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.










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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 52:2559–2562
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 204:90–96
Capello C, Fischer U, Hungerbuhler K (2007) What is a green solvent? A comprehensive framework for the environmental assessment of solvents. Green Chem. 9:927–934
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, Baltimore
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 5:465–471
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 269:89–98
Gericke M, Trygg J, Fardim P (2013) Functional cellulose beads: preparation, characterization, and applications. Chem Rev 113:4812–4836
Hempel A, Camerman N, Mastropaolo D, Camerman A (2000) Ranitidine hydrochloride, a polymorphic crystal form. Acta Crystallogr Sect C 56:1048–1049
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 78:330–335
Isogai A, Atalla R (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319
Klemm D, Philipp B, Heinze T, Heinze U, Wagenknecht W (1998) Comprehensive cellulose chemistry 2: functionalization of cellulose. Wiley, Weinhein
Larkin P (2011) Infrared and Raman spectroscopy; principles and spectral interpretation. Elsevier, Waltham, MA
Liu W, Budtova T, Navard P (2011) Influence of ZnO on the properties of dilute and semi-dilute cellulose-NaOH-water solutions. Cellulose 18:911–920
Lonkar KGKJSS, Kale M (2011) Dyes and chemicals used in biomaterial study as stains for invertebrates. Int J Chem Res 2:22–25
Luo X, Zhang L (2010) Creation of regenerated cellulose microspheres with diameter ranging from micron to millimeter for chromatography applications. J Chromatogr A 1217:5922–5929
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 9:5573–5578
Maekawa E, Koshijima T (1984) Properties of 2,3-dicarboxy cellulose combined with various metallic ions. J Appl Polym Sci 29:2289–2297
Oliveira WD, Glasser WG (1996) Hydrogels from polysaccharides. I. Cellulose beads for chromatographic support. J Appl Polym Sci 60:63–73
Qi H, Chang C, Zhang L (2008) Effects of temperature and molecular weight on dissolution of cellulose in NaOH/urea aqueous solution. Cellulose 15:779–787
Qtiplot (2011) Version 0.9. http://soft.proindependent.com/qtiplot.html. Accessed 30 Aug 2013
Rosenberg P, Suominen I, Rom M, Janicki J, Fardim P (2007) Tailored cellulose beads for novel applications. Cell Chem Technol 41:243–254
Schenzel K, Fischer S (2001) NIR FT Raman Spectroscopy—rapid analytical tool for detecting the transformation of cellulose polymorphs. Cellulose 8:49–57
Schindelin J (2008) Fiji Is Just ImageJ (batteries included). Version 1.44. ImageJ User and Developer Conference
Sen VD, Golubev VA (2009) Kinetics and mechanism for acid-catalyzed disproportionation of 2,2,6,6-tetramethylpiperidine-1-oxyl. J Phys Org Chem 22:138–143
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 46:759–765
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 2:343–358
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 81:592–598
Trygg J, Fardim P (2011) Enhancement of cellulose dissolution in water-based solvent via ethanol-hydrochloric acid pretreatment. Cellulose 18:987–994
Trygg J, Fardim P, Gericke M, Mkil E, Salonen J (2013) Physicochemical design of the morphology and ultrastructure of cellulose beads. Carbohydr Polym 93:291–299
Twu YK, Huang HI, Chang SY, Wang SL (2003) Preparation and sorption activity of chitosan/cellulose blend beads. Carbohydr Polym 54:425–430
Volkert B, Wolf B, Fischer S, Li N, Lou C (2009) Application of modified bead cellulose as a carrier of active ingredients. Macromol Symp 280:130–135
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)
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 39:1203–1219
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 64:2564–2566
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.
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Trygg, J., Yildir, E., Kolakovic, R. et al. Anionic cellulose beads for drug encapsulation and release. Cellulose 21, 1945–1955 (2014). https://doi.org/10.1007/s10570-014-0253-z
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DOI: https://doi.org/10.1007/s10570-014-0253-z


