Chitosan/halloysite nanotubes bionanocomposites: Structure, mechanical properties and biocompatibility

Incorporation of nanosized reinforcements into chitosan usually results in improved properties and changed microstructures. Naturally occurred halloysite nanotubes (HNTs) are incorporated into chitosan for forming bionanocomposite films via solution casting. The electrostatic attraction and hydrogen bonding interactions between HNTs and chitosan are confirmed. HNTs are uniformly dispersed in chitosan matrix. The tensile strength and Young's modulus of chitosan are enhanced by HNTs. The storage modulus and glass transition temperature of chitosan/HNTs films also increase significantly. Blending with HNTs induces changes in surface nanotopography and increase of roughness of chitosan films. In vitro fibroblasts response demonstrates that both chitosan and chitosan/HNTs nanocomposite films are cytocompatibility even when the loading of HNTs is 10%. In summary, these results provide insights into understanding of the structural relationships of chitosan/HNTs bionanocomposite films in potential applications, such as scaffold materials in tissue engineering.     

Preparation and characterization of polyaniline/chitosan blend film

Films consisting of a blend of a chitosan hydrogel and a conductive polymer, polyaniline (PANI), were prepared and characterized for their electrical and mechanical properties. Polyaniline in emeraldine base (EB) form was dispersed in chitosan solution and blend films were obtained by solution casting. The PANI particles in the blend films were then doped with HCl where we observed reductions in the film tensile strength and Young's modulus by about 30%, but the films electrical conductivity increased by 6 orders of magnitude. The highest electrical conductivity of the blend films was of the order 10⁻⁴ S/cm. The electrical and mechanical properties of the films varied with polyaniline content, acid dopant type, acid dopant concentration, and doping time.     

Mechanical properties of chitosan/bamboo charcoal composite films made with normal and surface oxidized charcoal

Chitosan/bamboo charcoal composite films were prepared by blending chitosan with either virgin bamboo charcoal or bamboo charcoal modified by nitric acid oxidation to provide more hydrophilic regions on the bamboo charcoal surface. Investigation of the physical properties of these composite films revealed that the tensile strength and Young’s modulus of the chitosan films were enhanced in a dose-dependent manner by the inclusion of modified bamboo charcoal at up to 1% (w/w), whilst the elongation at break was increased by inclusion of modified bamboo charcoal at up to 0.5% (w/w). In contrast, chitosan composites with virgin bamboo charcoal at up to 0.5% or 1.0% (w/w) showed no enhancement of the tensile strength or Young’s modulus, respectively, and both parameters were reduced with higher levels of virgin bamboo charcoal. Oil, and especially water, absorption of the composite films displayed a marked and dose-dependent increase compared to those of the pure chitosan film.     

Viscoelastic properties of linseed oil-based medium chain length poly(hydroxyalkanoate) films: effects of epoxidation and curing

Medium-chain-length poly(hydroxyalkanoate) (mcl-PHA) polymers derived from linseed oil (PHA-L) have a relatively small molar mass and contain a high concentration of unsaturated side-chains. As such, these polymers are amorphous and take on the consistency of a viscous liquid at room temperature. In order to increase the application potential of this material, the side-chain olefinic groups of PHA-L were converted to epoxy derivatives (PHA-LE) using m-chloroperoxybenzoic acid (m-CPBA). Epoxidation resulted in a 37% conversion of olefinic to epoxy groups. The epoxy groups enhanced the PHA-LE film susceptibility to crosslinking upon exposure to air. PHA-LE films began to crosslink and stiffen in less than 25 days, whereas PHA-L films began to crosslink between days 50 and 75. The PHA-LE films showed an increase in tensile strength (TS, from 4.8 to 20.7 MPa) and Young's modulus (YM, from 12.9 to 510.6 MPa) between 25 and 100 days. In contrast, PHA-L had a TS of 25.0 MPa and YM of 767.8 MPa after 100 days. Epoxidation helped induce crosslink formation; however, aging for 100 days ultimately resulted in crosslinked films from both PHA-L and PHA-LE with higher strength and durability than the original materials.     

The underestimation of Young's modulus in compressive testing of cancellous bone specimens

In order to determine the accuracy of measurements of Young's modulus of cancellous bone by conventional compression testing, two independent strain measurements were made simultaneously during non-destructive uniaxial compression to 0.8% strain of rectangular specimens (n = 18). Strain was measured by an extensometer attached to the compression anvils close to the specimen and by an optical system covering the central half of the specimens. Mean Young's modulus determined by the extensometer technique was 689 MPa, but was 871 MPa when determined by the optical technique (mean difference = 182 MPa, SED = 50 MPa, p less than 0.002). Uneven strain distribution due to lack of support of cut vertical trabeculae at the anvil-specimen interface is believed to be causing the underestimation of Young's modulus measured by the extensometer technique. The influence of friction at the specimen-anvil interface was studied by performing a finite element analysis. It is concluded that Young's modulus of specimens of the chosen geometry on average is underestimated by about 20% by conventional compressing testing. The underestimation seems not to be dependent upon specimen density.     

