, at room temperature. The
proposed structure of the glycomonomer, 2,3,4-tri-O-acetyl-1,6-di-
O-allyl-β-D-glucopyranose, was confirmed by FTIR, NMR and
HPLC-MS spectrometry. This glycomonomer will be further
submitted to copolymerization with certain acrylic or methacrylic
monomers in order to obtain competitive plastic materials for
applications in the biomedical field.
[1] D. Teng, W. Yin, X. Zhang, Z. Wang, C. Li, "New glycoconjugate
polyacrylamide with water-solubility and additional activated groups:
synthesis and characterization", Journal of Polymer Research, 16, 2009,
pp. 311-316.
[2] V. Ladmiral, E. Melia, D. M. Haddleton, "Synthetic glycopolymers: An
overview", European Polymer Journal, 40, 2004, pp. 431-449.
[3] S. Thadke, M. Kar, S.S. Gupta, S. Hortha, "Gold catalyzed
glycosidations for the synthesis of sugar acrylate/acrylamide hybrids and
their utility", Carbohydrate Research, 346, 2011, pp. 1511-1518.
[4] M.X. Hu, Z.K. Xu, "Carbohydrate decoration of microporous
polypropylene membranes for lectin affinity adsorption: comparison of
mono- and disaccharides", Colloids and Surfaces B: Biointerfaces, 85,
2011, pp. 19-25.
[5] K. Jain, P. Kercharwani, U. Gupta, N. Jain, "A review of glycosylated
carriers for drug delivery", Biomaterials, 33, 2012, pp. 4166-4186.
[6] Z. Yu, M.M. Cui, J. Yan, Y. You, "One-pot synthesis of hyperbranched
poly(amido amine) clicked with a sugar shell via Michael addition
polymerization and thiol click reaction", Science China Chemistry, 53:8,
2010, pp. 1663-1668.
[7] N. Peppas, Y. Huang, "Polymers and gels as molecular recognition
agents", Pharmaceutical Research,, 19:5, 2002, pp. 578-587.
[8] Y. Wang, X. Zhang, Y. Han, C. Cheng, C. Li, "pH- and glucosesensitive
glycopolymer nanoparticles based on phenylboronic acid for
triggered release of insulin", Carbohydrate Polymers, 89, 2012, pp. 124-
131.
[9] A. Munoz-Bonilla, V. Bordege, O. Leon, R. Cuervo-Rodriguez, M.
Sanchez-Chaves, M. Fernandez-Garcia, "Influence of glycopolymers
structure on the copolymerization reaction and on their binding behavior
with lectins", European Polymer Journal, 48, 2012, pp. 963-973.
[10] J. Nicolas, Y Guillaneuf, C. Lefay, D. Bertin, D. Gigmes, B. Charleux,
"Nitroxide-Mediated polymerization", Progress in Polymer Science,
2012, accepted manuscript, doi:10.1016/j.progpolymsci.2012.06.002.
[11] M .I. Osborn, Academic Press, 2002, pp. 50.
[12] D. D. Reynolds, W. Lloyd Evans, Organic Synthese, 3, 1955, pp.432.R.
W. Lucky, "Automatic equalization for digital communication," Bell
Syst. Tech. J., vol. 44, no. 4, pp. 547-588, Apr. 1965.
[13] L.M ┼×tefan, A.M. Panâ, C. Pascariu, E. ┼×i┼ƒu, G. Bandur, L.M. Rusnac,
"Synthesis and characterization of a new methacrylic glycomonomer",
Turk J Chem, 35, 2011, pp. 657-667.
[14] A.M. Panâ, L.Rusnac, G.Bandur, E. ┼×i┼ƒu, V.Badea, M. Silion,
"Synthesis and Characterization of New Glycopolymers Based on
Monosachharides and Maleic Anhydride I. Glucose derivatives",
Materiale Plastice, Bucure┼ƒti, 2010, 47(1), ´Çápp.28-34.
[15] Panâ A.M., Rusnac L.M., Bandur G., Silion M., Deleanu C., and Bâlan
M., "Novel D-glucose and D-mannose based oligomers. Synthesis and
characterization", e-Polymers, 2011, no.004, pp. 1-13.
[1] D. Teng, W. Yin, X. Zhang, Z. Wang, C. Li, "New glycoconjugate
polyacrylamide with water-solubility and additional activated groups:
synthesis and characterization", Journal of Polymer Research, 16, 2009,
pp. 311-316.
[2] V. Ladmiral, E. Melia, D. M. Haddleton, "Synthetic glycopolymers: An
overview", European Polymer Journal, 40, 2004, pp. 431-449.
[3] S. Thadke, M. Kar, S.S. Gupta, S. Hortha, "Gold catalyzed
glycosidations for the synthesis of sugar acrylate/acrylamide hybrids and
their utility", Carbohydrate Research, 346, 2011, pp. 1511-1518.
