Cellulosic nanofibers (NFs) from kenaf bast were used to reinforce glycerol plasticized thermoplastic starch (TPS) matrices with varying contents (0-10wt%). The composites were prepared by casting/evaporation method. Raw fibers (RFs) reinforced TPS films were prepared with the same contents and conditions. The aim of study was to investigate the effects of filler dimension and loading on linear and non-linear mechanical performance of fabricated materials. Obtained results clearly demonstrated that the NF-reinforced composites had significantly greater mechanical performance than the RF-reinforced counterparts. This was attributed to the high aspect ratio and nano dimension of the reinforcing agents, as well as their compatibility with the TPS matrix, resulting in strong fiber/matrix interaction. Tensile strength and Young's modulus increased by 313% and 343%, respectively, with increasing NF content from 0 to 10wt%. Dynamic mechanical analysis (DMA) revealed an elevational trend in the glass transition temperature of amylopectin-rich domains in composites. The most eminent record was +18.5°C shift in temperature position of the film reinforced with 8% NF. This finding implied efficient dispersion of nanofibers in the matrix and their ability to form a network and restrict mobility of the system.
In this study, an amphiphilic chitosan derivative namely N,N-dimethylhexadecyl carboxymethyl chitosan (DCMC) was synthesised and applied for the first time as a carrier agent for rotenone. The physical and chemical properties of DCMC were characterised by using Fourier Transform Infrared Spectrometer (FTIR), Proton Nuclear Magnetic Resonance Spectrometer ((1)H NMR), CHN-O Elemental Analyser, Thermogravimetric Analyser (TGA) and Differential Scanning Calorimeter (DSC). DCMC was soluble in acidic (except pH 4), neutral and basic media with percent of transmittance (%T) values ranged from 67.2 to 99.4%. The critical micelle concentration (CMC) was determined as 0.095mg/mL. Transmission Electron Microscopy (TEM) analysis confirmed that DCMC has formed self-aggregates and exhibited spherical shape with the size of 65.5-137.0nm. The encapsulation efficiency (EE) and loading capacity (LC) of DCMC micelles with different weight ratios (DCMC:rotenone; 5:1, 50:1 and 100:1) were determined by using High Performance Liquid Chromatography (HPLC). The weight ratio of 100:1 gave the best EE with the value of more than 95.0%. DCMC micelles performed an excellent ability to control the release of rotenone, of which 99.0% of rotenone was released within 48h. Overall, DCMC has several key features to be an effective carrier agent for pesticide formulations.
In this study, the catalase-like activity of monomeric tau protein was reported in the presence of of zinc (Zn(II)) ions at low pH value. Monomeric tau protein contains two SH groups that are a target of disulfide bond formation. However these SH groups are able to interact with Zn(II) ion at pH 7.2 which creates a thiol bond as a mimetic model of chloroperoxidase active site which performs catalase like activity at low pH. Zn(II)/tau protein complex decomposed H2O2 with a high rate (Vm) as well as an efficient turn oven number (kcat) at pH 3. This remarkable catalase like activity is may be attributed to the conformational reorientation of protein at low pH. Circular dichroism (CD) studies did not demonstrate any secondary structural changes of tau protein after addition of Zn(II) ions at pH 7.2. In addition, tau protein shows identical CD bands at pH 7.2 and 3. Moreover, fluorescence quenching of tau by Zn(II) at pH 7.2 was initiated by complex formation rather than by dynamic collision. A significant red shift (6nm) was observed in the emission maximum of the fluorescence spectra when the protein was dissolved at pH 3 compared to pH 7.2. This conformational change can provide information regarding the rearrangements of the protein structure and exposure of Cys-Zn(II) group to the solvent which induces easy access of active site to H2O2 molecules and corresponding enhanced catalytic activity of Zn(II)/tau protein complex. This study introduces tau protein as a bio-inspired high performing scaffold for transition metal encapsulation and introducing an engineered apoprotein-induced biomimetic enzyme.
The aim of this work is to study the behavior of biodegradable sugar palm starch (SPS) based thermoplastic containing agar in the range of 10-40wt%. The thermoplastics were melt-mixed and then hot pressed at 140°C for 10min. SEM investigation showed good miscibility between SPS and agar. FT-IR analysis confirmed that SPS and agar were compatible and inter-molecular hydrogen bonds existed between them. Incorporation of agar increased the thermoplastic starch tensile properties (Young's modulus and tensile strength). The thermal stability and moisture uptake increased with increasing agar content. The present work shows that starch-based thermoplastics with 30wt% agar content have the highest tensile strength. Higher content of agar (40wt%) resulted to more rough cleavage fracture and slight decrease in the tensile strength. In conclusion, the addition of agar improved the thermal and tensile properties of thermoplastic SPS which widened the potential application of this eco-friendly material. The most promising applications for this eco-friendly material are short-life products such as packaging, container, tray, etc.