Ultrastrong and high gas-barrier nanocellulose/clay-layered composites

Nanocellulose/montmorillonite (MTM) composite films were prepared from 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with an aspect ratio of >200 dispersed in water with MTM nanoplatelets. The composite films were transparent and flexible and showed ultrahigh mechanical and oxygen barrier properties through the nanolayered structures, which were formed by compositing the anionic MTM nanoplatelet filler in anionic and highly crystalline TOCN matrix. A composite film with 5% MTM content had Young's modulus 18 GPa, tensile strength 509 MPa, work of fracture of 25.6 MJ m(-3), and oxygen permeability 0.006 mL μm m(-2) day(-1) kPa(-1) at 0% relative humidity, respectively, despite having a low density of 1.99 g cm(-3). As the MTM content in the TOCN/MTM composites was increased to 50%, light transmittance, tensile strength, and elongation at break decreased, while Young's modulus was almost unchanged and oxygen barrier property was further improved to 0.0008 mL μm m(-2) day(-1) kPa(-1).     

New nanocomposite materials reinforced with flax cellulose nanocrystals in waterborne polyurethane

New nanocomposite films were prepared from a suspension of cellulose nanocrystals as the filler and a polycaprolactone-based waterborne polyurethane (WPU) as the matrix. The cellulose nanocrystals, prepared by acid hydrolysis of flax fiber, consisted of slender rods with an average length of 327 +/- 108 nm and diameter of 21 +/- 7 nm, respectively. After the two aqueous suspensions were mixed homogeneously, the nanocomposite films were obtained by casting and evaporating. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of attenuated total reflection Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and tensile testing. The results indicated that the cellulose nanocrystals could disperse in the WPU uniformly and resulted in an improvement of microphase separation between the soft and hard segments of the WPU matrix. The films showed a significant increase in Young's modulus and tensile strength from 0.51 to 344 MPa and 4.27 to 14.86 MPa, respectively, with increasing filler content from 0 to 30 wt %. Of note is that the Young's modulus increased exponentially with the filler up to a content of 10 wt %. The synergistic interaction between fillers and between the filler and WPU matrix played an important role in reinforcing the nanocomposites. The superior properties of the new nanocomposite materials could have great potential applications.     

Characterization of nano-clay reinforced phytagel-modified soy protein concentrate resin

Phytagel and nano-clay particles were used to improve the mechanical and thermal properties and moisture resistance of soy protein concentrate (SPC) resin successfully. SPC and Phytagel were mixed together to form a cross-linked structure. The Phytagel-modified SPC resin (PH-SPC) showed improved tensile strength, modulus, moisture resistance, and thermal stability as compared to the unmodified SPC resin. The incorporation of 40% Phytagel and 20% glycerol led to an overall 340% increase in the tensile strength (over 50 MPa) and approximately 360% increase in the Young's modulus (over 710 MPa) of the SPC resin. Nano-clay was uniformly dispersed into PH-SPC resin to further improve the properties. The PH-SPC (40% Phytagel) resin modified with 7% clay nanoparticles (CPH-SPC) had a modulus of 2.1 GPa and a strength of 72.5 MPa. The dynamic mechanical properties such as storage modulus together with the glass transition temperature of the modified resins were also increased by the addition of clay nanoparticles. The moisture resistance of the CPH-SPC resin was higher as compared to both SPC and PH-SPC resins. The thermal stability of the CPH-SPC resin was seen to be higher as compared to the unmodified SPC.     

Influence of peripheral hydrogen bonding on the mechanical properties of photo-cross-linked star-shaped poly(D,L-lactide) networks

Four-arm, star-shaped poly(D,L-lactide) (PDLLA) oligomers of controlled molar mass and narrow molar mass distribution were successfully synthesized by use of an ethoxylated pentaerythritol initiator. Derivatization of the terminal hydroxyl groups with either methacrylic anhydride (MAAH) or 2-isocyanatoethyl methacrylate (IEM) to yield PDLLA-M (M = methacrylate end group) and PDLLA-UM (UM = urethane methacrylate end group), respectively, was monitored by in situ Fourier transform infrared (FTIR) spectroscopy. Photo-cross-linking of the functional oligomers yielded networks with high gel contents (>95%). The glass transition temperature (T(g)) of these networks was strongly dependent on prepolymer molar mass, and networks based on low molar mass precursors were more rigid than the networks obtained from higher molar mass oligomers. The tensile strength (TS) and Young's modulus of the PDLLA-M samples, approximately 7 and 17 MPa, respectively, were significantly lower than the values of 19 MPa (TS) and 113-354 MPa (Young's modulus) for the PDLLA-UM samples. The introduction of terminal hydrogen-bonding sites that were adjacent to the photo-cross-linking site resulted in higher performance poly(lactide)-based bioadhesives.     

Synthesis, characterization, and in vitro degradation of a biodegradable photo-cross-linked film from liquid poly(epsilon-caprolactone-co-lactide-co-glycolide) diacrylate

There has been little study on the effect of composition or molecular weight on the biodegradation rate of photo-cross-linked biodegradable aliphatic polyesters though such information is important for tissue engineering scaffolds. We have synthesized a new series of photopolymerizable linear poly(epsilon-caprolactone-co-lactide-co-glycolide) diacrylates with different molecular weights (Mn = 1800, 4800, and 9300 Da) and compositions (20%, 40%, and 60% epsilon-CL) and studied their biodegradation rates. The resultant oligomers were amorphous and appeared as viscous liquids at room temperature. Liquid-to-solid polymerization was carried out by UV irradiation in the presence of a photoinitiator. The photocuring yield was high (greater than 95%), and the photo-cross-linked polymers were amorphous and rubbery. Mechanical measurements showed that the polymers can be stretchable or rigid; the high molecular weight/low epsilon-CL network has a strain of 176% and a modulus of 1.66 MPa while the low molecular weight/high epsilon-CL network has a strain of 21% and a modulus of 12.3 MPa. In a 10 week in vitro biodegradation study, the polymers exhibited a two-stage degradation behavior. In the first stage, the polymer weight and strain remained almost constant, but a linear decrease in the Young's modulus (E) and ultimate stress (sigma) were observed. Lower oligomer molecular weight or epsilon-CL content correlated with a faster decrease in Young's modulus. In the second stage, which began when the Young's modulus dropped below 1 MPa, there was rapid weight loss and strain increase. The lower the epsilon-CL content, the earlier the second stage happened. Low molecular weight and high epsilon-CL content correlated with a longer modulus half-life (time for the modulus to degrade to 50% of its initial value). The degradation results suggest principles that may be helpful in predicting the biodegradation behavior of similar polymeric cross-linked networks. Films formed from these new polymers have excellent biocompatibility with smooth muscle cells.     

Cross-linking chitosan nanofibers

In the present study, we have electrospun various grades of chitosan and cross-linked them using a novel method involving glutaraldehyde (GA) vapor, utilizing a Schiff base imine functionality. Chemical, structural, and mechanical analyses have been conducted by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and Kawabata microtensile testing, respectively. Additionally, the solubilities of the as-spun and cross-linked chitosan mats have been evaluated;solubility was greatly improved after cross-linking. SEM images displayed evidence that unfiltered low, medium, and high molecular weight chitosans, as well as practical-grade chitosan, can be electrospun into nanofibrous mats. The as-spun medium molecular weight chitosan nanofibers have a Young's modulus of 154.9 +/- 40.0 MPa and display a pseudo-yield point that arose due to the transition from the pulling of a fibrous mat with high cohesive strength to the sliding and elongation of fibers. As-spun mats were highly soluble in acidic and aqueous solutions. After cross-linking, the medium molecular weight fibers increased in diameter by an average of 161 nm, have a decreased Young's modulus of 150.8 +/- 43.6 MPa, and were insoluble in basic, acidic, and aqueous solutions. Though the extent to which GA penetrates into the chitosan fibers is currently unknown, it is evident that the cross-linking resulted in increased brittleness, a color change, and the restriction of fiber sliding that resulted in the loss of a pseudo-yield point.     

Influence of kepok banana bunch as new cellulose source on thermal,mechanical, and biodegradability properties of Thai cassava starch/polyvinyl alcohol hybrid-based bioplastic

Bioplastics were developed to overcome environmental problems that are difficult to decompose in the environment. This study analyzes Thai cassava starch-based bioplastics' tensile strength, biodegradability, moisture absorption, and thermal stability. This study used Thai cassava starch and polyvinyl alcohol (PVA) as matrices, whereas Kepok banana bunch cellulose was employed as a filler. The ratios between starch and cellulose are 10:0 (S1), 9:1 (S2), 8:2 (S3), 7:3 (S4), and 6:4 (S5), while PVA was set constant. The tensile test showed the S4 sample's highest tensile strength of 6.26 MPa, a strain of 3.85%, and a modulus of elasticity of 166 MPa. After 15 days, the maximum soil degradation rate in the S1 sample was 27.9%. The lowest moisture absorption was found in the S5 sample at 8.43%. The highest thermal stability was observed in S4 (316.8°C). This result was significant in reducing the production of plastic waste for environmental remediation.     

A biomimetic tubular scaffold with spatially designed nanofibers of protein/PDS® bio‐blends

Electrospun tubular conduit (4 mm inner diameter) based on blends of polydioxanone (PDS II®) and proteins such as gelatin and elastin having a spatially designed trilayer structure was prepared for arterial scaffolds. SEM analysis of scaffolds showed random nanofibrous morphology and well‐interconnected pore network. Due to protein blending, the fiber diameter was reduced from 800–950 nm range to 300–500 nm range. Fourier‐transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) results confirmed the blended composition and crystallinity of fibers. Pure PDS scaffold under hydrated state exhibited a tensile strength of 5.61 ± 0.42 MPa and a modulus of 17.11 ± 1.13 MPa with a failure strain of 216.7 ± 13%. The blending of PDS with elastin and gelatin has decreased the tensile properties. A trilayer tubular scaffold was fabricated by sequential electrospinning of blends of elastin/gelatin, PDS/elastin/gelatin, and PDS/gelatin (EG/PEG/PG) to mimic the complex matrix structure of native arteries. Under hydrated state, the trilayer conduit exhibited tensile properties (tensile strength of 1.77 ± 0.2 MPa and elastic modulus of 5.74 ± 3 MPa with a failure strain of 75.08 ± 10%) comparable to those of native arteries. In vitro degradation studies for up to 30 days showed about 40% mass loss and increase in crystallinity due to the removal of proteins and “cleavage‐induced crystallization” of PDS. Biotechnol. Bioeng. 2009; 104: 1025–1033. © 2009 Wiley Periodicals, Inc.     

Evaluation of a novel poly(epsilon-caprolactone)-organosiloxane hybrid material for the potential application as a bioactive and degradable bone substitute

A novel poly(epsilon-caprolactone)-organosiloxane hybrid material containing calcium salt (Si-O-PCL) was prepared and evaluated as a bioactive and degradable bone substitute material. The Si-O-PCL hybrid was synthesized by the end-capping of 3-isocyanatopropyl triethoxysilane with alpha,omega-hydroxyl PCL following sol-gel reaction with calcium nitrate tetrahydrate. Its tensile mechanical properties were evaluated, and additional specimens were exposed to simulated body fluid (SBF) for the time range from 3 h to 7 days. The SBF exposure led to the deposition of a layer of apatite crystals on the surface of the Si-O-PCL hybrid within 9 h of soaking. The tensile strength was around 18 MPa, Young's modulus was around 200 MPa, and the strain at break was around 290%. This material is likely to have a potential application as a bioactive and degradable bone substitute because of its apatite forming ability, biodegradability, and mechanical properties comparable to those of human cancellous bone.     

Tensile experiments and SEM fractography on bovine subchondral bone

Subchondral bone undecalcified samples, extracted from bovine femoral heads, are subjected to a direct tensile load. The Young's modulus of each sample is determined from repeated tests within the elastic limit. In a last test, the tensile load is increased up to the specimen failure, determining the ultimate tensile strength. The investigation is performed on both dry and wet specimens. The measured Young's modulus for dry samples is 10.3+/-2.5GPa, while that of wet samples is 3.5+/-1.2GPa. The ultimate tensile strengths are 36+/-10 and 30+/-7.5MPa for dry and wet specimens, respectively. SEM micrographs of failure surfaces show characteristic lamellar bone structures, with lamellae composed of calcified collagen fibers. Rudimentary osteon-like structures are also observed. Failure surfaces of wet samples show a marked fiber pull-out, while delamination predominates in dry samples. The obtained results are interpreted on the basis of the deformation mechanisms typical of fiber-reinforced laminated composite materials.     

