The principle objectives of this research were to chemically modify cellulose using either carboxylic acids or phosphorus containing acids. Carboxylic acids were reacted with isocyanic acid derived from sodium cyanate, in order to synthesise reactive anhydrides, amides and polyamide compounds. The application of these intermediate compounds to cellulose was in tempted. The phosphonation of cellulose using phosphorous acid resulted in a substrate which exhibited flame retardant properties. Firstly, the stability and the nature of the reagents were investigated by Fourier transform infrared spectroscopy (FTIR), Fourier transform Raman (FT-Raman) and Capillary electrophoresis (CE). Secondly, the process of phosphonation was investigated to determine the optimum reagents / concentrations / pH and other application conditions on various cellulose substrates. The treated cotton fabrics were found to give excellent flame retardancy; such fabrics were analysed by different technique, including FTIR, FT -Raman, Nuclear magnetic resonance (NMR), Thermogravimetric analysis (TGA), Scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDX), fluorescence microscopy and cationic dye staining. All the analysis results clearly showed that these phosphonation treatments introduced flame retardant properties to cotton fabrics which were durable to repeated alkaline launderings. The results of this research have been used to help launch a commercially viable flame retardant product. Compared to other products currently occupying the market huge advantages in terms of avoidance of formaldehyde are evident.

This thesis describes the fabrication of novel green materials using nanocellulose as the building block. Bacterial cellulose (BC) was used as the nanocellulose predominantly in this work. BC is highly crystalline pure cellulose with an inherent fibre diameter in the nano-scale. A single BC nanofibre was found to possess a Young’s modulus of 114 GPa. All these properties are highly favourable for using BC as a nanofiller/reinforcement in green nanocomposite materials. In this work, the surface of BC was rendered hydrophobic by grafting organic acids with various aliphatic chain lengths. These surface-modified BC was used as nanofiller for poly(L-lactide) (PLLA). Direct wetting measurements showed that the BC nanofibre-PLLA interface was improved due to the hydrophobisation of BC with organic acids. This led to the production of BC reinforced PLLA nanocomposites with improved tensile properties. Nanocellulose can also be obtained by grinding of wood pulp, producing nanofibrillated cellulose (NFC). The surface and bulk properties of one type of NFC and BC were compared in this work. Furthermore, the reinforcing ability of NFC and BC was also studied and it was observed that there is no significant difference in the mechanical performance of NFC or BC reinforced nanocomposites. A novel method based on slurry dipping to coat sisal fibres with BC was developed to modify the surface of natural fibres. This method can produce either (i) a densely BC coating layer or (ii) “hairy” BC coated sisal fibres. Randomly oriented short BC coated sisal fibre reinforced hierarchical composites were manufactured. It was found that hierarchical (nano)composites containing BC coated sisal fibres and BC dispersed in the matrix were required to produce composites with improved mechanical properties. This slurry dipping method was also extended to produce robust short sisal fibre preforms. By infusing this preform with a bio-based thermosetting resin followed by curing, green composites with significantly improved mechanical properties were produced. BC was also used as stabiliser and nano-filler for the production of macroporous polymers made by frothing of acrylated epoxidised soybean oil followed by microwave curing.

Thesis (M.Sc. (Microbiology)) --University of Limpopo, 2013 / The production of cellulase is a key factor in the hydrolysis of cellulosic materials and it is essential to make the process economically viable. Cellulases are the most studied multi- enzyme complex and comprise of endo-glucanases (EG), cellobiohydrolases (CBH) and β- glucosidases (BGL). The complete cellulase system; comprising CBH, EG and BGL components thus acts synergistically to convert crystalline cellulose to glucose. Cellulases are currently the third largest industrial enzyme worldwide. This is due to their wide applications in cotton processing, paper recycling, juice extraction, as detergent enzymes and additives in animal feed. In this study, production of cellulase by five fungal isolates (BTU 251-BTU 255) isolated from mushrooms, was investigated and optimised. Internal transcribed spacer regions (ITS1 and ITS4) were applied to identify the five fungal microorganisms. Isolates were identified as follows: BTU 251 as Aspegillus niger,BTU 253 as Penicillium polonicum, and BTU 255 as Penicillium polonicum. Cellulase was produced in shake flask cultures using Mandel’s mineral solution medium and Avicel as a carbon source. Cellulase activity was tested using 3, 5-Dinitrosalicylic acid assay and zymography, A. niger BTU 251 showed five activity bands ranging from 25- 61 kDa had an average nkat of 7000. Cultures from BTU 252 were the least active with an average nkat/ml of 200 and one activity band of 25 kDa. P. polonicum BTU 253 showed three activity bands ranging between 45 and 60 kDa and had an average nkat/ml of 2200. BTU 254 showed five activity bands ranging from 22- 116 kDa and had average nkat of 350. P. polonicum BTU 255 produced the highest cellulase activity of 8000 nkat/ml and with three activity bands estimated at 45-60 kDa on zymography. The optimal temperature for activity of the cellulases was between 55-70°C and enzymes were most active within a pH range of 4-6. Optimal pH for production of cellulases by P. polonicum BTU 255, P. polonicum BTU 253 and A. niger BTU 251 was 4 while optimal temperature for production of the cellulases was between 50-55°C. Total cellulase activity was determined using Whatman No.1 filter paper as a substrate and β- glucosidase production was determined in polyacrylamide gels using esculin as a substrate. In the hydrolysis of crystalline cellulose (Avicel), a combination of A. niger BTU 251 and P. polonicum BTU 255 (1:1), (1:9), (1:3), and (1:2) produced maximum glucose as follows: 1:1 (0.83g/L), 1:9 (10.4g/L), 1:3 (0.77g/L) and 1:2 (0.73g/L). Cellulases from P. polonicum BTU 255 were partially purified using affinity precipitation and analysed using MALDI- TOF/TOF. Peptide sequences of P. polonicum obtained from MALDI-TOF/TOF analysis were aligned by multiple sequence alignment with C. pingtungium. Conserved regions were identified using BLAST anaylsis as sequences of cellobiohydrolases. More research is required in producing a variety of cellulases that are capable of hydrolysing crystalline cellulose, the current study contributes to possible provision of locally developed combinations of cellulases that can be used in the production of bioethanol.