The lignin by-product of the conversion of lignocellulosic biomass to 5-(chloromethyl)furfural (CMF) has been characterised by thermogravimetric analysis, N2 physisorption porosimetry, attenuated internal reflectance IR spectroscopy, elemental analysis and solid-state NMR spectroscopy. The lignin (LCMF) has a moderate level of mesoporosity before thermal treatment and a surface area of 63 m(2)  g(-1) , which increases dramatically on pyrolysis at temperatures above 400 °C. An assessment of the functionality and textural properties of the material was achieved by analysing LCMF treated thermally over a range of pyrolysis temperatures. Samples were sulfonated to test their potential as heterogeneous acid catalysts in the esterification of levulinic acid. It was shown that unpyrolysed catalysts gave the highest ester yields of up to 93 %. To the best of our knowledge, this is the first example of mesoporous lignin with an appreciable surface area that is produced directly from a bio-refinery process and with further textural modification of the material demonstrated.

A one-pot esterification and hydrolysis of cellulose was carried outby treating cellulose fibres with molten oxalic acid dihydrate. Eachcellulose oxalate had a free carboxyl content above 1.2 mmol g−1and an average molecular weight of approximately 40 kDa.Aqueous suspensions of the oxalates were sonicated to preparecellulose nanocrystals with a gravimetric yield of 80.6%

Since the introduction of materials based on cellulose nanofibrils (CNFs), these materials have been studied extensively and are suggested to be suitable for use in, for example, hygiene and health care products. A property not very well studied but that could further increase the usability of CNF products is the possibility of controlling bacterial adhesion to the materials. Controlling and fine-tuning the bacterial adhesion makes it possible to produce contact-active antibacterial materials as well as anti-adhesive materials.

The current thesis shows how the number of bacteria adhering to CNF-based materials can be altered through the adsorption of polyelectrolyte multilayers. Polyvinylamine (PVAm) and polyacrylic acid (PAA) were adsorbed in multilayers to achieve differently charged materials. The CNF substrates consisted of both crosslinked and non-crosslinked films with different surface charges and structures as well as porous aerogels.

The results show the possibility of adsorbing PVAm/PAA to recharge the surfaces and construct multilayers. The polyelectrolyte adsorption was affected both by crosslinking and by changing the surface charge of the CNF films. Increasing the surface charge resulted in a decreased PVAm adsorption after the first polymer layer. Crosslinking the films resulted in a low initial PVAm adsorption, but as more layers were adsorbed, the PVAm adsorption increased similarly to the non-crosslinked films. The PVAm adsorption to the aerogels was lower than expected, taking into account their high surface area and surface charge, possibly due to crowding effects on the surface due to geometric limitations.

Only the CNF films with the lowest surface charge and the aerogels adsorbed high numbers of bacteria from bacterial suspensions. The bacterial adsorption to the films was affected by the surface charge, the PAA adsorption and the PVAm adsorption, with a higher net surface charge leading to higher bacterial adsorption. The aerogels efficiently removed bacteria from the bacterial suspensions by adsorbing them onto their surface, with some samples removing over 99.9 % of the bacteria. The results presented in this thesis are believed to lead to a better understanding of both polyelectrolyte adsorption on CNF materials and bacterial adhesion to CNF materials and how polyelectrolyte multilayer adsorption can alter it.

Nanocellulose is a material which can be extracted from wood, and in recent years it has received great attention for its interesting properties and wide range of possible applications. With the aim of further expanding the applications of nanocellulose, this work has studied a new way to produce nanocellulose as well as the possibility of using polyelectrolyte adsorption to alter the interaction with bacteria of materials made from nanocellulose.

Nanocellulose was produced by a novel concurrent esterification and hydrolysis of wood pulp in molten oxalic acid dihydrate. The resulting mixture was washed using ethanol, acetone or tetrahydrofuran before the cellulose oxalate was dried and fibrillated. The nanocellulose obtained with a high yield had a high surface charge (up to 1.4 mmol g^-1) and contained particles with a morphology similar to both cellulose nanocrystals and cellulose nanofibrils. The material was used to prepare both Pickering emulsions and thin films with a strength of up to 197 MPa, a strain at break of up to 5 %, a modulus of up to 10.6 GPa and an oxygen permeability as low as 0.31 cm³ µm m^-2 day^-1 kPa^-1.

