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Synthesis of Altrose Poly-amido-saccharides with ß-N-(1→2)-d-amide Linkages: A Right-Handed Helical Conformation Engineered in at the Monomer Level.
Xiao, Ruiqing; Dane, Eric L; Zeng, Jialiu; McKnight, Christopher J; Grinstaff, Mark W.
Afiliación
  • Xiao R; Department of Chemistry and ‡Department of Biomedical Engineering, Boston University , Boston, Massachusetts 02215, United States.
  • Dane EL; Department of Physiology and Biophysics and ∥Department of Medicine, Boston University School of Medicine , Boston, Massachusetts 02118, United States.
  • Zeng J; Department of Chemistry and ‡Department of Biomedical Engineering, Boston University , Boston, Massachusetts 02215, United States.
  • McKnight CJ; Department of Physiology and Biophysics and ∥Department of Medicine, Boston University School of Medicine , Boston, Massachusetts 02118, United States.
  • Grinstaff MW; Department of Chemistry and ‡Department of Biomedical Engineering, Boston University , Boston, Massachusetts 02215, United States.
J Am Chem Soc ; 139(40): 14217-14223, 2017 10 11.
Article en En | MEDLINE | ID: mdl-28902504
The design and synthesis of amide-linked saccharide oligomers and polymers, which are predisposed to fold into specific ordered secondary structures, is of significant interest. Herein, right-handed helical poly amido-saccharides (PASs) with ß-N-(1→2)-d-amide linkages are synthesized by the anionic ring-opening polymerization of an altrose ß-lactam monomer (alt-lactam). The right-handed helical conformation is engineered into the polymers by preinstalling the ß configuration of the lactam ring in the monomer via the stereospecific [2+2] cycloaddition of trichloroacetyl isocyanate with a d-glycal possessing a 3-benzyloxy group oriented to the α-face of the pyranose. The tert-butylacetyl chloride initiated polymerization of the alt-lactam proceeds smoothly to afford stereoregular polymers with narrow dispersities. Birch reduction of the benzylated polymers gives water-soluble altrose PASs (alt-PASs) in high yields without degradation of the polymer backbone. Circular dichroism analysis shows the alt-PASs adopt a right-handed helical conformation in aqueous solutions. This secondary conformation is stable over a wide range of different conditions, such as pH (2.0 to 12.0), temperature (5 to 75 °C), ionic salts (2.0 M LiCl, NaCl, and KCl), as well as in the presence of protein denaturants (4.0 M urea and guanidinium chloride). Cytotoxicity studies reveal that the alt-PASs are nontoxic to HEK, HeLa, and NIH3T3 cells. The results showcase the ability to direct solution conformation of polymers through monomer design. This approach is especially well-suited and straightforward for PASs as the helical conformations formed result from constraints imposed by the relatively rigid and sterically bulky repeating units.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Polisacáridos / Amidas / Lactamas Límite: Animals / Humans Idioma: En Revista: J Am Chem Soc Año: 2017 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Polisacáridos / Amidas / Lactamas Límite: Animals / Humans Idioma: En Revista: J Am Chem Soc Año: 2017 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos