No description available.

The development of a "cradle-to-cradle" mindset with both material performance during utilization and end of life disposal is a critical need for both ecological and economic considerations. The main limitation to the use of the biopolymers is their mechanical properties. Reinforcements are therefore a good alternative but disposal concerns then arise. Thus the objective of this dissertation is to investigate a biopolymer nanocomposite where the filler is a synthetically prepared layer double hydroxide (inorganic interface); and a biopolymer paper (organic interface) based coating or laminate. The underlying issues driving performance are the packing density of the biopolymer and the interaction with the reinforcement. Since the polyhydroxyalkanoates or PHAs (the biopolymers used for the manufacture of the nanocomposites and coatings) are semicrystalline materials, the glass transition was investigated using dynamic mechanical analysis (DMA) and dielectric spectroscopy (DES), whereas the melt crystallization, cold crystallization and melting points were investigated using differential scanning calorimetry (DSC). Fourier transform infrared (FTIR) spectroscopy was used to estimate crystallinity in the coated material given the low thermal mass of the PHA in the PHA coating. The significant enhancement of the crystallization rate in the PHA nanocomposite was probed using DSC and polarized optical microscopy (POM) and analyzed using Avrami and Lauritzen-Hoffman models. Both composites showed a significant improvement in the mechanical performance obtained by DMA, tensile and impact testing. The degradation and decomposition of the two composites were investigated in low microbial activity soil for the cellulose paper (to slow down the degradation rate that occurs in compost) and in compost. An in-house system according to the American Society for Testing and Materials ASTM D-98 (2003) was engineered. Soil decomposition showed that PHA coating into and onto the cellulose paper can be considered to be a useful method for the assessment of the degradability of the biopolymer. PHA nanocomposite showed enhanced compostability.

No description available.

Thesis(M.Sc.(Chemistry)) -- University of Limpopo, 2020 / An extensive search for a highly efficient, reusable, and non-toxic adsorbent materials for the removal of organic dyes from wastewater continues to be of great importance to the world. Activated carbon is the most widely used adsorbent material for treating dye contaminants from water owing to its high removal capacity and large surface area. However, activated carbon is expensive and not easy to regenerate. Hence, the use of biodegradable, non-toxic, and cost-effective biopolymer-based hydrogel adsorbents has attracted great attention. These adsorbents have high swelling capacity and number of adsorptive functional groups to allow adsorption of methylene blue dye. Hence in this work, we present carboxymethyl cellulose crosslinked with poly (acrylic acid) incorporated with magnetic cloisite 30B clay (CMC-cl-pAA/Fe3O4-C30B) and sodium alginate crosslinked with poly (acrylic acid) incorporated with zinc oxide (SA-cl pAA/ZnO) hydrogel nanocomposites (HNCs) for the removal of methylene blue from aqueous solution. The hydrogel nanocomposites were synthesised through in situ free radical polymerisation. The structural properties of the prepared materials were studied using Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The FTIR and XRD confirmed the successful synthesis of the CMC-cl-pAA and SA-cl-pAA hydrogels, Fe3O4-C30B and ZnO nanoparticles (NPs) and their hydrogel nanocomposites. Furthermore, the co-existence of the metal oxide nanoparticles in the CMC-cl-pAA and SA-cl-pAA hydrogel matrices was confirmed by XRD. The SEM revealed that upon the incorporation of the Fe3O4- C30B NPs onto CMC-cl-pAA, the resulting material showed spherical particles of the magnetite nanoparticles on the irregular shaped hydrogel structure. As well as on the SA-cl-pAA after modification by ZnO nanoparticles, the spherical ZnO particles were embedded on the hydrogel surface. The successful modification with metal oxide nanoparticles was also confirmed by the presence of characteristic elements of the incorporated materials on the EDS. The TEM coupled with selected area electron diffraction (SAED) confirmed the presence of Fe3O4-C30B on the hydrogel structure, in which circular bright dotted lines were observed corresponding to light diffracted by the lattice planes of different energies on the Fe3O4 structure. The thermogravimetric analysis was conducted to study the thermal stability of the materials, the results showed that the incorporation of Fe3O4-C30B and ZnO nanoparticles on CMC-cl-pAA and SA-cl-pAA hydrogels, respectively improved their thermal stability. Furthermore, DMA was used to study the mechanical stability of the prepared hydrogels and their composites. In the case of CMC-cl-pAA hydrogel, the storage modulus of CMC-cl pAA/Fe3O4-C30B nanocomposite was higher than of the hydrogel, indicating improved mechanical stability, and on SA-cl-pAA hydrogel the storage modulus decreased, indicating a decrease in mechanical stability on the SA-cl-pAA/ZnO HNC. Consequently, the swelling studies revealed that the SA/AA/ZnO HNC was highly efficient for water uptake in comparison to SA/AA hydrogel. Whereas, CMC-cl pAA/Fe3O4-C30B had lower swelling capacity than CMC-cl-pAA hydrogel. Various factors influencing the adsorption of adsorbents were systematically investigated. The kinetics, isotherms, and thermodynamics of adsorption were examined, and results showed that equilibrium data fitted the Langmuir isotherm model, and the adsorption kinetics of MB followed pseudo-second-order model in both the CMC-based HNC and SA-based HNC. Maximum adsorption capacities of 1129 and 1529.6 mg/g were achieved for SA/AA hydrogel and SA/AA/ZnO HNC, respectively, in 0.25 g/L MB solution at pH 6.0 within 40 min. Whereas maximum capacities of 1165 mg/g (pH 5) and 806.51 mg/g (pH 7) for CMC-cl-pAA hydrogel and CMC-cl-pAA/Fe3O4- C30B HNC, respectively. Thermodynamic parameters for SA/AA and CMC-cl-pAA hydrogels exhibited exothermic adsorption processes and their nanocomposites SA/AA/ZnO and CMC-cl-pAA/Fe3O4-C30B exhibited endothermic nature of the adsorption processes, respectively. Moreover, the CMC-cl-pAA/Fe3O4-C30B NCH showed improved mechanical and thermal properties as compared to CMC-cl-pAA hydrogel. In contrast, the SA/AA/ZnO HNC presented outstanding reusability with relatively better adsorption efficiencies than SA/AA hydrogel. / Sasol bursary and National Research Foundation (NRF)