Polyelectrolyte adsorption of polyvinylamine and polyacrylic acid was used to modify materials made from nanocellulose. Materials in the form of films and aerogels were used as substrates. By altering the surface charge of the material, the surface structure and the number of layers of polyvinylamine/polyacrylic acid adsorbed, it was possible to prepare materials with both high and low bacterial adhesion. By changing the material properties it is possible to tailor materials with either contact-active or non-adhesive antibacterial properties, both of which are sustainable alternatives to the currently used antibacterial materials.

Nanocellulose is a material which in the near future will probably be used in many applications. In order to improve the suitability of nanocellulose in certain applications it will be necessary to use production methods which differ from the existing methods, for example by using oxalation as a pre-treatment. By modifying the bacterial adhesion to materials prepared from nanocellulose, new medical and health applications emerge.

Fossil resources are the major source from which carbon based materials and chemicals are produced, this is not sustainable. With diminishing supplies and increasing prices and environmental concern, alternative resources must be developed. By using chemical-catalytic methods it is possible to utilize solar energy stored as biomass for production of a wide variety of chemicals and materials. It has previously been established that it is possible to produce 5-(chloromethyl)furfural (CMF) from a wide variety of biomass containing sucrose, glucose or cellulose. CMF is a platform chemical that can be converted into fuels, monomers for consumer plastics and highly valuable pharmaceuticals. When performing the process on lignocellulosic material a residue containing lignin is left as byproduct. Much is still to be investigated around the CMF process, and the present study aims to analyze the lignin from the CMF process (performed on spruce sawdust) in terms of its composition and heating value, to find a simple method to produce the promising monomer (2,5-furandicarboxylic acid, FDCA) from CMF in one catalytic step, and to depolymerize and hydrogenate lignin from the CMF process using HI and H2 in a catalytic cycle.

Composition analysis of the CMF lignin showed low ash content with a decrease in ash-forming inorganic elements compared with the feedstock. During the process chlorine is introduced in the material to a concentration of 1.7%. The heating value of CMF lignin is ~30% higher than the feedstock. Attempts to oxidize CMF with H2O2 to FDCA revealed a fast and efficient reaction between CMF and H2O2 with 5-(hydroperoxymethyl)furfural (HPMF) as the product. HPMF is a novel structure and may prove interesting in future derivatization of CMF. Experiments were performed to investigate the effect of HI on CMF lignin. Results show that HI depolymerizes lignin to organic soluble fragments to a maximum of 31% dissolution after 6 hours at 125 °C. A higher temperature and reaction time is desirable to achieve higher dissolution. The soluble fraction is a mixture of compounds.

Clean lignin is highly desirable in many processes. Removal of chlorine would yield a clean lignin suitable for combustion or as a component in materials. The possibility to depolymerize CMF lignin is also promising as a way to produce products from it. HPMF may prove to be interesting as an intermediate when oxidizing CMF.

The use of cellulose aerogels as antibacterial materials has been investigated by applying a contact-active layer-by-layer modification to the aerogel surface. Studying the adsorption of multilayers of polyvinylamine (PVAm) and polyacrylic acid to aerogels comprising crosslinked cellulose nanofibrils and monitoring the subsequent bacterial adhesion revealed that up to 26 mg PVAm g aerogel⁻¹ was adsorbed without noticeably affecting the aerogel structure. The antibacterial effect was tested by measuring the reduction of viable bacteria in solution when the aerogels were present. The results show that >99.9% of the bacteria adhered to the surface of the aerogels. Microscopy further showed adherence of bacteria to the surfaces of the modified aerogels. These results indicate that it is possible to create materials with three-dimensional cellulose structures that adsorb bacteria with very high efficiency utilizing the high specific surface area of the aerogels in combination with their open structure.

