The purpose of this thesis work was to investigate possible in-, on- or at-line methods to determine the degree of oxidation in dialdehyde cellulose. Several technologies were reviewed which led to a feasibility study into a possible on-line or at-line method using near infrared spectroscopy for determining the degree of oxidation in wet dialdehyde cellulose. A calibration model was built using the near infrared spectra of 19 samples created from kraft pulp with a degree of oxidation between 0 and 52.1 %. The obtained model uses five significant principal components and has a goodness of fit (R2) of 0.998 and a goodness ofprediction (Q2) of 0.991. The first principal component describes the degree of oxidation and the second the water content. A validation set of six samples was used to test the model and the predicted values resulted in a root mean square error of prediction of 0.85 in comparison with the reference method which had a pooled standard deviation of 0.69.

Thesis (Ph.D.) -- University of Texas Southwestern Medical Center at Dallas, 2006. / Not embargoed. Vita. Bibliography: 129-137.

Cellulose, a sustainable raw material derived from nature, can be used for various applications following its functionalization and oxidation. Nanocellulose, inheriting the properties of cellulose, can offer new properties due to nanoscale effects, in terms of high specific surface area and porosity. The oxidation of cellulose can provide more active sites on the cellulose chains, improving its functionalization and broadening applications. Two kinds of oxidation and their corresponding applications are described in this thesis: periodate oxidation and Oxone® oxidation. 2,3-dialdehyde cellulose (DAC) beads were prepared from Cladophora nanocellulose via periodate oxidation, and were further modified with amines via reductive amination. Several diamines were selected as possible crosslinkers to produce porous DAC beads, which showed higher porosity, stability in alkaline solution and enhanced thermal stability. After functionalization of DAC beads with L-cysteine (DAC-LC), thiol, amine and carboxyl groups were introduced into the DAC beads, endowing the DAC-LC beads with high adsorption capacity for palladium. The synthesized DAC-LC beads were character­ized with SEM, FTIR, XPS, TGA, BET and XRD and the palladium adsorption process was investigated. Chitosan was employed as a crosslinker in functionalization of DAC beads (DAC-CS). The conditions for the synthesis of DAC-CS beads were screened and verifying the stability of the beads in alkaline solution. The DAC-CS beads produced were investigated using SEM, FTIR, XPS, TGA and BET, and the adsorption and desorption capacity of Congo red was studied, indicating DAC-CS beads have potential as sorbent. Oxone oxidation of cellulose is a novel one-pot oxidation method in which mainly the hydroxyl groups on C6 are oxidized to produce carboxylic acid groups on the cellulose chains. To increase the efficiency of Oxone oxidation, several reaction parameters were studied. Cellulose pulp and Cladophora nanocellulose were chosen as prototypes to investigate the effects of oxidation, and the physico­chemical properties of the oxidized products were characterized. Cellulose pulp, pretreated with Oxone oxidation, was disintegrated by homogenization to prepare cellulose nanofibers (CNF). The effect of pre­treat­ment on the preparation of CNF was studied, and the results indicated that Oxone oxidation was efficient in the production of CNF.

Detta examensarbete är en del av CelluFil-projektet och syftar till att optimera förhållandena för upplösning av cellulosa i vattenlösning av natriumhydroxid följd av regenering i form av ett garn. Tidigare arbeten har visa tatt cellulosa kan lösas i vattenlösning vid -10°C, men sådana förhållanden är inte tillämpliga i industriell skala. Målet med detta projekt är att arbeta vid rumstemperatur.  För detta kommer karboxylgrupper att införas i cellulosakedjorna för att öka cellulosans lighet i ett alkaliskt vattenbaserat medium. Därefter kommer cellulosan att fällas ut igen i en sur lösning. Natriumperjodat gör det möjligt att oxidera alkoholgrupperna i cellulosakedjan på C2- och C3- positionerna genom att öppna glukosenheterna för att skapa två karbonylfunktioner (aldehyde) som sedan lätt kan oxideras till karboxylgrupper med överoxidering med natriumklorit.  Den första delen av rapporten är tillägnad litteraturöversikten om ämnet med focus på natriumperjodat oxidation. Därefter föreslås ett allmänt protokoll från natriumperjodat oxidation till regenering av cellulosa till garn i en svavelsyralösning. Flera förhållanden för natriumperjodat oxidationen testas vid olika temperaturer, med eller utan metallsalter och med olika oxidationsdoser.  Upplösningsutbytet är direkt kopplat till karboxylinnehållet infört i cellulosakedjorna. Periodatoxidationen leder också till minskningen av polymerisationsgraden men cellulosas DPv förblir tillräckligt hög med det riktade COOH-innehållet och för textilapplikationer. Den möjliga produktionen av hydroxylradikaler under natriumperjodat oxidationen har undersökts med EPR/Spin-trapping. Endast försök gjorda med UV-strålning visade OH°. Således förklaras fortfarande inte depolymerisationen av cellulosa under perjodat oxidation framställd under mörka förhållanden. Eftersom, konsumtion av natriumperjodat är låg under oxidationen är dess återvinning en nyckelfråga för en industriell applikation. Det har visat sig att oxidationsfiltraten kan återanvändas flera gånger före total konsumtion av periodat. Kvaliteten på celluloser oxiderade med återvunna filtrat, särskilt deras upplösningsförmåga, bör kontrolleras. / This master thesis is part of the Cellufil Project and aims to optimize the conditions for dissolving cellulose in aqueous sodium hydroxide solution followed by regeneration it in the form of a yarn. Previous works have shown that cellulose could be dissolved in soda at -10°C, but such conditions are not applicable at industrial scale. The objective of the present project is to work at room temperature.  For that, carboxyl groups will be introduced in the cellulose chains in order to increase cellulose solubility in an alkaline aqueous medium, after this it is reprecipitated it in acidic solutions. Periodate makes it possible to oxidize the alcohol groups of cellulose on C2 and C3 positions by opening the glucose units to create two carbonyls functions (aldehyde) which can then be easily oxidized into carboxylic groups with overoxidation using sodium chlorite. A first part of the report is dedicated to the literature review on the subject, focusing on periodate oxidation. Then, a general protocol is proposed from the periodate oxidation to the regeneration of cellulose into yarn in sulfuric acid solutions. Several conditions for the periodate oxidation are tested, at different temperatures, with or without metal salts and with different oxidant dosages.  The dissolution yield is directly linked to the carboxyl content introduced in the cellulose chains. The periodate oxidation also leads to the decrease of the cellulose degree of polymerization but cellulose DPv still remains sufficiently high in the case of the targeted COOH contents and for textile applications. The possible production of hydroxyl radicals during the periodate oxidation has been investigated by EPR/Spin-trapping. Only trials made with UV radiations showed OH°. Thus, cellulose depolymerization during periodate oxidation made in dark conditions is still not explained. Because the periodate consumption is low during the oxidation, its recycling is a key issue for an industrial application. It has been shown that the oxidation filtrates could be reused several times before total oxidant consumption. The quality of celluloses oxidized with recycled filtrates, especially their dissolving ability, should be checked.

