Abstract
A facile approach has been established to generate cellulose/chitosan hybrid nanofibers with full range of compositions by electrospinning of their ester derivatives, cellulose acetate (CA) and dibutyryl chitin (DBC), followed by alkaline hydrolysis to cellulose (Cell) and chitosan (CS). DBC was synthesized by acid-catalyzed acylation of chitin (CHI) with butyric anhydride and the newly formed butyl groups on C3 and C6 were confirmed by FT-IR and 1HNMR. DBC had robust solubility in acetone, DMAc, DMF, ethanol, and acetic acid, all except ethanol were also solvents for CA, allowing mixing of these ester derivatives. Fiber formation by electrospinning of either DBC or CA alone and together in these common solvents and their mixtures were studied. The 1/1 acetone/acetic acid was found to be the optimal solvent system to generate fibers from either DBC or CA as well as their mixtures at all CA/DBC ratios, resulting in hybrid fibers with diameters ranging from 30 to 350 nm. DBC and CA were well mixed and showed no phase separate in the hybrid fibers. Alkaline hydrolysis (NaOH) of the equal mass CA/DBC nanofibers regenerated Cell and CHI readily via O-deacylation, then proceeded to further deacetylate CHI to CS via N-deacetylation at higher alkaline concentrations and/or temperatures. Under conditions studied, hydrolysis with 5N NaOH at 100 °C for 3 h was optimal to regenerate cellulose/chitosan hybrid nanofibers.
Similar content being viewed by others
References
Blasinska A, Mikolajczyk T (2005) Wet spinning of dibutyrylchitin fibres from ethanol solution. Fibres Text East Eur 13:36–40
Blasinska A, Krucinska I, Chrzanowski M (2004) Dibutyrylchitin nonwoven biomaterials manufactured using electrospinning method. Fibres Text East Eur 12:51–55
Ciechanska D (2004) Multifunctional bacterial cellulose/chitosan composite materials for medical applications. Fibres Text East Eur 12:69–72
Du J, Hsieh YL (2007) PEGylation of chitosan for improved solubility and fiber formation via electrospinning. Cellulose 14:543–552. doi:10.1007/s10570-007-9122-3
Du J, Hsieh YL (2008) Nanofibrous membranes from aqueous electrospinning of carboxymethyl chitosan. Nanotechnology 19:125707. doi:10.1088/0957-4484/19/12/125707
El-Tahlawy K, Abdelhaleem E, Hudson SM, Hebeish A (2007) Acylation of iminochitosan: its effect on blending with cellulose acetate. J Appl Polym Sci 104:727–734. doi:10.1002/app.24136
Geng X, Kwon OH, Jang J (2005) Electrospinning of chitosan dissolved in concentrated acetic acid solution. Biomaterials 26:5427–5432. doi:10.1016/j.biomaterials.2005.01.066
Kim CW, Frey MW, Marquez M, Joo YL (2005) Preparation of submicron-scale, electrospun cellulose fibers via direct dissolution. J Polym Sci Part B Polym Phys 43:1673–1683. doi:10.1002/polb.20475
Kim CW, Kim DS, Kang SY, Marquez M, Joo YL (2006) Structural studies of electrospun cellulose nanofibers. Polymer (Guildf) 47:5097–5107. doi:10.1016/j.polymer.2006.05.033
Kurita K (2006) Chitin and chitosan: functional biopolymers from marine crustanceans. Mar Biotechnol 8:203–226. doi:10.1007/s10126-005-0097-5
Linhardt RJ, Murugesan S, Park T (2008) Blood compatible nanomaterials. PCT Int Appl WO 2008045021
Liu CX, Bai RB (2006) Adsorptive removal of copper ions with highly porous chitosan/cellulose acetate blend hollow fiber membranes. J Membr Sci 284:313–322. doi:10.1016/j.memsci.2006.07.045
Liu H, Hsieh YL (2002) Ultrafine fibrous cellulose membranes from electrospinning of cellulose acetate. J Polym Sci Part B Polym Phys 40:2119–2129. doi:10.1002/polb.10261
Min BM, You Y, Kim JM, Lee SJ, Park WH (2004) Formation of nanostructured poly(lactic-co-glycolic acid)/chitin matrix and its cellular response to normal human keratinocytes and fibroblasts. Carbohydr Polym 57:285–292. doi:10.1016/j.carbpol.2004.05.007
Neamnark A, Rujiravanit R, Supaphol P (2006) Electrospinning of hexanoyl chitosan. Carbohydr Polym 66:298–305. doi:10.1016/j.carbpol.2006.03.015
Ohkawa K, Cha D, Kim H, Nishida A, Yamamoto H (2004) Electrospinning of chitosan. Macromol Rapid Commun 25:1600–1605. doi:10.1002/marc.200400253
Poirier M, Charlet G (2002) Chitin fractionation and characterization in N,N-dimethylacetamide/lithium chloride solvent system. Carbohydr Polym 50:363–370. doi:10.1016/S0144-8617(02)00040-1
Szosland L, East GC (1995) The dry spinning of dibutyrylchitin fibers. J Appl Polym Sci 58:2459–2466. doi:10.1002/app.1995.070581313
Tolaimate A, Desbrieres J, Rhazi M, Alagui A, Vincendon M, Vottero P (2000) On the influence of deacetylation process on the physicochemical characteristics of chitosan from squid chitin. Polymer (Guildf) 41:2463–2469. doi:10.1016/S0032-3861(99)00400-0
Wlochowicz A, Szosland L, Binias D, Szumilewicz J (2004) Crystalline structure and mechanical properties of wet-spun dibutyrylchitin fibers and products of their alkaline treatment. J Appl Polym Sci 94:1861–1868. doi:10.1002/app.20760
Zhang LF, Hsieh YL (2007) Ultra-fine cellulose acetate/poly(ethylene oxide) bicomponent fibers. Carbohydr Polym 71:196–207. doi:10.1016/j.carbpol.2007.05.031
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Du, J., Hsieh, YL. Cellulose/chitosan hybrid nanofibers from electrospinning of their ester derivatives. Cellulose 16, 247–260 (2009). https://doi.org/10.1007/s10570-008-9266-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-008-9266-9