Pinto bean pod polysaccharide (PBPP) was successfully extracted with yield of 38.5g/100g and the PBPP gave total carbohydrate and uronic acid contents of 286.2mg maltose equivalent/g and 374.3mgGal/g, respectively. The Mw of PBPP was 270.6kDa with intrinsic viscosity of 0.262dm(3)/g, which composed of mannose (2.5%), galacturonic acid (15.0%), rhamnose (4.0%), glucose (9.0%), galactose (62.2%), xylose (2.9%) and arabinose (4.3%) with trace amount of ribose and fucose. The result suggested that PBPP has a spherical conformation with a highly branched structure. Fourier Transform Infrared analysis showed that PBPP has a similar structure as commercial pectin with an esterification degree of 59.9%, whereas scanning electron microscopy study showed that the crude polysaccharide formed a thin layer of film that was made of multiple micro strands of fibre. PBPP exhibited substantial free radical scavenging activity (7.7%), metal reducing capability (2.04mmol/dm(3)) and α-amylase inhibitory activity (97.6%) at a total amount of 1mg. PBPP also exhibited high water- and oil-holding capacities (3.6g/g and 2.8g/g, respectively). At a low concentration, PBPP exhibited emulsifying activity of 39.6% with stability of 38.6%. Apart from that, PBPP was able to show thickening capability at low concentration (0.005kg/dm(3)).
Alginate-based bipolymeric-nanobioceramic composite matrices for sustained drug release were developed through incorporation of nano-hydroxyapatite [nHAp] powders within ionotropically-gelled calcium ion-induced alginate-poly (vinyl pyrrolidone) blends polymeric systems. nHAp powders were synthesized by precipitation technique using calcium hydroxide [Ca(OH)2] and orthophosphoric acid [H3PO4] as raw materials. The average particle size of these was synthesized. nHAp powders was found as 19.04 nm and used to prepare nHAp-alginate-PVP beads containing DS. These beads exhibited drug entrapment efficiency (%) of 65.82±1.88 to 94.45±3.72% and average bead sizes of 0.98±0.07 to 1.23±0.15 mm. These beads were characterized by scanning electron microscopy (SEM) and Fourier transform-infra red (FTIR) spectroscopy analyses. Various nHAp-alginate-PVP beads containing DS exhibited prolonged sustained drug release and followed the Koresmeyer-Peppas model of drug release (R2=0.9908-0.9978) with non-Fickian release (anomalous transport) mechanism (n=0.73-0.84) for drug release over 8 h.
The water-soluble bioactive polysaccharides can contribute to the health benefits of Lycium barbarium fruit. However, the structure characteristics of these polysaccharides remain unclear yet. An important polysaccharide (LBPA) was isolated and purified from L. barbarium in this work. It was identified by chemical and spectroscopic methods as arabinogalactan with β-d-(1→6)-galactan as backbone, which was different to any reported polysaccharides from this species before. This arabinogalactan was comprised of Araf, Galp, GlcpA and Rhap with a molar ratio of 9.2:6.6:1.0:0.9. The side chains, including α-l-Araf-(1→, α-l-Araf-(1→5)-α-l-Araf-(1→, β-l-Araf-(1→5)-α-l-Araf-(1→ and α-l-Rhap-(1→4)-β-d-GlcpA-(1→6)-β-d-Galp-(1→, were linked to β-d-(1→6)-galactan at O-3. The putative structure was drawn as below. The molecular weight was determined to be 470,000g/mol by gel permeation chromatography.
A new approach to design multifunctional chitosan based nanohydrogel with enhanced glucose sensitivity, stability, drug loading and release profile are reported. Two approaches were followed for functionalization of chitosan based nanohydrogel with 3-APBA via EDC and 3-APTES. The effective functionalization, structure and morphology of Chitosan based IPN respectively were confirmed by FTIR, SEM and AFM. At physiological conditions, the glucose-induced volume phase transition and release profile of the model drug Alizarin Red with 1,2-diol structure (comparative to insulin as a drug as well as a dye for bio separation) were studied at various glucose concentrations, pH and ionic strengths. The results suggested a new concept for diabetes treatment and diols sensitivity in view of their potential hi-tech applications in self-regulated on-off response to the treatment (drug delivery and bio separation concurrently).
