Adsorption performance of chitosan (CS) hydrogel beads was investigated after impregnation of CS with hexadecylamine (HDA) as a cationic surfactant, for the elimination of reactive blue 4 (RB4) from wastewater. The CS/HDA beads formed with 3.8% HDA were the most effective adsorbent. The adsorption capacity was increased by 1.43 times from 317 mg/g (CS) to 454 mg/g (CS/HDA). The RB4 removal increased with decrease in the pH of dye solution from 4 to 9. The isotherm data obtained from RB4 adsorption on CS and CS/HDA are adequately described by Freundlich model (R(2)=0.946 and 0.934, χ(2)=22.414 and 64.761). The kinetic study revealed that the pseudo-second-order rate model (R(2)=0.996 and 0.997) was in better agreement with the experimental data. The negative values of ΔG° (-2.28 and -6.30 kJ/mol) and ΔH° (-172.18 and -101.62 kJ/mol) for CS beads and HDA modified CS beads, respectively; suggested a spontaneous and exothermic process for RB4 adsorption.
This study designed chitosan species-coated calcium alginate beads through concurrent core-coat formation. Chitosan oleate was synthesized by carbodiimide chemistry and characterized by 1H NMR and FTIR techniques. Chitosan or chitosan oleate was coated onto the forming alginate or alginate/tripolyphosphate core using vibratory nozzle extrusion-microencapsulation approach, followed by calcium crosslinking. Chlorpheniramine maleate served as a model water-soluble drug. The molecular characteristics, size, shape, morphology, swelling, erosion, water uptake, drug content and drug release profiles of beads were evaluated. Discrete spherical coated beads were obtained through minimizing successive bead adhesion through an interplay of nozzle vibrational frequency and polymeric solution flow rate. The tripolyphosphate ions in the core possessed higher diffusional kinetics than alginate and were better able to attract chitosan species onto bead surfaces to facilitate alginate-chitosan coacervation. Amphiphilic chitosan oleate formed smaller aggregates than chitosan. It interacted with greater ease with core alginate and tripolyphosphate. The gain in alginate/tripolyphosphate interaction with chitosan oleate at the core-coat interface enhanced bead robustness against swelling and water uptake with drug release consequently dependent on the loss of alginate-drug interaction.
Development of new materials for different applications especially as bio-composites has received great attention. This study concentrates on development of a biopolymer based on chitosan (CT) and halloysite nanotubes (HNT) and evaluates the copper removal intake as a potential application of this bio-composite. In this study, CT/HNT beads were prepared by ultrasonic-assisted extrusion-dripping method for the first time. Two sources of HNTs (i.e. Dragonite and Matauri Bay) were added into a chitosan solution (2wt.%) at various loading fractions (25, 50, 75wt.%). The effect of ultrasound as a mixing device was also studied by varying the amplitude at constant frequency of 25%, 50% and 75%. Characteristics and physical properties of the prepared CT/HNT beads were also analyzed by SEM, FTIR, TGA and BET the results show that introducing HNT to chitosan increases the adsorption capacity toward copper ions; however HNT loading fraction above 50wt.% resulted in a decrease in adsorption capacity attributed to limited accessibility of the amino groups. The adsorption capacity of the CT/HNT beads prepared from Dragonite source had a larger adsorption capacity of 14.2mg/g as compared to that of Matauri Bay, 10.55mg/g. It was observed that the adsorption capacity of the beads toward copper ions decreased when the loading fraction of HNT is increased at constant ultrasound amplitude. The result of this study helps to understand the links between the characteristics and adsorption abilities of CT/HNT beads.
Conventional alginate pellets underwent rapid drug dissolution and failed to exert colon targeting unless subjected to complex coating. This study designed coatless delayed-release oral colon-specific alginate pellets for ulcerative colitis treatment. Alginate pellets, formulated with water-insoluble ethylcellulose and various calcium salts, were prepared using solvent-free melt pelletization technique which prevented reaction between processing materials during agglomeration and allowed reaction to initiate only in dissolution. Combination of acid-soluble calcium carbonate and highly water-soluble calcium acetate did not impart colon-specific characteristics to pellets due to pore formation in fragmented matrices. Combination of moderately water-soluble calcium phosphate and calcium acetate delayed drug release due to rapid alginate crosslinking by soluble calcium from acetate salt followed by sustaining alginate crosslinking by calcium phosphate. The use of 1:3 ethylcellulose-to-alginate enhanced the sustained drug release attribute. The ethylcellulose was able to maintain the pellet integrity without calcium acetate. Using hydrophobic prednisolone as therapeutic, hydrophilic alginate pellets formulated with hydrophobic ethylcellulose and moderately polar calcium phosphate exhibited colon-specific in vitro drug release and in vivo anti-inflammatory action. Coatless oral colon-specific alginate pellets can be designed through optimal formulation with melt pelletization as the processing technology.