Hemicelluloses (HC) are the second most abundant plant polysaccharides after cellulose, constituting 25-30% of plant materials. In spite of their abundance, HC are not effectively utilized. Recently, considerable interest has been directed to HC-based biomaterials because of their high oxygen barrier properties, which has potential in food packaging applications. In this study, HC were extracted from sugarcane bagasse and southern yellow pine using a hydrothermal technique which utilizes hot compressed water without catalyst. The parameters affecting the yield of extracted HC such as temperature, time and pressure, were tested and optimized. Eighty four percent of xylose was extracted from sugarcane bagasse at the optimum condition, 180 °C 30 min and 1 MPa pressure. In the case of southern yellow pine, 79% of the mannose was extracted at 190 °C for 10 min and 2 MPa pressure. Concentration and isolation of HC from bagasse and southern yellow pine HC extract were performed by membrane filtration and freeze drying systems. Isolated HC were characterized by FT-IR and 13C NMR techniques and used as a starting material for film preparation. Films were prepared in 0/100, 50/50, 60/40, 70/30 and 80/20% ratios of HC and sodium carboxymethylcellulose (CMC). Thirty five percent of sorbitol (w/w of HC and CMC weight) was also added as a plasticizer. Films were evaluated by measuring water absorption, water vapor permeability (WVP), tensile property and oxygen barrier capability. At 55% relative humidity (RH) and 25 °C the water absorption of both sugarcane bagasse and southern yellow pine HC-based films tended to increase as HC content increased. The lowest WVP of sugarcane bagasse (3.84e-12 g/Pa h m) and southern yellow pine HC films (2.18e-12 g/Pa h m) were determined in 60/40 HC/CMC films. Tensile test results showed that as HC content increases the Young’s modulus decreases, deflection at maximum load and percentage of strain at break increase. It implies that the film properties are changing from stiff to elastic. The oxygen permeability for 60/40 bagasse HC/CMC film was 0.005265 cc μm / (m2 day kPa) and for 70/30 pine HC/CMC film was 0.007570 cc μm /(m2 day kPa).

No description available.

Yes / A novel fully biosbased poly(lactic acid)-b-poly(lactide-co-caprolactone) (PLA-b-PLCL) with a two-phase structure and long-chain branches was specifically designed and prepared through reactive melt processing. The results showed that PLCL segments were introduced onto PLA chains successfully. With the increase of PLCL content, the blockier distribution of LA/CL chain sequences of the sample was exhibited. PLA-b-PLCL showed two distinct thermal transitions, corresponding to the glass transition of PLA and PLCL domains, respectively, whereas the phase morphology changed from a sea-island to a co-continuous structure with increasing PLCL content. Because of the long-chain branched structure, PLA-b-PLCL samples showed a much higher viscoelasticity, strong molecular entanglement, and obvious strain-hardening behavior, resulting in a high draw ratio of the sample during orientation process, whereas the tensile strength and the modulus of the oriented sample reached up to 173 MPa and 5.4 GPa, respectively, which basically met the requirements of bone screws. Moreover, PLA-b-PLCL showed a triple-shape memory effect at 55 and 120 °C, respectively. For PLA-b-30 wt % PLCL, the recovery ratio can reach up to 98.1% under 55 °C, while high mechanical properties can be maintained, realizing self-reinforcement and self-fastening effect simultaneously as a smart bone fixation material.

