Development of chitosan-tripolyphosphate fibers through pH dependent ionotropic gelation.
ABSTRACT Incorporation of phosphate groups into a material may be of particular interest as they act as templates for hydroxyapatite growth through complexation with Ca(2+) and thus improve the osteoconduction property. The phosphate groups can be incorporated into chitosan through ionotropic gelation with tripolyphosphate (TPP). Interestingly, the ion pairs formed through negatively charged phosphate groups with protonated amine functionality of chitosan in ionotropic gelation are expected to provide chitosan with an amphoteric character, which may facilitate protein adhesion following enhanced attachment of anchorage dependant cells than chitosan, which shows poor cell adhesion properties. In this study, chitosan-tripolyphosphate (TPP) fibers with varying phosphate contents were prepared through wet spinning in STPP baths of different pH. Gelation kinetics and gel strength of chitosan with STPP solutions of three different pH were evaluated and compared with that of NaOH solution for evaluation of their influence on nature of gelation. The solution pH of STPP baths was found to have significant control on the extent of ionic cross-linking and physico-chemical properties of the fibers. Moreover, this kinetically driven ionotropic gelation of chitosan by TPP results in low degree of crystallinity of chitosan-TPP fibers and consequently their lower thermal stability than chitosan fibers.
- SourceAvailable from: Emmanuel N Koukaras[show abstract] [hide abstract]
ABSTRACT: This work reports details pertaining to the formation of chitosan nanoparticles that we prepare by the ionic gelation method. The molecular interactions of the ionic cross-linking of chitosan with tripolyphosphate have been investigated and elucidated by means of all-electron density functional theory. Solvent effects have been taken into account using implicit models. We have identified primary-interaction ionic cross-linking configurations that we define as H-link, T-link, and M-link, and we have quantified the corresponding interaction energies. H-links, which display high interaction energies and are also spatially broadly accessible, are the most probable cross-linking configurations. At close range, proton transfer has been identified, with maximum interaction energies ranging from 12.3 up to 68.3 kcal/mol depending on the protonation of the tripolyphosphate polyanion and the relative coordination of chitosan with tripolyphosphate. On the basis of our results for the linking types (interaction energies and torsion bias), we propose a simple mechanism for their impact on the chitosan/TPP nanoparticle formation process. We introduce the β ratio, which is derived from the commonly used α ratio but is more fundamental since it additionally takes into account structural details of the oligomers.Molecular Pharmaceutics 07/2012; 9(10):2856-62. · 4.57 Impact Factor
- [show abstract] [hide abstract]
ABSTRACT: The fibrous scaffolds are promising for tissue engineering applications because of their close structural resemblance with native extracellular matrix. Additionally, the chemical composition of scaffold is also an important consideration as they have significant influences on modulating cell attachment, morphology and function. In this study, chitosan-tripolyphosphate (TPP) non-woven fibrous scaffolds were prepared through wetspinning process. Interestingly, at physiological pH these scaffolds release phosphate ions, which have significant influences on cellular function. For the first time, cell viability in presence of varying concentration of sodium TPP solution was analyzed and correlated with the phosphate release from the scaffolds during 30 days incubation period. In vitro degradation of the chitosan-TPP scaffolds was higher than chitosan scaffolds, which may be due to decrease in crystallinity as a result of instantaneous ionic cross-linking during fiber formation. The scaffolds with highly interconnected porous structure present a remarkable cytocompatibility for cell growing, and show a great potential for tissue engineering applications.Journal of Materials Science Materials in Medicine 02/2012; 23(4):1085-96. · 2.14 Impact Factor