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Cellulose

, Volume 23, Issue 3, pp 1687–1704 | Cite as

Cellulosic polyelectrolytes: synthetic pathways to regioselectively substituted ammonium and phosphonium derivatives

  • Joyann A. Marks
  • S. Carter Fox
  • Kevin J. Edgar
Original Paper

Abstract

Cationic polysaccharide polyelectrolytes are important synthetic targets for drug and gene delivery, especially by encapsulation of nucleic acids and proteins through electrostatic interactions. They also have potential as paracellular permeability enhancers that may increase transport across the gastrointestinal (GI) epithelium, especially for therapeutic hydrophilic macromolecules. Semisynthetic chitosan has been more heavily investigated as a cationic polysaccharide polyelectrolyte. This study explores the synthetic conditions needed to produce ammonio and phosphonio cellulose derivatives regioselectively by halogen displacement at C-6 while maximizing the degree of substitution (DS) of cationic substituent. Regioselective substitution was successful, however there were found to be some limitations to the DS and solubility of ammonium derivatives prepared in this way (highest DS 0.43); conversely, water-soluble 6-phosphonio-6-deoxycellulose derivatives were produced with DS > 0.5, with highest DS of 0.73. The repulsion between accumulating positive charges was confirmed as a likely source of DS limitation since high DS (0.9) of 6-triethylamino cellulose was synthesized under comparable conditions. Further reaction of 6-ammonio-co-6-bromo derivatives with a thiol produced 6-ammonio-co-6-thiolated products with improved aqueous solubility. The thiol DS of 0.68 determined by elemental analysis confirmed substitution of residual bromide from low DS (0.30) ammonium products to give essentially complete substitution at C-6.

Keywords

Cellulose polyelectrolytes Water-soluble Phosphonium derivatives Regioselective substitution Thiolated derivatives 

Notes

Acknowledgments

We thank the Institute for Critical Technologies and Applied Science (ICTAS), the Macromolecules Innovation Institute (MII), and the Department of Sustainable Biomaterials (SBIO) at Virginia Tech for their financial, facilities and educational support. We thank Mr. Geno Iannaccone and Mr. Ken Knott in the NMR Spectroscopy Lab within the Department of Chemistry at Virginia Tech for their valuable assistance in executing kinetic experiments. We also thank Ms. Brittany Nichols and Mr. Xiangtao Meng for providing assistance with polymer characterization. We thank the USDA for partial financial support through Grant No. 2011-67009-20090.

Supplementary material

10570_2016_929_MOESM1_ESM.docx (8.3 mb)
Supplementary material 1 (DOCX 8545 kb)

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Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Joyann A. Marks
    • 1
  • S. Carter Fox
    • 1
  • Kevin J. Edgar
    • 1
  1. 1.Department of Sustainable Biomaterials, College of Natural Resources and Environment, Macromolecules Innovation InstituteVirginia TechBlacksburgUSA

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