Polylactic acid (PLA) nanocomposites reinforced with hybrid montmorillonite/cellulose nanowhiskers [MMT/CNW(SO4)] were prepared by solution casting. The CNW(SO4) nanofiller was first isolated from microcrystalline cellulose using acid hydrolysis treatment. PLA/MMT/CNW(SO4) hybrid nanocomposites were prepared by the addition of various amounts of CNW(SO4) [1-9 parts per hundred parts of polymer (phr)] into PLA/MMT nanocomposite at 5 phr MMT content, based on highest tensile strength values as reported previously. The biodegradability, thermal, tensile, morphological, water absorption and transparency properties of PLA/MMT/CNW(SO4) hybrid nanocomposites were investigated. The Biodegradability, thermal stability and crystallinity of hybrid nanocomposites increased compared to PLA/MMT nanocomposite and neat PLA. The highest tensile strength of hybrid nanocomposites was obtained by incorporating 1 phr CNW(SO4) [∼ 36 MPa]. Interestingly, the ductility of hybrid nanocomposites increased significantly by 87% at this formulation. The Young's modulus increased linearly with increasing CNW(SO4) content. This is due to the relatively good dispersion of nanofillers in the hybrid nanocomposites, as revealed by transmission electron microscopy. Fourier transform infrared spectroscopy indicated the formation of some polar interactions. In addition, water resistance of the hybrid nanocomposites improved and the visual transparency of neat PLA film did not affect by addition of CNW(SO4).
Three strains of Spirulina platensis isolated from different locations showed capability of synthesizing poly(3-hydroxybutyrate) [P(3HB)] under nitrogen-starved conditions with a maximum accumulation of up to 10 wt.% of the cell dry weight (CDW) under mixotrophic culture conditions. Intracellular degradation (mobilization) of P(3HB) granules by S. platensis was initiated by the restoration of nitrogen source. This mobilization process was affected by both illumination and culture pH. The mobilization of P(3HB) was better under illumination (80% degradation) than in dark conditions (40% degradation) over a period of 4 days. Alkaline conditions (pH 10-11) were optimal for both biosynthesis and mobilization of P(3HB) at which 90% of the accumulated P(3HB) was mobilized. Transmission electron microscopy (TEM) revealed that the mobilization of P(3HB) involved changes in granule quantity and morphology. The P(3HB) granules became irregular in shape and the boundary region was less defined. In contrast to bacteria, in S. platensis the intracellular mobilization of P(3HB) seems to be faster than the biosynthesis process. This is because in cyanobacteria chlorosis delays the P(3HB) accumulation process.
In this article, modified κ-carrageenan hydrogel nanocomposites were synthesized to increase the release ability of carrageenan hydrogels under gastrointestinal conditions. The effect of MgO nanoparticle loading in a model drug (methylene blue) release is investigated. Characterization of hydrogels were carried out using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM) and Differential Scanning Calorimetry (DSC). Genipin was used to increase the delivery performance in gastrointestinal tract delivery by decreasing release in simulated stomach conditions and increasing release in simulated intestine conditions. It is shown that the amount of methylene blue released from genipin-cross-linked nanocomposites can be 67.5% higher in intestine medium and 56% lower in the stomach compared to κ-carrageenan hydrogel. It was found that by changing the nanoparticle loading and genipin concentration in the composite, the amount of drug released can be monitored. Therefore, applying nanoparticles appears to be a potential strategy to develop controlled drug delivery especially in gastrointestinal tract studies.
The ability of Delftia acidovorans to incorporate a broad range of 3-hydroxyvalerate (3HV) monomers into polyhydroxyalkanoate (PHA) copolymers was evaluated in this study. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] containing 0-90 mol% of 3HV was obtained when a mixture of sodium 3-hydroxybutyrate and sodium valerate was used as the carbon sources. Transmission electron microscopy analysis revealed an interesting aspect of the P(3HB-co-3HV) granules containing high molar ratios of 3HV whereby, the copolymer granules were generally larger than those of poly(3-hydroxybutyrate) [P(3HB)] granules, despite having almost the same cellular PHA contents. The large number of P(3HB-co-3HV) granules occupying almost the entire cell volume did not correspond to a higher amount of polymer by weight. This indicated that the granules of P(3HB-co-3HV) contain polymer chains that are loosely packed and therefore have lower density than P(3HB) granules. It was also interesting to note that a decrease in the length of the side chain from 3HV to 4-hydroxybutyrate (4HB) corresponded to an increase in the density of the respective PHA granules. The presence of longer side chain monomers (3HV) in the PHA structure seem to exhibit steric effects that prevent the polymer chains in the granules from being closely packed. The results reported here have important implications on the maximum ability of bacterial cells to accumulate PHA containing monomers with longer side chain length.