In this study, a biodegradable photodynamic antibacterial film (Car-Cur) was prepared using casting method with κ-Carrageenan (κ-Car) as film-forming substrate and curcumin-β-cyclodextrin (Cur-β-CD) complex as photosensitizer. The comprehensive performance of this Car-Cur film was investigated. The obtained results showed that the concentration of Cur-β-CD was an important factor determining the properties of film including tensile strength (TS) elongation at break (EB), water vapor permeability (WVP), water content (WC) and thermal stability. When the concentration of Cur-β-CD is 1%, the film demonstrated the maximum TS and EB, increased thermal stability, with desirable WVP and WC. Furthermore, this film also showed good photodynamic antibacterial potential against Staphylococcus aureus and Escherichia coli upon irradiation of blue LED light. Moreover, the film can be degraded in the soil in one week. In conclusion, our results suggested Car-Cur photodynamic film could be developed as biodegradable antimicrobial packaging material for food preservation.
The Box-Behnken design was applied to optimize the extraction of pectin from Averrhoa bilimbi (ABP) using deep eutectic solvents (DES). The four variables of extraction were percentage of DES (X1), extraction time (X2), temperature (X3), and molar ratio of DES components (X4). The quadratic regression equation was established as a predicted model with R2 value of 0.9375. The optimal condition was X1 = 3.74% (w/v), X2 = 2.5 h, X3 = 80 °C, and X4 = 1:1. No significant difference between the predicted (14.70%) and experimental (14.44%) maximum yield of sample was noted. Characterization of physico-chemical properties characterization of ABP was performed. The main components of ABP were galacturonic acids, arabinoses, and xyloses. ABP also showed good functional properties such as water holding capacity (3.70 g/g), oil holding capacity (2.40 g/g), and foaming capacity (133.33%). The results also showed that ABP exhibited free radical scavenging activity (41.46%) and ferric reducing antioxidant power (1.15 mM).
Vitexin of Ficus deltoidea exhibits intestinal α-glucosidase inhibitory and blood glucose lowering effects. This study designs oral intestinal-specific alginate nanoparticulate system of vitexin. Nanospray-dried alginate, alginate/stearic acid and alginate-C18 conjugate nanoparticles were prepared. Stearic acid was adopted to hydrophobize the matrix and minimize premature vitexin release in stomach, whereas C-18 conjugate as immobilized fatty acid to sustain hydrophobic effect and drug release. Nanoparticles were compacted with polyethylene glycol (PEG 3000, 10,000 and 20,000). The physicochemical, drug release, in vivo blood glucose lowering and intestinal vitexin content of nanoparticles and compact were determined. Hydrophobization of alginate nanoparticles promoted premature vitexin release. Compaction of nanoparticles with PEG minimized vitexin release in the stomach, with stearic acid loaded nanoparticles exhibiting a higher vitexin release in the intestine. The introduction of stearic acid reduced vitexin-alginate interaction, conferred alginate-stearic acid mismatch, and dispersive stearic acid-induced particle breakdown with intestinal vitexin release. Use of PEG 10,000 in compaction brought about PEG-nanoparticles interaction that negated initial vitexin release. The PEG dissolution in intestinal phase subsequently enabled particle breakdown and vitexin release. The PEG compacted nanoparticles exhibited oral intestinal-specific vitexin release, with positive blood glucose lowering and enhanced intestinal vitexin content in vivo.
Microencapsulation of polysaccharidic nanoparticles is met with nanoscale and biological performance changes. This study designs soft agglomerates as nanoparticle vehicle without nanoparticles undergoing physical processes that alter their geometry. The nanoparticles were made of high molecular weight chitosan/pectin with covalent 5-fluorouracil/folate. Nanoparticle aggregation vehicle was prepared from low molecular weight chitosan. The nanoparticles and aggregation vehicle were blended in specific weight ratios to produce soft agglomerates. Nanoparticles alone are unable to agglomerate. Adding aggregation vehicle (< 2 μm) promoted soft agglomeration with nanoparticles deposited onto its surfaces with minimal binary coalescence. The large and rough-surfaced aggregation vehicle promoted nanoparticles deposition and agglomeration. A rounder vehicle allowed assembly of nanoparticles-on-aggregation vehicle into agglomerates through interspersing smaller between larger populations. Soft agglomeration reduced early drug release, and was responsive to intracapsular sodium alginate coat to further sustain drug release. The soft agglomerates can serve as a primary oral colon-specific vehicle.