Systematic review and meta-analysis of the biomechanical properties of the human dura mater applicable in computational human head models

Accurate biomechanical properties of the human dura mater are required for computational models and to fabricate artificial substitutes for transplantation and surgical training purposes. Here, a systematic literature review was performed to summarize the biomechanical properties of the human dura mater that are reported in the literature. Furthermore, anthropometric data, information regarding the mechanically tested samples, and specifications with respect to the used mechanical testing setup were extracted. A meta-analysis was performed to obtain the pooled mean estimate for the elastic modulus, ultimate tensile strength, and strain at maximum force. A total of 17 studies were deemed eligible, which focused on human cranial and spinal dura mater in 13 and 4 cases, respectively. Pooled mean estimates for the elastic modulus (n?=?448), the ultimate tensile strength (n?=?448), and the strain at maximum force (n?=?431) of 68.1 MPa, 7.3 MPa and 14.4% were observed for native cranial dura mater. Gaps in the literature related to the extracted data were identified and future directions for mechanical characterizations of human dura mater were formulated. The main conclusion is that the most commonly used elastic modulus value of 31.5 MPa for the simulation of the human cranial dura mater in computational head models is likely an underestimation and an oversimplification given the morphological diversity of the tissue in different brain regions. Based on the here provided meta-analysis, a stiffer linear elastic modulus of 68 MPa was observed instead. However, further experimental data are essential to confirm its validity.

     

Improved film properties of radiation-treated medium-chain-length poly(hydroxyalkanoates)

Medium-chain-length poly(hydroxyalkanoates) (mcl-PHAs) were synthesized from coconut oil (PHA-C), tallow (PHA-T), and soybean oil (PHA-S) by bacterial fermentation using Pseudomonas resinovorans as the producer strain. Films were solution-cast and subjected to 50 kGy of -irradiation. This resulted in crosslink formation based on the number of olefinic groups present in the polymer side-chains. In each case, radiation improved the tensile strength (104% and 63%), percent elongation (49% and 13%), and Young's modulus (30% and 76%) of PHA-C and PHA-T films, respectively. The greatest effect was on PHA-S, which was converted from an amorphous, liquid-like material to a solid elastomeric film. © Rapid Science Ltd. 1998     

Mechanical characteristics of biological soft tissue]

In a detailed study mechanical properties of tendons, muscles, nerves, blood-vessels and skin of just slaughtered pigs have been investigated in nearly stationary stress tests. Tensile tests have produced tensile strength, ultimate stress and their appropriate strains, Young's modulus and the work up to fatigue of samples. In hysteresis tests the deformation work has been determined as a function of numbers of stress cycles. The hysteresis decrease with the number of stress cycles and approaches asymptotically to cero. By preconditioning of tendons, nerves and blood-vessels to steady state significant differences of strain at tensile strength and of Young's modulus have been established. Moreover for nerves the tests have revealed significant deviations of tensile strength. Bruise tests have been carried out with muscle tissue. For the described setup the limit force can be specified, at which pathological changes appear. Subsequently conducted histological investigations have demonstrated this. In dynamical bruise tests there appeared no pathological changes in muscle tissue in spite of higher transmitted energy.     

Determination of Young's modulus for nanofibrillated cellulose multilayer thin films using buckling mechanics

The Young's modulus of multilayer films containing nanofibrillated cellulose (NFC) and polyethyleneimine (PEI) was determined using the strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) technique. (1) Multilayer films were built up on polydimethylsiloxane substrates using electrostatic layer-by-layer assembly. At 50% relative humidity, SIEBIMM gave a constant Young's modulus of 1.5 ± 0.2 GPa for 35-75 nm thick films. Conversely, in vacuum, the Young's modulus was 10 times larger, at 17.2 ± 1.2 GPa. A slight decrease in buckling wavelength with increasing strain was observed by scanning electron microscopy with in situ compression, and above 10% strain, extensive cracking parallel to the compressive direction occurred. We conclude that whereas PEI acts as a "glue" to hold multiple layers of NFC together, it prevents full development of hydrogen bonding and specific fibril-fibril interactions, and at high humidity, its hygroscopic nature decreases the elastic modulus when compared with pure NFC films.     

Chitosan–caffeic acid–genipin films presenting enhanced antioxidant activity and stability in acidic media

The use of chitosan films has been limited due to their high degradability in aqueous acidic media. In order to produce chitosan films with high antioxidant activity and insoluble in acid solutions caffeic acid was grafted to chitosan by a radical mechanism using ammonium cerium (IV) nitrate (60 mM). Genipin was used as cross-linker. This methodology originated films with 80% higher antioxidant activity than the pristine film. Also, these films only lost 11% of their mass upon seven days immersion into an aqueous solution at pH 3.5 under stirring. The films surface wettability (contact angle 105°), mechanical properties (68 MPa of tensile strength and 4% of elongation at break), and thermal stability for temperatures lower than 300 °C were not significantly influenced by the covalent linkage of caffeic acid and genipin to chitosan. Due to their characteristics, mainly higher antioxidant activity and lower solubility, these are promising materials to be used as active films.