Cellulose is an attractive raw material that has lately become more interesting thanks to its degradability and renewability and the environmental awareness of our society. With the intention to find new material properties and applications, studies on cellulose derivatization have increased. Dialdehyde cellulose (DAC) is a derivative that is produced by selective cleavage of the C2-C3 bond in an anhydroglucose unit in the cellulose chain, utilizing sodium periodate (NaIO4) that works as a strong oxidant. At a fixed temperature, the reaction time as well as the amount of added periodate affect the resulting aldehyde content. DAC has shown to have promising properties, and by disintegrating the dialdehyde fibers into fibrils, thin films with extraordinary oxygen barrier at high humidity can be achieved. Normally, barrier properties of polysccharide films deteriorate at higher humidity due to their hygroscopic character. This DAC barrier could therefore be a potential environmentally-friendly replacement for aluminum which is utilized in many food packages today. The aim of this study was to investigate the possibilities to produce dialdehyde cellulose at an industrial level, where the regeneration of consumed periodate plays a significant role to obtain a feasible process. A screening of the periodate oxidation of cellulose containing seven experiments was conducted by employing the program MODDE for experimental design. The reaction time was varied between 2-8 hours and the ratio NaIO4 to fiber in was between 1-2 (w/w) for small-scale experiments (1 g fiber), which resulted in an aldehyde content between 14-80 %. An oxidation degree around 30 % was set as a goal, and the optimal point at a fixed temperature of 50°C was assessed to be a ratio of 1.5 and a reaction time of 2.5 h, including 30 min of cooling. Furthermore, the MODDE evaluation suggested that the time and quantity of added periodate equally effected the reaction. An up-scaling of the system with 22.5 g of NaIO4 and 15 g of cellulose fibers and a total reaction time of 3h, resulted in 39 % oxidation degree and a yield of 92 %. For the regeneration of periodate, Oxone® was tested, but too low yields were obtained. More studies are needed in order to understand and optimize this process. Better results where gained when utilizing a 10 % hypochlorite solution (NaOCl) that was refluxed with the filtrate from the periodate oxidation of cellulose. A spectrophotometric method was developed to be able to quantify the amount of periodate and thereby the amount of residual iodate (IO3-), i.e. the byproduct to oxidize back to IO4-. An optimization study was performed with eleven experiments with the time varying between 1-4 hours and the molar ratio of NaOCl to IO3- between 1-4. However, it was found that the residual periodate also consumed the hypochlorite, so the real molar ratio of NaOCl to IO3- and IO4- was only 0.38-1.52. The highest ratio of 1.52 with a reaction time of 4 h generated the highest regeneration of 81 %. From the MODDE evaluation it was suggested that the reaction time does not have as significant effect upon the process as the amount of added NaOCl has. By optimizing this reaction further, it should be possible to reach even more satisfying results. However, it was proved that the precipitated product was sodium paraperiodate, Na3H2IO6, and this regenerated product was successfully used to oxidize cellulose fibers to DAC. Surprisingly, the oxidation degree became much higher, 43 %, despite that the same condition was employed as before, but the reason for this can be the lower pH that was utilized. Even though there still are questions to be answered, this study has contributed to knowledge that could be utilized to take the oxidation process