Hydrogels are an attractive system for a myriad of applications. While most hydrogels are usually formed from synthetic materials, lignocellulosic biomass appears as a sustainable alternative for hydrogel development. The valorization of biomass, especially the non-woody biomass to meet the growing demand of the substitution of synthetics and to leverage its benefits for cellulose hydrogel fabrication is attractive. This review aims to present an overview of advances in hydrogel development from non-woody biomass, especially using native cellulose. The review will cover the overall process from cellulose depolymerization, dissolution to crosslinking reaction and the related mechanisms where known. Hydrogel design is heavily affected by the cellulose solubility, crosslinking method and the related processing conditions apart from biomass type and cellulose purity. Hence, the important parameters for rational designs of hydrogels with desired properties, particularly porosity, transparency and swelling characteristics will be discussed. Current challenges and future perspectives will also be highlighted.
Crosslinked carboxymethyl cellulose grafted carboxymethyl polyvinyl alcohol (CMC-g-CMPVA) was loaded with modified magnetite iron oxide (Fe3O4) nanoparticles to synthesise a new and easily separable adsorbent for the removal of copper (II) ions from water. The novel adsorbents were characterised by the presence of the functional group, surface morphology, crystallinity and magnetic property. The equilibrium time from the adsorption studies was found to be less than 240min for both film and bead forms while the rate of Cu2+removal decreased as the initial Cu2+concentration increased. In addition, CMC-g-CMPVA film loaded with Fe3O4/SiO2nanoparticles was the best adsorbent with maximum adsorption capacity of 35.34mg/g and exhibited a reusable potential. The properties exhibited by the new heterogeneous material is a promising adsorbent for the removal and recovery of copper (II) from wastewater.
Sugar palm fibre (SPF) was treated with NaClO2, bleached with NaOH and subsequently hydrolyzed with acid to obtain sugar palm nanocrystalline cellulose (SPNCCs). Bionanocomposites in the form of films were prepared by mixing sugar palm starch (SPS) and sorbitol/glycerol with different nanofiller SPNCCs compositions (0-1.0 wt%) using solution casting method. The resulting fibres and nanocomposites were characterized in terms of morphology (FESEM and TEM), footprint, crystallinity (XRD), light transmittance, biodegradability, physical, water barrier, thermal (TGA, DSC and DMA) and mechanical properties. The length (L), diameter (D) and L/D values of the SPNCCs were 130 ± 30.23, 8.5 ± 1.82 nm, and 15.3, respectively. The SPS/SPNCCs nanocomposite films exhibited higher crystallinity, tensile strength, Young's modulus, thermal and water-resistance compared to the neat SPS film. The results showed that the tensile strength and moduli of the bionanocomposites increased after being reinforced with SPNCCs and the optimum nanofiller content was 0.5%.
The development and characterization of environmentally friendly bilayer films from sugar palm starch (SPS) and poly(lactic acid) (PLA) were conducted in this study. The SPS-PLA bilayer films and their individual components were characterized for their physical, mechanical, thermal and water barrier properties. Addition of 50% PLA layer onto 50% SPS layer (SPS50-PLA50) increased the tensile strength of neat SPS film from 7.74 to 13.65MPa but reduced their elongation at break from 46.66 to 15.53%. The incorporation of PLA layer significantly reduced the water vapor permeability as well as the water uptake and solubility of bilayer films which was attributed to the hydrophobic characteristic of the PLA layer. Furthermore, scanning electron microscopy (SEM) image of SPS50-PLA50 revealed lack of strong interfacial adhesion between the SPS and PLA. Overall, the incorporation of PLA layer onto SPS films enhances the suitability of SPS based films for food packaging.
Previously, studies have demonstrated that topical application of simvastatin can promote wound healing in diabetic mice via augmentation of angiogenesis and lymphangiogenesis. This study aimed to formulate and characterize simvastatin in alginate-based composite film wound dressings. Biopolymers used for composite films were sodium alginate blended with pectin or gelatin. The films were prepared and characterized based on their physical properties, surface morphology, mechanical strength and rheology. Then, in vitro drug releases from the films were investigated and, finally, the cell viability assay was performed to assess the cytotoxicity profile. From the pre-formulation studies, alginate/pectin composite film showed to possess desirable wound dressing properties and superior mechanical properties. The in vitro drug release profile revealed that alginate/pectin film produced a controlled release drug profile, and cell viability assay showed that the film was non-toxic. In summary, alginate/pectin composite film is suitable to be formulated with simvastatin as a potential wound dressing.
