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Cellulose

, Volume 21, Issue 3, pp 1945–1955 | Cite as

Anionic cellulose beads for drug encapsulation and release

  • Jani TryggEmail author
  • Emrah Yildir
  • Ruzica Kolakovic
  • Niklas Sandler
  • Pedro Fardim
Original Paper

Abstract

Cellulose beads were prepared from water-based solvent and oxidised by modified Anelli’s reaction at 20–\(80\,^\circ \hbox {C}\) for 2–48 h (Fig. 1). The maximum amount of anionic groups (AGs) was \(1.85\,\hbox {mmol}\,\hbox {g}^{-1}\). The distribution of AGs was verified by absorption of cationic dyes and imaging with confocal fluorescent microscopy. Structural changes were studied spectroscopically and with electron microscopy. Oxidation of the beads drastically increased the swelling capacity of air-dried beads. Uptake of model drug was more than doubled in never-dried beads. This is due to the changes in pore size distribution, mainly opening and widening of the closed pores and narrow cavities. Release profiles of the drug were studied at physiological pH of 7.4 and showed a controlled release rate independently of the amount of the drug encapsulated and amount of AGs.

Keywords

TEMPO oxidation Cellulose beads Microsphere Drug delivery 

Notes

Acknowledgments

This work is part of Future Biorefine (FuBio) Cellulose, funded by TEKES and coordinated by Finnish Bioeconomy Cluster (FiBiC). We would also like to acknowledge the department of biology in Åbo Akademi for the fluorescent microscopy measurements.

Supplementary material

10570_2014_253_MOESM1_ESM.pdf (223 kb)
Supplementary material 1 (f 223 KB)