closer to industrialization. / Cellulosa är en attraktiv råvara som blivit alltmer intressant tack vare dess nedbrytbarhet och förnybarhet samt samhällets miljömedvetenhet. Med avsikt att hitta nya materialegenskaper och applikationer har studier på derivatiseringen av cellulosa ökat. Dialdehydcellulosa (DAC) är ett derivat som framställs genom selektiv klyvning av C2-C3-bindningen i en vattenfri glukosenhet i cellulosakedjan där natriumperjodat (NaIO4) fungerar som ett starkt oxidationsmedel. Vid en konstant temperatur påverkar reaktionstiden liksom mängden tillsatt perjodat det resulterande aldehydinnehållet. DAC har visat sig ha lovande egenskaper och genom att lösa upp dialdehydfibrerna till fibriller kan tunna filmer med en utomordentlig syrebarriär vid hög fuktighet erhållas. Normalt sett blir den fina barriären gjord av polysackaridfilmer försämrad vid högre luftfuktighet på grund av den hygroskopiska karaktären. Denna DAC barriär kan därför vara en potentiell och miljövänlig ersättare till det aluminium som används i många livsmedelsförpackningar idag. Syftet med denna studie var att undersöka möjligheterna att kunna producera dialdehydcellulosa på en industriell nivå, där regenerering av förbrukad perjodat spelar en viktig roll för att erhålla en genomförbar process. En screening av perjodatoxidering av cellulosa innehållande sju experiment utfördes genom att använda programmet MODDE för experimentell design. Reaktionstiden varierade mellan 2-8 timmar och förhållandet NaIO4 till fibrer i gram mellan 1-2 för småskaliga experiment (1 g fiber), vilket resulterade i en aldehydhalt mellan 14-80 %. En oxidationsgrad omkring 30 % sattes som ett mål och den optimala punkten vid en konstant temperatur av 50° C bedömdes vara ett förhållande på 1,5 och en reaktionstid om 2,5 timmar inklusive 30 min avsvalning. Vidare föreslog MODDE-utvärderingen att tiden och mängden tillsatt perjodat påverkade reaktionen likvärdigt. En uppskalning av systemet med 22,5 g NaIO4 och 15 g cellulosafibrer och en total reaktionstid om 3 timmar resulterade i en oxidationsgrad på 39 % och ett utbyte på 92 %. För att återgenerera perjodat testades Oxone® men alltför låga utbyten erhölls. Fler studier behövs för att förstå och optimera denna process. Bättre resultat erhölls när en 10 % hypokloritlösning (NaOCl) användes, vilken återloppskokades med filtratet från perjodatoxideringen av cellulosa. En spektrofotometrisk metod utvecklades för att kunna kvantifiera mängden perjodat och därmed mängden kvarvarande jodat (IO3-), dvs. biprodukten att oxidera tillbaka till IO4-. En optimeringsstudie utfördes med elva experiment där tiden varierade mellan 1-4 timmar och det molära förhållandet av NaOCl till IO3- mellan 1-4. Efter detta visade det sig att den kvarvarande perjodaten också konsumerade hypoklorit, så det verkliga molförhållandet mellan NaOCl till IO3- och IO4- var endast 0,38-1,52. Det högsta förhållandet 1,52 med en reaktionstid om 4 timmar genererade den högsta återgenereringen på 81 %. Från MODDE-utvärderingen föreslogs att reaktionstiden inte har lika stor inverkan på processen som mängden tillsatt NaOCl har. Genom att optimera denna reaktion ytterligare bör det vara möjligt att nå än mer tillfredsställande resultat. Hur som helst bevisades det att den utfällda produkten var natriumparaperjodat, Na3H2IO6 och denna regenererade produkt användes framgångsrikt för att oxidera cellulosafibrer till DAC. Överraskande nog blev oxidationsgraden mycket högre, 43 %, trots applicering av samma betingelser som tidigare, men orsaken till detta kan vara att ett lägre pH användes. Även om det fortfarande finns frågor kvar att besvara så har denna studie bidragit till kunskap som kan användas för att ta denna oxidationsprocess närmre industrialisering.