The search for alternatives to the fossil-based products has dramatically surged during past few decades primarily due to the problems associated with the scarcity of these sources and global environmental concerns. Among those many alternatives, exploitation of cellulose, as a raw material to develop novel products has been a constant attempt since it has never lost its both economic and industrial impact. Cellulose is known for its significant contribution as a raw material and as a fascinating sustainable macromolecule, which exhibits wide availability and versatile chemical reactivity to discover novel derivatives for broad range of applications. Conversion of cellulose C2/C3 secondary hydroxyl groups to dialdehyde groups in the presence of periodate is an extremely useful method for regioselective oxidation of cellulose and to activate the polymer for further derivatization. This thesis is primarily focused on synthesis and characterization of wide range of cellulose derivatives exploiting facile periodate oxidation methodology. The first study investigated the use of periodate oxidation as a potential method to synthesize a novel water soluble derivative of cellulose from bleached hardwood Kraft pulp. The work focused on the effect of periodate oxidation and sulfonation reaction on water solubility, morphology and structure of cellulose fibers. The results showed a significant increase in water solubility (2.85 -28.5 g/L) and complete change in surface morphology of the fibers due to the introduction of sulfonic acid groups. In the second study, the same reaction scheme was employed on bead cellulose to prepare anionic 2,3-disulfonated beads. Due to the presence of negatively charged sulfonic acid groups, the beads were found to be agglomerated in presence of cationic starch, exhibiting their future application in chromatographic separation. In the third study, model primary amine compounds such as methyl and butyl amines were grafted to nanowhisker surfaces following periodate oxidation and reductive amination. Then, based on the grafting procedure, in the following study, gamma aminobutyric acid (spacer) and syringyl alcohol (linker) was attached to periodate oxidized nanowhiskers to synthesize a novel drug delivery system. The final study investigated the application of periodate oxidized nanowhiskers as chemical cross-linkers to stabilize gelatin gels. It was concluded that the chemical cross-linking has a significant effect on relative increase in percentage of rigid protons, reduced water uptake ability and reduced pore size of the gels. Not only did the chemical cross-linking improve the storage modulus of the gels (150%) and but it also increased the thermal resistance until 50 oC.

Content: Different tanning materials endow leather with varying colors observable in undyed leathers. Periodateoxidized starch tanned leathers have a yellow tinge or light brown color and get darker with age. The color change in situ is ascribable to iodate ions that are byproducts of periodate oxidation. Iodate ions undergo reduction to form iodine molecules that are yellow or brown in low or at higher concentrations. This study focuses on the removal of iodate ions from Dialdehyde Tapioca Starch (DTS) using a simple precipitation method. Preparation of DTS is by periodate oxidation and precipitation of iodate ions using an inorganic precipitant. The experiments for manufacturing wet-white leathers used pickled goatskins and DTS (unmodified and modified) tanning agents at various percentages based on pelt weight. Glutaraldehyde (GTA) tanning was the control. The percentage removal of iodate ions in modified DTS was 98%. Both unmodified and modified DTS had an aldehyde content of 70%. FT-IR and 1H-NMR confirmed the aldehyde groups. GTA, unmodified, and modified DTS tanned leathers had shrinkage temperatures of 80, 87, and 89°C, respectively. The physico-mechanical properties of the control and experimental leathers are comparable. GTA tanned leather had the typical brown color associated with GTA tannages. The ‘b’ color value of unmodified DTS tanned leather was high confirming yellowing of leathers upon ageing. Wet-white leather tanned with modified DTS had no discernible color change. Analysis of the spent tan liquor shows a reduction in the BOD, COD, TS, and TDS load when compared to GTA tanning system evincing the biodegradability of DTS. This study has overcome the drawback associated with periodate-oxidized starch tanning agents, viz. leather darkening over time, considering the chemical and physico-mechanical properties of the resultant leathers. The novel iodate free DTS can be scaled-up for commercial availability. Take-Away: Removal of iodate ions from periodate-oxidized starch before its use as a tanning agent is imperative to avoid leather color change over time. This study reports the successful removal of iodate ions from Dialdehyde Tapioca Starch (DTS). Wet-white leather tanned with the modified DTS had no observable color change upon ageing.