Cellulose nanofibril (CNF) materials have been widely studied in recent years and are suggested for a wide range of applications, e.g., medical and hygiene products. One property not very well studied is the interaction between bacteria and these materials and how this can be controlled. The current work studies how bacteria adhere to different CNF materials modified with polyelectrolyte multilayers. The tested materials were TEMPO-oxidized to have different surface charges, periodate-oxidized to vary the water interaction and hot-pressed to alter the surface structure. Then, multilayers were constructed using polyvinylamine (PVAm) and polyacrylic acid. Both the material surface charge and water interaction affect the amount of polymer adsorbed to the surfaces. Increasing the surface charge decreases the adsorption after the first PVAm layer, possibly due to conformational changes. Periodate-oxidized and crosslinked films have low initial polymer adsorptions; the decreased swelling prevents polymer diffusion into the CNF micropore structure. Microscopic analysis after incubating the samples with bacterial suspensions show that only the materials with the lowest surface charge enable bacteria to adhere to the surface because, when adsorbing up to 5 layers PVAm/PAA, the increased anionic surface charge appears to decrease the net surface charge. Both the amounts of PVAm and PAA influence the net surface charge and thus the bacterial adhesion. The structure generated by the hot-pressing of the films also strongly increases the number of bacteria adhering to the surfaces. These results indicate that the bacterial adhesion to CNF materials can be tailored using polyelectrolyte multilayers on different CNF substrates.

Nanocellulose prepared from cellulose oxalate has been discussed as an alternative to other methods to prepare cellulose nanofibrils or crystals. The current work describes the use of a bulk reaction between pulp and oxalic acid dihydrate to prepare cellulose oxalate followed by homogenization to produce nanocellulose. The prepared nanocellulose is on average 350 nm long and 3–4 nm wide, with particles of size and shape similar to both cellulose nanofibrils and cellulose nanocrystals. Films prepared from this nanocellulose have a maximum tensile stress of 140–200 MPa, strain at break between 3% and 5%, and oxygen permeability in the range of 0.3–0.5 cm 3 μm m −2 day −1 kPa −1 at 50% relative humidity. The presented results illustrate that cellulose oxalates may be a low-cost method to prepare nanocellulose with properties reminiscent of those of both cellulose nanofibrils and cellulose nanocrystals, which may open up new application areas for cellulose nanomaterials.

Water filtration is a popular way to remove particles and microorganisms from drinking water but is generally based on size exclusion of the particles. Bacteria can be modeled as small particles with a diameter of 1-2 µm, which is usually too small to be excluded by paper filters. In this article, commercial available paper filters have been surface modified by polyelectrolyte multilayer adsorption to create a positively charged filter that can trap the negatively charged bacteria through electrostatic interactions. The polyelectrolyte modified filters bind the bacteria to there surface and will thereby remove bacteria from the water instead of inactivated them through addition of biocides. The modified filters can remove more than 99.9 % of bacteria in water, depending on filter design, and has successfully been compared to a commercial cellulose water filter, based on the release of silver to inactivate bacteria. This cheap and easy modification of filter paper has potential to create disposable water purification filters that could be used in emergency situations to prevent outbreak of lethal diarrheal diseases.

Filtration is a common way to obtain pure drinking water by removing particles and microorganisms based on size exclusion. Cellulose-based filters are affordable and biobased option for the removal of particles but bacteria are usually too small to be removed by size exclusion alone. In this article, the surfaces of cellulose fibres in two types of commercial paper filters have been given a positive net charge to trap bacteria through electrostatic interactions without releasing any biocides. The fibres were modified with the cationic polyelectrolyte polyvinylamine polymer in single layers (1 L) or in multilayers together with the anionic polyelectrolyte polyacrylic acid (3 L or 5 L) using a water-based process at room temperature. Filtration tests show that all filters, using both types of filter papers and a number of layers, can physically remove more than 99.9% of E. coli from water and that the 3 L modified filters can remove more than 97% of cultivatable bacteria from natural water samples. The bacterial reduction increased with increasing number of filter sheets used for the filtration and the majority of the bacteria were trapped in the top sheets of the filter. The results show the potential for creating water purification filters from bio-based everyday consumable products with a simple modification process. The filters could be used in the future for point-of-use water purification that may be able to save lives without releasing bactericides.