Siegen, Universiẗat, Diss., 2001.

No description available.

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.

Malaria is a disease caused by the protozoan parasite Plasmodium where the species that causes the most severe form of malaria in humans is known as Plasmodium falciparum. At least 40% of the global population is at risk of contracting malaria with 627 000 people dying as a result of this disease in 2012. Approximately 90% of all malaria deaths occur in sub-Saharan Africa, where approximately every 30 seconds a young child dies, making malaria the leading cause of death in children under the age of five years old. The malaria parasite has a complex life cycle utilising both invertebrate and vertebrate hosts across sexual and asexual stages. The erythrocyte invasion stage of the life cycle in the human whereby the invasive merozoite form of the parasite enters the erythrocyte is a central and essential step, and it is during this stage that the clinical symptoms of malaria manifest themselves. Merozoites invade erythrocytes utilising multiple, highly specific receptor-ligand interactions in a series of co-ordinated events. The aim of this study was to better understand the interactions occurring between the merozoite and erythrocyte during invasion by using modern, cutting-edge proteomic techniques. This was done in the hope of laying the foundation for the discovery of new key therapeutic targets for antimalarial drug and vaccine-based strategies, as there is currently no commercially available antimalarial vaccine and no drug to which the parasite has not at least started showing resistance. In this study healthy human erythrocytes were treated separately with different protein-altering enzymes and chemicals being trypsin, the potent oxidant sodium periodate (NaIO4), the amine cross-linker tris(2-chloroethyl)amine hydrochloride (TCEA) and the thiol cross-linker 1,11-bis(maleimido)triethylene glycol (BM(PEG)3). The resulting erythrocyte protein alterations were visualised as protein band differences on sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE), where treated and untreated control erythrocyte ghost protein fingerprints were visually compared to one another. The protein bands showing differences between treated and control samples were in-gel digested using trypsin then sequenced by liquid chromatography tandem mass spectrometry (LC-MS/MS) and identified using proteomics-based software. In this way, the erythrocyte proteins altered by each enzyme/chemical treatment were identified. Malaria invasion assays were performed where each treatment group of erythrocytes as well as the control erythrocytes were incubated separately with schizont stage malaria parasites for the duration of one complete life cycle. Using fluorescent staining and flow cytometry, the invasion inhibition efficiency for each treatment group was evaluated. By utilising these methods, the identification and the relative importance of the erythrocyte proteins involved in the invasion process were determined. Protein fingerprints of control and treated erythrocyte ghosts were visualised and optimised on SDS PAGE where induced protein band differences were successfully identified by LC-MS/MS. It was found that each treatment altered erythrocyte proteins with changes found in Band 3, actin, phosphoglycerate kinase 1, spectrin alpha, spectrin beta, ankyrin, haemoglobin, Bands 4.1 and 4.2, glycophorin A and stomatin. The invasion assays revealed that TCEA inhibited invasion to the greatest extent as compared to the other treatments, followed by BM(PEG)3 and trypsin. Sodium periodate-treated erythrocytes could not be assessed using the invasion assay due to auto-haemolysis. Band 3, glycophorin A, Band 4.1 and stomatin appear to be of higher relative importance in the invasion process as compared to the other altered erythrocyte proteins. These results confirmed the known roles of spectrin alpha, spectrin beta, glycophorin A, Band 3 and Band 4.1 in invasion, and suggested that ankyrin, Band 4.2 and stomatin may also be involved. This study highlighted the potential that modern, cutting-edge proteomic techniques provide when applied to previous comparative studies found in older literature, as previously unidentified proteins that can be involved in invasion were revealed. These results can be used as a foundation in future studies in order to identify new key targets for the development of new antimalarial drug- and vaccine-based strategies, with the hope of preventing the suffering of the millions of malaria-inflicted people worldwide, and ultimately eradicating this deadly disease. / Dissertation (MSc)--University of Pretoria, 2014. / tm2015 / Pharmacology / MSc / Unrestricted

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.

1. Investigations of styrene polymerized in wood using ionizing radiation as the chain initiator indicate that property improvements are of the same order as for thermally initiated polymerization. 2. Free radicals have been detected in irradiated cellulose, Dioxane lignin, Spruce Periodate lignin and Beaun’s “Isolated Native Lignin” as well as in wood subjected to radiation. Consequently, wood radical identification is not possible. 3. Analysis of radical concentrations and decay suggest the presence of one or more decaying radical species in irradiated wood. The persistent maximum in radical concentration found corresponds to one or two unique radical sites per molecule; possibly the terminal hydroxyl group. 4. Results suggest that in the grafting reaction the initiation is a direct radical-monomer couple and does not involve decomposing peroxides. / Thesis / Master of Engineering (ME)

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.