Chitosan-derived hemostatic agents with various formulations may have distinct potential in hemostasis. This study assessed the ability of different grades and forms of chitosan derivatives as hemostatic agents to enhance platelet adhesion and aggregation in vitro. The chitosan derivatives utilized were 2% NO-CMC, 7% NO-CMC (with 0.45 mL collagen), 8% NO-CMC, O-C 52, 5% O-CMC-47, NO-CMC-35, and O-C 53. Samples of chitosan derivatives weighing 5mg were incubated at 37°C with 50 μL of phosphate buffer saline (PBS) (pH 7.4) for 60 min. The morphological features of the platelets upon adherence to the chitosan were viewed using scanning electron microscope (SEM), and the platelet count was analyzed with an Automated Hematology Analyzer. For platelet aggregation, we added an adenosine diphosphate (ADP) agonist to induce the chitosan-adhered platelets. O-C 52 bound with platelets exhibited platelet aggregates and clumps on the surface of the membrane layer with approximately 70-80% coverage. A statistically significant correlation (p<0.01) for the platelet count was identified between the baseline value and the values at 10 min and 20 min. The results indicate that O-C 53 and O-C 52 were able to promote clotting have the potential to induce the release of platelets engaged in the process of hemostasis.
The adsorption of Cu(II) ions from aqueous solution by chitosan and chitosan/PVA beads was studied in a batch adsorption system. Chitosan solution was blended with poly(vinyl alcohol) (PVA) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. The adsorption capacities and rates of Cu(II) ions onto chitosan and chitosan/PVA beads were evaluated. The Langmuir, Freundlich and BET adsorption models were applied to describe the isotherms and isotherm constants. Adsorption isothermal data could be well interpreted by the Langmuir model. The kinetic experimental data properly correlated with the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step. The Cu(II) ions can be removed from the chitosan and chitosan/PVA beads rapidly by treatment with an aqueous EDTA solution. Results also showed that chitosan and chitosan/PVA beads are favourable adsorbers.
In this study, hybrid montmorillonite/cellulose nanowhiskers (MMT/CNW) reinforced polylactic acid (PLA) nanocomposites were produced through solution casting. The CNW filler was first isolated from microcrystalline cellulose by chemical swelling technique. The partial replacement of MMT with CNW in order to produce PLA/MMT/CNW hybrid nanocomposites was performed at 5 parts per hundred parts of polymer (phr) fillers content, based on highest tensile strength values as reported in our previous study. MMT were partially replaced with various amounts of CNW (1, 2, 3, 4 and 5phr). The tensile, thermal, morphological and biodegradability properties of PLA hybrid nanocomposites were investigated. The highest tensile strength of hybrid nanocomposites was obtained with the combination of 4phr MMT and 1phr CNW. Interestingly, the ductility of hybrid nanocomposites increased significantly by 79% at this formulation. The Young's modulus increased linearly with increasing CNW content. Thermogravimetric analysis illustrated that the partial replacement of MMT with CNW filler enhanced the thermal stability of the PLA. This is due to the relatively good dispersion of fillers in the hybrid nanocomposites samples as revealed by transmission electron microscopy. Interestingly, partial replacements of MMT with CNW improved the biodegradability of hybrid nanocomposites compared to PLA/MMT and neat PLA.
The manufacture and potential application of biodegradable films for food application has gained increased interest as alternatives to conventional food packaging polymers due to the sustainable nature associated with their availability, broad and abundant source range, compostability, environmentally-friendly image, compatibility with foodstuffs and food application, etc. Gelatin is one such material and is a unique and popularly used hydrocolloid by the food industry today due to its inherent characteristics, thereby potentially offering a wide range of further and unique industrial applications. Gelatin from different sources have different physical and chemical properties as they contain different amino acid contents which are responsible for the varying characteristics observed upon utilization in food systems and when being utilized more specifically, in the manufacture of films. Packaging films can be successfully produced from all gelatin sources and the behaviour and characteristics of gelatin-based films can be altered through the incorporation of other food ingredients to produce composite films possessing enhanced physical and mechanical properties. This review will present the current situation with respect to gelatin usage as a packaging source material and the challenges that remain in order to move the manufacture of gelatin-based films nearer to commercial reality.