Blends of poly (1, 8-octanediol citrate) (POC) and chitosan (CS) were prepared through solution casting technique. Films with different component fractions (POC/CS: 100/0, 90/10, 80/20, 70/30, 60/40, and 0/100) were successfully prepared and characterized for their mechanical, thermal, structural and morphological properties as well as biocompatibility. The incorporation of CS to POC significantly increased tensile strength and elastic modulus and presented limited influences on pH variation which is important to the biocompatibility of biomaterial implants. The assessment of surface topography indicated that blending could enhance and control the surface roughness of the pure films. POC/CS blends well-supported human dermal fibroblast cells attachment and proliferation, and thus can be used for a range of tissue engineering applications.
In this study, regenerated cellulose/halloysites (RC/HNT) nanocomposites with different nanofillers loading were fabricated by dissolving the cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid. The films were prepared via solution casting method and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mechanical properties were investigated by tensile testing. It clearly displayed a good enhancement of both tensile strength and Young's modulus with HNT loading up to 5 wt%. As the HNT loadings increased to 5 wt%, the thermal behaviour and water resistance rate was also increased. The TEM and SEM images also depicted even dispersion of the HNT and a good intertubular interaction between the HNT and the cellulose matrix.
This study is focused on nanocrystalline cellulose (NCC) flakes for methylene blue (MB) removal via adsorption. NCC flakes exhibit a high adsorption capacity (188.7 mg/g fixed at 0.7 g/L adsorbent dosage, 25 °C and pH 6) compared to other nanomaterials, such as carbon nanotube and other cellulosic materials, such as coffee husks. Unlike NCC powder, it was observed that NCC flakes can be easily separated from wastewater containing MB. Further adsorption studies were conducted on NCC flakes, and it was found that 0.7 g/L was the optimum adsorbent dosage, which fitted well with the Langmuir Isotherm. The mean free energy value from Dubinin-Radushkevich isotherm was less than 8 kJ/mol. ΔGo values at different temperatures were within the -20 kJ/mol to 0 kJ/mol range. In conclusion, NCC flakes is a promising and practical 'green' nanomaterial that can be further developed for industrial applications.
Sulphated polysaccharides (SPs) are carbohydrate macromolecules with sulphate esters that are found among marine algae, seagrasses, mangroves and some terrestrial plants. The sulphate concentration in the ocean (28 mM) since ancient time could have driven the production of SPs in marine algae. SPs have a gelatinous property that can protect marine algae against desiccation and salinity stress. Agar and carrageenan are red algal SPs that are widely used as gelling agents in the food and pharmaceutical industries. The information on the SPs from freshwater and land plants are limited. In this review, we reviewed the taxonomic distribution and composition of SPs in different photosynthetic lineages, and explored the association of SP production in these diversified photosynthetic organisms with evolution history and environmental stresses. We also reviewed the genes/proteins involved in SP biosynthesis. Insights into SP biosynthetic machinery may shed light on the evolution that accompanied adaptation to life on earth.
The effect of hydroxypropyl methylcellulose (HPMC) concentration on β-cyclodextrin (β-CD) solubilization of norfloxacin was examined. The solubility and dissolution of norfloxacin/β-CD and norfloxacin/β-CD/HPMC inclusion complexes were studied. The presence of β-CD increased significantly the solubility and dissolution of norfloxacin. The addition of HPMC until 5% (w/w) improved the solubilization of norfloxacin but further addition above 5% (w/w), decreased norfloxacin solubilization. Fourier transformed Infra-red (FTIR) showed that norfloxacin was successfully included into β-CD. Differential scanning calorimetry (DSC) showed that the norfloxacin endothermic peak shifted to a lower temperature with reduced intensity indicating the formation of inclusion complex. The addition of HPMC reduced further the intensity of norfloxacin endothermic peak. Most of the sharp and intense peaks of norfloxacin disappeared with the addition of HPMC. In conclusion, the concentration of hydrophilic polymer used to enhance β-CD solubilization of poorly soluble drugs is very critical.
Recently, surface functionality and thermal property of the green nanomaterials have received wide attention in numerous applications. In this study, microcrystalline cellulose (MCC) was used to prepare the nanocrystalline celluloses (NCCs) using acid hydrolysis method. The NCCs was treated with TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxy radical]-oxidation to prepare TEMPO-oxidized NCCs. Cellulose nanofibrils (CNFs) also prepared from MCC using TEMPO-oxidation. The effects of rapid cooling and chemical treatments on the thermo-structural property studies of the prepared nanocelluloses were investigated through FTIR, thermogravimetric analysis-derivative thermogravimetric (TGA-DTG), and XRD. A posteriori knowledge of the FTIR and TGA-DTG analysis revealed that the rapid cooling treatment enhanced the hydrogen bond energy and thermal stability of the TEMPO-oxidized NCC compared to other nanocelluloses. XRD analysis exhibits the effect of rapid cooling on pseudo 2Ihelical conformation. This was the first investigation performed on the effect of rapid cooling on structural properties of the nanocellulose.