[4] M.X. Hu, Z.K. Xu, "Carbohydrate decoration of microporous
polypropylene membranes for lectin affinity adsorption: comparison of
mono- and disaccharides", Colloids and Surfaces B: Biointerfaces, 85,
2011, pp. 19-25.
[5] K. Jain, P. Kercharwani, U. Gupta, N. Jain, "A review of glycosylated
carriers for drug delivery", Biomaterials, 33, 2012, pp. 4166-4186.
[6] Z. Yu, M.M. Cui, J. Yan, Y. You, "One-pot synthesis of hyperbranched
poly(amido amine) clicked with a sugar shell via Michael addition
polymerization and thiol click reaction", Science China Chemistry, 53:8,
2010, pp. 1663-1668.
[7] N. Peppas, Y. Huang, "Polymers and gels as molecular recognition
agents", Pharmaceutical Research,, 19:5, 2002, pp. 578-587.
[8] Y. Wang, X. Zhang, Y. Han, C. Cheng, C. Li, "pH- and glucosesensitive
glycopolymer nanoparticles based on phenylboronic acid for
triggered release of insulin", Carbohydrate Polymers, 89, 2012, pp. 124-
131.
[9] A. Munoz-Bonilla, V. Bordege, O. Leon, R. Cuervo-Rodriguez, M.
Sanchez-Chaves, M. Fernandez-Garcia, "Influence of glycopolymers
structure on the copolymerization reaction and on their binding behavior
with lectins", European Polymer Journal, 48, 2012, pp. 963-973.
[10] J. Nicolas, Y Guillaneuf, C. Lefay, D. Bertin, D. Gigmes, B. Charleux,
"Nitroxide-Mediated polymerization", Progress in Polymer Science,
2012, accepted manuscript, doi:10.1016/j.progpolymsci.2012.06.002.
[11] M .I. Osborn, Academic Press, 2002, pp. 50.
[12] D. D. Reynolds, W. Lloyd Evans, Organic Synthese, 3, 1955, pp.432.R.
W. Lucky, "Automatic equalization for digital communication," Bell
Syst. Tech. J., vol. 44, no. 4, pp. 547-588, Apr. 1965.
[13] L.M ┼×tefan, A.M. Panâ, C. Pascariu, E. ┼×i┼ƒu, G. Bandur, L.M. Rusnac,
"Synthesis and characterization of a new methacrylic glycomonomer",
Turk J Chem, 35, 2011, pp. 657-667.
[14] A.M. Panâ, L.Rusnac, G.Bandur, E. ┼×i┼ƒu, V.Badea, M. Silion,
"Synthesis and Characterization of New Glycopolymers Based on
Monosachharides and Maleic Anhydride I. Glucose derivatives",
Materiale Plastice, Bucure┼ƒti, 2010, 47(1), ´Çápp.28-34.
[15] Panâ A.M., Rusnac L.M., Bandur G., Silion M., Deleanu C., and Bâlan
M., "Novel D-glucose and D-mannose based oligomers. Synthesis and
characterization", e-Polymers, 2011, no.004, pp. 1-13.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:62176", author = "M.S. Mazăre and A. M. Pană and L. M. Ştefan and M. Silion and M. Bălan and G. Bandur and L. M. Rusnac", title = "Novel D- glucose Based Glycomonomers Synthesis and Characterization", abstract = "In the last decade, carbohydrates have attracted great
attention as renewable resources for the chemical industry.
Carbohydrates are abundantly found in nature in the form of
monomers, oligomers and polymers, or as components of
biopolymers and other naturally occurring substances. As natural
products, they play important roles in conferring certain physical,
chemical, and biological properties to their carrier molecules.The
synthesis of this particular carbohydrate glycomonomer is part of our
work to obtain biodegradable polymers. Our current paper describes
the synthesis and characterization of a novel carbohydrate
glycomonomer starting from D-glucose, in several synthesis steps,
that involve the protection/deprotection of the D-glucose ring via
acetylation, tritylation, then selective deprotection of the aromaticaliphatic
protective group, in order to obtain 1,2,3,4-tetra-O-acetyl-
6-O-allyl-β-D-glucopyranose. The glycomonomer was then obtained
by the allylation in drastic conditions of 1,2,3,4-tetra-O-acetyl-6-Oallyl-
β-D-glucopyranose with allylic alcohol in the presence of
stannic chloride, in methylene chloride, at room temperature. The
proposed structure of the glycomonomer, 2,3,4-tri-O-acetyl-1,6-di-
O-allyl-β-D-glucopyranose, was confirmed by FTIR, NMR and
HPLC-MS spectrometry. This glycomonomer will be further
submitted to copolymerization with certain acrylic or methacrylic
monomers in order to obtain competitive plastic materials for
applications in the biomedical field.", keywords = "allylation, D-glucose, glycomonomer, trityl chloride", volume = "6", number = "8", pages = "821-4", }