Facile synthesis of extremely biocompatible double-network hydrogels based on chitosan and poly(vinyl alcohol) with enhanced mechanical properties (original) (raw)
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The objective of this work was to correlate the physical and chemical properties of chitosan/poly(vinyl alcohol)/genipin (CS/PVA/GEN) and chitosan/poly(vinyl alcohol)/glutaraldehyde (CS/PVA/GA) hydrogels with their structural and mechanical responses. In addition, their molecular structures were determined and confirmed using FTIR spectroscopy. The results indicated that the hybrid hydrogels crosslinked with genipin showed similar crystallinity, thermal properties, elongation ratio and structural parameters as those crosslinked with glutaraldehyde. However, it was found that the elastic moduli of the two hybrid hydrogels were slightly different: 2.82 ± 0.33 MPa and 2.08 ± 0.11 MPa for GA and GEN, respectively. Although the hybrid hydrogels crosslinked with GEN presented a lower elastic modulus, the main advantage is that GEN is five to ten thousand times less cytotoxic than GA. This means that the structural and mechanical properties of hybrid hydrogels crosslinked with GEN can easily be tuned and could have potential applications in the tissue engineering, regenerative medicine, food, agriculture and environmental industries.
Gels
In recent years, the antimicrobial activity of chitosan-based hydrogels has been at the forefront of research in wound healing and the prevention of medical device contamination. Anti-infective therapy is a serious challenge given the increasing prevalence of bacterial resistance to antibiotics as well as their ability to form biofilms. Unfortunately, hydrogel resistance and biocompatibility do not always meet the demands of biomedical applications. As a result, the development of double-network hydrogels could be a solution to these issues. This review discusses the most recent techniques for creating double-network chitosan-based hydrogels with improved structural and functional properties. The applications of these hydrogels are also discussed in terms of tissue recovery after injuries, wound infection prevention, and biofouling of medical devices and surfaces for pharmaceutical and medical applications.
J. Mater. Chem. B, 2015
A novel physically linked double-network (DN) hydrogel based on natural polymer konjac glucomannan (KGM) and synthetic polymer polyacrylamide (PAAm) has been successfully developed. Polyvinyl alcohol (PVA) was used as a macro-crosslinker to prepare the PVA-KGM first network hydrogel by a cycle freezing and thawing method for the first time. Subsequent introduction of a secondary PAAm network resulted in super-tough DN hydrogels. The resulting PVA-KGM/PAAm DN hydrogels exhibited unique ability to be freely shaped, cell adhesion properties and excellent mechanical properties, which do not fracture upon loading up to 65 MPa and a strain above 0.98. The mechanical strength and microstructure of the DN hydrogels were investigated as functions of acrylamide (AAm) content and freezing and thawing times. A unique embedded micro-network structure was observed in the PVA-KGM/PAAm DN gels and accounted for the significant improvement in toughness. The fracture mechanism is discussed based on the yielding behaviour of these physically linked hydrogels. † Electronic supplementary information (ESI) available: The frequency (a) and amplitude (b) dependence of storage modulus G 0 of the PVA-KGM hydrogels; the frequency (a) and amplitude (b) dependence of storage modulus G 0 of the PVA-KGM/PAAm DN hydrogels; the effect of MBAA concentration on the compressive strength of the PVA-KGM/PAAm DN hydrogel. See
Improving Mechanical Properties of Starch-Based Hydrogels Using Double Network Strategy
Polymers
This work aims to improve the mechanical properties of starch-based hydrogels using a double-network (DN) strategy. The single network (SN) starch hydrogel was first prepared using glutaraldehyde as a crosslinker. The compressive properties of the SN hydrogels were influenced by both crosslinker content and crosslinking time. The SN starch hydrogel possessing the best mechanical properties was then fabricated into DN hydrogels. Poly(vinyl alcohol) (PVA) and borax were used as a secondary polymer and a crosslinker, respectively. The PVA–borax complexation partly enhanced the DN hydrogel’s compressive modulus by 30% and its toughness by 39%. DN hydrogels were found to have denser microstructures than SN hydrogels. To be specific, their walls thickened and grew more continuous while their pores shrank. The increased crosslinking density resulted in changes to the microstructure, which were well correlated with their porosity and water uptake capacity. An in vitro cytotoxicity test of t...
