Packaging plays a critical role in ensuring food safety and shelf life by protecting against e.g., moisture, gases, and light. Polyethylene (PE) is widely used in food packaging, but it is mainly produced from non-renewable resources and it is an inefficient oxygen and light barrier. In this study, the layer-by-layer (LbL) assembly of a sustainably produced lignin-based polymer (EH) with polyethylenimine (PEI) or chitosan (CH) was used to fabricate (partially or fully) bio-based coatings with the aim of improving barrier properties of PE films. The charge density of EH was calculated using a polyelectrolyte titration method and the hydrodynamic diameters of EH, PEI and CH were determined by Dynamic Light Scattering (DLS). LbL assembly was monitored in situ via Quartz Crystal Microbalance with Dissipation (QCM-D) and Stagnation Point Adsorption Reflectometry (SPAR). PE films were coated with a variable number of PEI/EH or CH/EH bilayers (BL) using an immersive LbL assembly method. Coated films were studied in terms of light-blocking ability, wettability, thermal behaviour, surface structure, as well as oxygen and water vapor barrier properties. QCM-D and SPAR data showed a stepwise multilayer formation and strong interactions between the oppositely charged polymers, with PEI/EH coating having a greater amount of deposited polymer compared to CH/EH coating at the same number of BL. Overall, light barrier properties and wettability of the coated films increased with the number of deposited bilayers. Coated PE films maintained the overall thermal behaviour of PE. A number of BL of 20 was found to be the most promising based on the studied properties. Selected samples showed improved oxygen and water vapor barrier properties, with PEI/EH coating performing better than CH/EH coating. Taken altogether, we demonstrated that a novel and sustainable lignin-based polymer can be combined with PEI or CH to fabricate (partially or fully) bio-based coatings for food packaging.

The characteristics of two novel types of technical lignin, namely Ecohelix (EH) and CleanFlow black lignin (CFBL), isolated from two different pulping process side streams, were analyzed. EH and CFBL were analyzed in terms of general composition, chemical functionalities, molar mass distribution, and thermal stability. For comparison, two relevant types of commercially available lignosulfonate and kraft lignin were used. The results showed that EH contains a large amount of sulfonated lignin, together with carbohydrates and ash. As such, it can be considered a lignin-carbohydrate hybrid molecule. CFBL was found to contain 91.5% Klason lignin and the lowest amount of carbohydrates (0.3%). EH showed the highest content of aliphatic OH groups (5.44 mmol/g) and CFBL a high content of phenols (4.73 mmol/g). EH had a molecular weight of 31.4 kDa and a sufficient thermal stability. CFBL had the lowest molecular weight (M-w = 2.0 kDa) and thermal stability of all kraft lignins analyzed in this study. These properties highlighted that EH is a suitable building block for material development and that CFBL is a promising material for the production of biofuel and biochemicals.

Cancer represents a significant global public health challenge and ranks as the second mostcommon cause of death in the United States. The onset of cancer entails an initial phasewhere cells lose their polarity and disconnect from the normal basement membrane, allowingthem to form distinct three-dimensional (3D) configurations that interact with adjacent cellsand the surrounding microenvironment. Cells grown in 2D monolayers demonstrate differentgene expression patterns and different activation of signaling pathways compared to cellscultivated within the natural structure of tumor tissue of the same cell type. Multicellulartumor spheroids (MCTS) are extensively investigated as a well-studied model of organotypiccancer. These spheroids are formed by tumor cells, either alone or in combination with othercell types, and they can be created with or without the application of supportive scaffolds.The MCTSs are also considered promising models for preclinical assessments of chemosensitivity.However, the creation of these tumor spheroids presents challenges, as not alltumor cell lines can consistently form regular spheroids.Cellulose nanofibrils (CNF) have become essential as a sustainable and environmentallyfriendly material. For example, thin films, with inherent mechanical properties, and flexibility,offer versatility across various applications. Also known for its biocompatibility and non-toxicnature, native CNF is a natural option to use. Its fibrous structure closely mimics the collagenmatrix in human tissue, showing potential as an effective scaffold for 3D cell culture. In thisregard, an innovative Layer-by-Layer (LbL) coating technique using CNF-polyelectrolytebilayers was investigated to generate spheroids. This method constructs bilayers of CNFand polyelectrolytes and can coat various surfaces. In this thesis, the first focus was ondemonstrating the spheroid formation capability using low molecular weight polyelectrolytesin LbL assembly. Secondly, an investigation was conducted involving embedding of LbLgrownspheroids in a decellularized extracellular matrix (ECM) aiming to determine howECM, possessing suitable mechanical characteristics, could influence the cancer stem celltraits in spheroids. Thirdly, the thesis demonstrated the utilization of LbL for capturing andreleasing of circulating tumor cells. Lastly, the shift from using low molecular weightpolyelectrolytes in the LbL assembly to high molecular weight counterparts and analyzingthe differences in spheroid formation abilities to assess the underlying differences inmolecular weights of the polyelectrolytes was explored. All-in-all, employing the CNF-basedLbL surface coating strategy explored in the thesis has proven to be promising for thedevelopment of spheroid models closely resembling in vivo conditions and holds significantpotential for applications in drug development.