References

  1. Anelli LP, Biffi C, Montanari F, Quici S (1987) Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions. J Org Chem 52:2559–2562CrossRefGoogle Scholar
  2. Bussemer B, Dreiling I, Grummt UW, Mohr GJ (2009) Spectroscopic and quantum chemical study of the brönsted acid sites in zeolite L channels with acidochromic cyanine dyes. J Photochem Photobiol A 204:90–96CrossRefGoogle Scholar
  3. Capello C, Fischer U, Hungerbuhler K (2007) What is a green solvent? A comprehensive framework for the environmental assessment of solvents. Green Chem. 9:927–934CrossRefGoogle Scholar
  4. Conn HJ (1953) Biological stains; a handbook on the nature and uses of the dyes employed in the biological laboratory, 6th edn. The Williams & Wilkins Company, BaltimoreGoogle Scholar
  5. De Luca L, Giacomelli G, Porcheddu A, Salaris M, Taddei M (2003) Cellulose beads: a new versatile solid support for microwave- assisted synthesis. Preparation of pyrazole and isoxazole libraries. J Comb Chem 5:465–471CrossRefGoogle Scholar
  6. de Nooy AE, Besemer AC, van Bekkum H (1995) Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans. Carbohydr Res 269:89–98CrossRefGoogle Scholar
  7. Gericke M, Trygg J, Fardim P (2013) Functional cellulose beads: preparation, characterization, and applications. Chem Rev 113:4812–4836CrossRefGoogle Scholar
  8. Hempel A, Camerman N, Mastropaolo D, Camerman A (2000) Ranitidine hydrochloride, a polymorphic crystal form. Acta Crystallogr Sect C 56:1048–1049CrossRefGoogle Scholar
  9. Hirota M, Tamura N, Saito T, Isogai A (2009) Oxidation of regenerated cellulose with \(\text{ NaClO}_2\) catalyzed by TEMPO and NaClO under acid-neutral conditions. Carbohydr Polym 78:330–335CrossRefGoogle Scholar
  10. Isogai A, Atalla R (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319CrossRefGoogle Scholar
  11. Klemm D, Philipp B, Heinze T, Heinze U, Wagenknecht W (1998) Comprehensive cellulose chemistry 2: functionalization of cellulose. Wiley, WeinheinCrossRefGoogle Scholar
  12. Larkin P (2011) Infrared and Raman spectroscopy; principles and spectral interpretation. Elsevier, Waltham, MAGoogle Scholar
  13. Liu W, Budtova T, Navard P (2011) Influence of ZnO on the properties of dilute and semi-dilute cellulose-NaOH-water solutions. Cellulose 18:911–920CrossRefGoogle Scholar
  14. Lonkar KGKJSS, Kale M (2011) Dyes and chemicals used in biomaterial study as stains for invertebrates. Int J Chem Res 2:22–25Google Scholar
  15. Luo X, Zhang L (2010) Creation of regenerated cellulose microspheres with diameter ranging from micron to millimeter for chromatography applications. J Chromatogr A 1217:5922–5929CrossRefGoogle Scholar
  16. Ma Y, Loyns C, Price P, Chechik V (2011) Thermal decay of TEMPO in acidic media via an N-oxoammonium salt intermediate. Org Biomol Chem 9:5573–5578CrossRefGoogle Scholar
  17. Maekawa E, Koshijima T (1984) Properties of 2,3-dicarboxy cellulose combined with various metallic ions. J Appl Polym Sci 29:2289–2297CrossRefGoogle Scholar
  18. Oliveira WD, Glasser WG (1996) Hydrogels from polysaccharides. I. Cellulose beads for chromatographic support. J Appl Polym Sci 60:63–73CrossRefGoogle Scholar
  19. Qi H, Chang C, Zhang L (2008) Effects of temperature and molecular weight on dissolution of cellulose in NaOH/urea aqueous solution. Cellulose 15:779–787CrossRefGoogle Scholar
  20. Qtiplot (2011) Version 0.9. http://soft.proindependent.com/qtiplot.html. Accessed 30 Aug 2013
  21. Rosenberg P, Suominen I, Rom M, Janicki J, Fardim P (2007) Tailored cellulose beads for novel applications. Cell Chem Technol 41:243–254Google Scholar
  22. Schenzel K, Fischer S (2001) NIR FT Raman Spectroscopy—rapid analytical tool for detecting the transformation of cellulose polymorphs. Cellulose 8:49–57CrossRefGoogle Scholar
  23. Schindelin J (2008) Fiji Is Just ImageJ (batteries included). Version 1.44. ImageJ User and Developer ConferenceGoogle Scholar
  24. Sen VD, Golubev VA (2009) Kinetics and mechanism for acid-catalyzed disproportionation of 2,2,6,6-tetramethylpiperidine-1-oxyl. J Phys Org Chem 22:138–143CrossRefGoogle Scholar
  25. Sescousse R, Gavillon R, Budtova T (2011) Wet and dry highly porous cellulose beads from cellulose-NaOH-water solutions: influence of the preparation conditions on beads shape and encapsulation of inorganic particles. J Mater Sci 46:759–765CrossRefGoogle Scholar
  26. Stone J, Scallan A (1968) A structural model for the cell wall of water-swollen wood pulp fibres based on their accessibility to macromolecules. Cell Chem Technol 2:343–358Google Scholar
  27. Tamura N, Hirota M, Saito T, Isogai A (2010) Oxidation of curdlan and other polysaccharides by 4-acetamide-\(\text{TEMPO}/\text{NaClO}/\text{NaClO}_2\) under acid conditions. Carbohydr Polym 81:592–598CrossRefGoogle Scholar
  28. Trygg J, Fardim P (2011) Enhancement of cellulose dissolution in water-based solvent via ethanol-hydrochloric acid pretreatment. Cellulose 18:987–994CrossRefGoogle Scholar
  29. Trygg J, Fardim P, Gericke M, Mkil E, Salonen J (2013) Physicochemical design of the morphology and ultrastructure of cellulose beads. Carbohydr Polym 93:291–299CrossRefGoogle Scholar
  30. Twu YK, Huang HI, Chang SY, Wang SL (2003) Preparation and sorption activity of chitosan/cellulose blend beads. Carbohydr Polym 54:425–430CrossRefGoogle Scholar
  31. Volkert B, Wolf B, Fischer S, Li N, Lou C (2009) Application of modified bead cellulose as a carrier of active ingredients. Macromol Symp 280:130–135CrossRefGoogle Scholar
  32. Yildir E, Kolakovic R, Genina N, Trygg J, Gericke M, Hanski L, Ehlers H, Rantanen J, Tenho M, Vuorela P, Fardim P, Sandler N (2013) Tailored beads made of dissolved cellulose—investigation of their drug release properties. Int J Pharmac (accepted)Google Scholar
  33. Zhang L, Cai J, Zhou J, Tang Y (2005) Adsorption of \(\text{Cd}^{2+}\) and \(\text{Cu}^{2+}\) on ion-exchange beads from cellulose/alginic acid blend. Sep Sci Technol 39:1203–1219CrossRefGoogle Scholar
  34. Zhao M, Li J, Mano E, Song Z, Tschaen DM, Grabowski EJJ, Reider PJ (1999) Oxidation of primary alcohols to carboxylic acids with sodium chlorite catalyzed by TEMPO and bleach. J Org Chem 64:2564–2566CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Jani Trygg
    • 1
    Email author
  • Emrah Yildir
    • 2
  • Ruzica Kolakovic
    • 2
  • Niklas Sandler
    • 2
  • Pedro Fardim
    • 1
  1. 1.Laboratory of Fibre and Cellulose TechnologyÅbo AkademiTurkuFinland
  2. 2.Laboratory of Pharmaceutical SciencesÅbo Akademi UniversityTurkuFinland

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