Double-network hydrogel with high mechanical strength prepared from two biocompatible polymers
Journal of Applied Polymer Science, 2009
Novel double-network (DN) hydrogels with high mechanical strength have been fabricated with two biocompatible polymers, poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG), through a simple freezing and thawing method. Some properties of the obtained hydrogels, such as the mechanical strength, rheological and thermodynamic behavior, drug release, and morphology, have been characterized. The results reveal that in sharp contrast to most common hydrogels made with simple natural or synthetic polymers, PVA/PEG hydrogels can sustain a compressive pressure as high as several megapascals, highlighting their potential application as biomedical materials. In addition, a model for describing the structural formation of PVA/PEG DN hydrogels is proposed: the condensed PVA-rich phase forms microcrystals first, which bridge with one another to form a rigid and inhomogeneous net backbone to support the shape of the hydrogel, and then the dilute PEG-rich phase partially crystallizes among the cavities or voids of the backbone; meanwhile, there are entanglements of molecular chains between the two polymers. Moreover, a mechanism is also proposed to explain the high mechanical strength of PVA/PEG DN hydrogels. It is suggested that the free motion of PEG clusters in the cavities of PVA networks can prevent the crack from growing to a macroscopic level because the linear PEG chains in the cavities effectively absorb the crack energy and relax the local stress either by viscous dissipation or by large deformation of the PEG chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
Polymers
Chitosan hydrogels are biomaterials with excellent potential for biomedical applications. In this study, chitosan hydrogels were prepared at different concentrations and molecular weights by freeze-drying. The chitosan sponges were physically crosslinked using sodium bicarbonate as a crosslinking agent. The X-ray spectroscopy (XPS and XRD diffraction), equilibrium water content, microstructural morphology (confocal microscopy), rheological properties (temperature sweep test), and cytotoxicity of the chitosan hydrogels (MTT assay) were investigated. XPS analysis confirmed that the chitosan hydrogels obtained were physically crosslinked using sodium bicarbonate. The chitosan samples displayed a semi-crystalline nature and a highly porous structure with mean pore size between 115.7 ± 20.5 and 156.3 ± 21.8 µm. In addition, the chitosan hydrogels exhibited high water absorption, showing equilibrium water content values from 23 to 30 times their mass in PBS buffer and high thermal stabili...
Polymer International, 2009
Chitosan is a biodegradable, non-toxic, biocompatible polymer convenient for use in drug delivery. In this study, hybrid polymeric networks (HPNs) based on chitosan, itaconic acid and poly(vinyl alcohol) (PVA) were prepared and characterized. Chitosan was dissolved in itaconic acid in order to obtain ionic crosslinking with the dicarboxylic acid. In the second step, this chitosan/itaconic acid network was mixed with PVA and chemically crosslinked with glutaraldehyde. The chitosan/itaconic acid ratio was kept constant, while the concentrations of PVA and glutaraldehyde were varied. All samples were characterized using swelling studies, dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy. The equilibrium degrees of swelling obtained for the HPNs were higher than most of the values reported for chitosan hydrogels obtained by dissolving chitosan in acetic acid or HCl aqueous solutions. This method of synthesis also resulted in hydrogels with better mechanical properties and thermal stability. By changing the PVA content and the degree of crosslinking, it is possible to finely tune the properties of the HPNs, which could make them suitable as potential matrices in controlled drug delivery.
Carbohydrate Polymers, 2009
A selectively cross-linking method, which is based on the ''di-diol" interaction between poly(vinyl alcohol) and borate and the strong electrostatic interaction between chitosan and tripolyphosphate, was developed. Chitosan/poly(vinyl alcohol) films cross-linked separately with borate, tripolyphosphate and borate/tripolyphosphate were then prepared in terms of this method. Water vapor permeation, mechanical strength, surface morphology and molecular interactions of the films were studied by water permeation test, texture test, atomic force microscopy and ATR-FTIR spectroscopy. With the introduction of cross-linking structure, there is a large improvement in elastic modulus from 271 ± 14.2 to 551 ± 14.7 MPa and a large decrease in water vapor permeability from (5.41 ± 0.21) Â 10 À7 g/m h Pa to (3.12 ± 0.24) Â 10 À7 g/m h Pa of chitosan/poly(vinyl alcohol) films. The surface morphology of the cross-linked films exhibits a nanoparticle aggregation structure. The size and aggregation behavior of these nanoparticles are strongly related to the type of cross-linker. Furthermore, ATR-FTIR results indicate that strong interaction between polymer matrix and cross-linker exists in our system. This work provides a simple and efficient way to prepare chitosan/poly(vinyl alcohol) films with controllable network structure.
Journal of Polymer Research, 2014
Combining different polymeric systems can be a useful tool to create new networks with different characteristics with respect to the starting materials. In this work, hydrogels composed of gellan gum (GG) and polyethylene glycol dimethacrylate (PEG-DMA) were realized to overcome the fragility problems of physical gels of GG, which limit their biological application as scaffold for tissue engineering. The two polymeric systems were combined using different synthetic approaches, with particular attention to the double network strategy (DN). The influence of several parameters on the mechanical properties, such as the time of diffusion and the molecular weight of PEG-DMA, were evaluated by rheological studies and compressive texture analyses. The hydrogels were also investigated for their ability to swell and release model molecules with different sterical hindrances, such as vitamin B12 and myoglobin. Finally, to estimate the biological safety of the hydrogels, their effect on mitochondrial function of human fibroblasts was investigated.
Synthesis, characterization and applications of N-quaternized chitosan/poly(vinyl alcohol) hydrogels
International journal of biological macromolecules, 2015
Hydrogels composed of N-quaternized chitosan (NQC) and poly(vinyl alcohol) (PVA) in different weight ratios (1:3), (1:1) and (3:1) chemically crosslinked by glutaraldehyde in different weight ratios – 1.0 and 5.0% – have been prepared. The prepared hydrogels were characterized via several analysis tools such as: Fourier transform IR (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM) and thermogravimetric analysis (TGA). Different applications have been done on NQC/PVA hydrogels including; metal ions uptake, swellability in different buffer solutions (pH: 4, 7 and 9), swellability and degradation studies in simulated body fluid (SBF) solutions and antimicrobial activity towards bacteria and fungi. The results indicated that crosslinked NQC/PVA hydrogels with glutaraldehyde (GA) are more thermallystable than non crosslinked hydrogels, NQC/PVA hydrogels swell highly in different buffer solutions as PVA content increases and the antimicrobial activity of NQC/PVA hydroge...