Potato starch nanocrystals were found to serve as an effective reinforcing agent for natural rubber (NR). Starch nanocrystals were obtained by the sulfuric acid hydrolysis of potato starch granules. After mixing the latex and the starch nanocrystals, the resulting aqueous suspension was cast into film by solvent evaporation method. The composite samples were successfully prepared by varying filler loadings, using a colloidal suspension of starch nanocrystals and NR latex. The morphology of the nanocomposite prepared was analyzed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). FESEM analysis revealed the size and shape of the crystal and their homogeneous dispersion in the composites. The crystallinity of the nanocomposites was studied using XRD analysis which indicated an overall increase in crystallinity with filler content. The mechanical properties of the nanocomposites such as stress-strain behavior, tensile strength, tensile modulus and elongation at break were measured according to ASTM standards. The tensile strength and modulus of the composites were found to improve tremendously with increasing nanocrystal content. This dramatic increase observed can be attributed to the formation of starch nanocrystal network. This network immobilizes the polymer chains leading to an increase in the modulus and other mechanical properties.
Effect of simulated honey sugar cocktail (SHSC) on chemical and thermal stability of ovalbumin (OVA) was investigated using multiple-spectroscopic techniques. Urea-induced denaturation of OVA produced a transition, characterized by the start-, the mid- and the end-points at 3.2 M, 5.9/5.6 M and 8.5/8.0 M urea, respectively, when studied by MRE222nm and tryptophan fluorescence measurements. Presence of 10% or 20% (w/v) SHSC in the incubation mixture shifted the transition curve towards higher urea concentration in a concentration dependent manner. A comparison of far- and near-UV CD, UV-difference, ANS fluorescence and 3-D fluorescence spectral results of native OVA and 5.9 M urea-denatured OVA (U-OVA), obtained in the absence and the presence of 20% (w/v) SHSC suggested SHSC-induced stabilization of U-OVA. Furthermore, a significant shift towards higher denaturant concentration was also noticed in the GdnHCl and thermal transition curves of OVA in the presence of 20% (w/v) SHSC. Taken together, all these results suggested stabilization of OVA against chemical and thermal denaturations by SHSC.
The vulnerability of probiotics at low pH and high temperature has limited their optimal use as nutraceuticals. This study addressed these issues by adopting a physicochemical driven approach of incorporating Lactobacillus plantarum LAB12 into chitosan (Ch) coated alginate-xanthan gum (Alg-XG) beads. Characterisation of Alg-XG-Ch, which elicited little effect on bead size and polydispersity, demonstrated good miscibility with improved bead surface smoothness and L. plantarum LAB12 entrapment when compared to Alg, Alg-Ch and Alg-XG. Sequential incubation of Alg-XG-Ch in simulated gastric juice and intestinal fluid yielded high survival rate of L. plantarum LAB12 (95%) at pH 1.8 which in turn facilitated sufficient release of probiotics (>7 log CFU/g) at pH 6.8 in both time- and pH-dependent manner. Whilst minimising viability loss at 75 and 90 °C, Alg-XG-Ch improved storage durability of L. plantarum LAB12 at 4 °C. The present results implied the possible use of L. plantarum LAB12 incorporated in Alg-XG-Ch as new functional food ingredient with health claims.
In this study, a chitosan co-polymer scaffold was prepared by mixing poly(vinyl alcohol) (PVA), NO, carboxymethyl chitosan (NOCC) and polyethylene glycol (PEG) solutions to obtain desirable properties for chondrocyte cultivation. Electron beam (e-beam) radiation was used to physically cross-link these polymers at different doses (30 kGy and 50 kGy). The co-polymers were then lyophilized to form macroporous three-dimensional (3-D) matrix. Scaffold morphology, porosity, swelling properties, biocompatibility, expression of glycosaminoglycan (GAG) and type II collagen following the seeding of primary chondrocytes were studied up to 28 days. The results demonstrate that irradiation of e-beam at 50 kGy increased scaffold porosity and pore sizes subsequently enhanced cell attachment and proliferation. Scanning electron microscopy and transmission electron microscopy revealed extensive interconnected microstructure of PVA-PEG-NOCC, demonstrated cellular activities on the scaffolds and their ability to maintain chondrocyte phenotype. In addition, the produced PVA-PEG-NOCC scaffolds showed superior swelling properties, and increased GAG and type II collagen secreted by the seeded chondrocytes. In conclusion, the results suggest that by adding NOCC and irradiation cross-linking at 50 kGy, the physical and biological properties of PVA-PEG blend can be further enhanced thereby making PVA-PEG-NOCC a potential scaffold for chondrocytes.