This study investigated the influence of cations on biopolymer characteristics and sludge properties. Settling and dewatering properties of sludges were measured and correlated to the biopolymer characteristics. In addition, effects of cations on sludge conditioning with polymer were studied. Experiment mainly consisted of two parts, reactor study and batch study. In re- actor study continuous-flow reactors were operated. Variables used included varying types of substrate, addition of magnesium or sodium, and changes in pH. The batch study included conditioning tests on the sludges with combinations of cationic polymer and salts. Biopolymers were extracted using alkali extraction followed by gel filtration and subsequent carbohydrate and protein analysis. The sludge settling and dewatering were measured in terms of SVI and specific resistance, respectively. Sludge filtering rate (TIF) was used to measure the conditioning efficiency. The results indicated that the influence of cations depended on the type and concentration of salt. An optimal concentration of Mg was found to improve biopolymer binding. The organic composition of feed also affected biopolymer characteristics. A higher pH combined with a high amount of sodium released biopolymer and resulted in sludge deflocculation. A relationship between unbound biopolymer and soluble effluent COD was observed but no discernible relation between biopolymer binding and sludge settling and dewatering properties was found. Cations were found to reduce polymer requirement during sludge conditioning. In addition, the amount of extractable biopolymers by alkali extraction was greatly influenced by salt. Magnesium inhibited the release of biopolymer, but sodium im- proved the efficiency of biopolymer extraction. / Master of Science

Submitted in fulfillment of the requirements of the degree of Doctor of Philosophy: Chemistry, Durban University of Technology, 2015. / Chitin, the second most abundant natural biopolymer, is composed of repeating units of N-acetyl-β-D-glucosamine and primarily forms the structural component of protective biological matrices such as fungal cell walls and exoskeletons of insects. Chitinases are a ubiquitous class of extracellular enzymes that have gained attention in the past few years due to their wide range of biotechnological applications, especially in the field of agriculture for bio-control of fungal phytopathogens. They play an important role in the defense of organisms against chitin-containing parasites by hydrolyzing the β-1,4-linkages in chitin and hence act as anti-fungal as well as anti-biofouling agents. Moreover, the effectiveness of conventional insecticides is increasingly compromised by the occurrence of resistance and thus, chitinases offer a potential alternative to the use of chemical fungicides. In recent years, thermostable enzymes isolated from thermophilic microorganisms have gained widespread attention in industrial, medical, environmental and biotechnological applications due to their inherent stability at high temperatures and a wide range of pH optima. Determination of the three- dimensional structure of a protein can provide important details about its biological functions and its mode of action. However, despite their significance, the precise three-dimensional structures of most of the chitinases, including those isolated from Thermomyces lanuginosus is not fully characterized so far. Hence, the main focus of the present study was to gain a better understanding of the structural features of chitinases obtained from this thermostable fungus using both experimental and computational techniques, and their relationship with their activity profiles. The genes encoding thermostable chitinase II from T. lanuginosus were isolated and cloned in both E. coli as well as the Pichia pastoris expression system. Analysis of the nucleotide sequences revealed that the chitinase II gene (1196 bp) encodes a 343 amino acid protein of molecular weight 36.65 kDa whereas the chitinase I gene (1538 bp) encodes a 400 amino acid protein of molecular weight 44.14 kDa. In silico protein modeling was helpful in predicting the 3D models of the novel chitinase II enzyme, followed by the prediction of its active sites. The presence of Glu176 was found to be essential for the activity of chitinase II. Similarly, analysis of chitinase I revealed several active sites in its structural framework. A 10 ns Molecular dynamics (MD) simulations was implemented to assess the conformational preferences of chitinases. The MD trajectories at different temperatures clearly revealed that the stability of the enzymes were maintained at higher temperatures. Additionally, a constant pH molecular dynamics simulations at a pH range 2-6 was performed to establish the optimum activity and stability profiles of chitinase I and chitinase II. For this purpose, the Molecular Dynamics simulations were carried out at fixed protonation states in an explicit water environment to evaluate the effect of the physiological pH on chitinase I and II enzymes obtained from T. lanuginosus. The results suggest a strong conformational pH dependence of chitinases. These enzymes retained their characteristic TIM Barrel fold at the respective protonated conditions, thus validated the experimental outcomes. Further, the different stability and flexibility predictions were used to assess the relation of point mutations and enzyme stabilities. Our results pave the way to engineer new and better thermostable enzymes.

published_or_final_version / abstract / Mechanical Engineering / Master / Master of Philosophy