Central nervous system (CNS) injuries such as stroke or trauma can lead to long-lasting disability, and there is no currently accepted treatment to regenerate functional CNS tissue after injury. Hydrogels can mimic the neural extracellular matrix by providing a suitable 3D structure and mechanical properties and have shown great promise in CNS tissue regeneration. Here we present successful synthesis of a thermosensitive hyaluronic acid-RADA 16 (Puramatrix (TM)) peptide interpenetrating network (IPN) that can be applied in situ by injection. Thermosensitive hyaluronic acid (HA) was first synthesized by combining HA with poly(N-isopropylacrylamide). Then, the Puramatrix (TM) self-assembled peptide was combined with the thermosensitive HA to produce a series of injectable thermoresponsive IPNs. The HA-Puramatrix (TM) IPNs formed hydrogels successfully at physiological temperature. Characterization by SEM, rheological measurements, enzymatic degradation and swelling tests was performed to select the IPN optimized for neurologic use. SEM images of the optimized dry IPNs demonstrated an aligned porous structure, and the rheological measurements showed that the hydrogels were elastic, with an elastic modulus of approximately 500 Pa, similar to that of brain tissue. An evaluation of the cell-material interactions also showed that the IPN had biological characteristics required for tissue engineering, strongly suggesting that the IPN hydrogel possessed properties beneficial for regeneration of brain tissue.

Three-dimensional (3D) tumor spheroids are regarded as promising models for utilization as preclinical assessments of chemo-sensitivity. However, the creation of these tumor spheroids presents challenges, given that not all tumor cell lines are able to form consistent and regular spheroids. In this context, we have developed a novel layer-by-layer coating of cellulose nanofibril–polyelectrolyte bilayers for the generation of spheroids. This technique builds bilayers of cellulose nanofibrils and polyelectrolytes and is used here to coat two distinct 96-well plate types: nontreated/non-sterilized and Nunclon Delta. In this work, we optimized the protocol aimed at generating and characterizing spheroids on difficult-to-grow pancreatic tumor cell lines. Here, diverse parameters were explored, encompassing the bilayer count (five and ten) and multiple cell-seeding concentrations (10, 100, 200, 500, and 1000 cells per well), using four pancreatic tumor cell lines—KPCT, PANC-1, MiaPaCa-2, and CFPAC-I. The evaluation includes the quantification (number of spheroids, size, and morphology) and proliferation of the produced spheroids, as well as an assessment of their viability. Notably, our findings reveal a significant influence from both the number of bilayers and the plate type used on the successful formation of spheroids. The novel and simple layer-by-layer-based coating method has the potential to offer the large-scale production of spheroids across a spectrum of tumor cell lines.

The lack of bioactivity in three-dimensional (3D)-printing of poly-epsilon-caprolactone (PCL) scaffolds limits cell-material interactions in bone tissue engineering. This constraint can be overcome by surface-functionalization using glycosaminoglycan-like anionic polysaccharides, e.g., carboxymethyl cellulose (CMC), a plant-based carboxymethylated, unsulfated polysaccharide, and kappa-carrageenan, a seaweed-derived sulfated, non-carboxymethylated polysaccharide. The sulfation of CMC and carboxymethylation of kappa-carrageenan critically improve their bioactivity. However, whether sulfated carboxymethyl cellulose (SCMC) and carboxymethyl kappa-carrageenan (CM-kappa-Car) affect the osteogenic differentiation potential of pre-osteoblasts on 3D-scaffolds is still unknown. Here, we aimed to assess the effects of surface-functionalization by SCMC or CM-kappa-Car on the physicochemical and mechanical properties of 3D-printed PCL scaffolds, as well as the osteogenic response of pre-osteoblasts. MC3T3-E1 pre-osteoblasts were seeded on 3D-printed PCL scaffolds that were functionalized by CM-kappa-Car (PCL/CM-kappa-Car) or SCMC (PCL/SCMC), cultured up to 28 days. The scaffolds' physicochemical and mechanical properties and pre-osteoblast function were assessed experimentally and by finite element (FE) modeling. We found that the surface-functionalization by SCMC and CM-kappa-Car did not change the scaffold geometry and structure but decreased the elastic modulus. Furthermore, the scaffold surface roughness and hardness increased and the scaffold became more hydrophilic. The FE modeling results implied resilience up to 2% compression strain, which was below the yield stress for all scaffolds. Surface-functionalization by SCMC decreased Runx2 and Dmp1 expression, while surface-functionalization by CM-kappa-Car increased Cox2 expression at day 1. Surface-functionalization by SCMC most strongly enhanced pre-osteoblast proliferation and collagen production, while CM-kappa-Car most significantly increased alkaline phosphatase activity and mineralization after 28 days. In conclusion, surface-functionalization by SCMC or CM-kappa-Car of 3D-printed PCL-scaffolds enhanced pre-osteoblast proliferation and osteogenic activity, likely due to increased surface roughness and hydrophilicity. Surface-functionalization by SCMC most strongly enhanced cell proliferation, while CM-kappa-Car most significantly promoted osteogenic activity, suggesting that surface-functionalization by CM-kappa-Car may be more promising, especially in the short-term, for in vivo bone formation.

The processing of hierarchical porous zeolitic imidazolate frameworks (ZIF-8) into a cellulose paper using sheet former Rapid-Kothen (R.K.) is reported. The procedure is a promising route to overcome a significant bottleneck towards applying metal-organic frameworks (MOFs) in commercial products. ZIF-8 crystals were integrated into cellulose pulp (CP) or TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-oxidized cellulose nanofibrils (TOCNF) following an in-situ or ex-situ process; the materials were denoted as CelloZIFPaper_In Situ and CelloZIFPaper_Ex Situ, respectively. The materials were applied as adsorbents to remove heavy metals from water, with adsorption capacities of 66.2-354.0 mg/g. CelloZIFPaper can also be used as a stand-alone working electrode for the selective sensing of toxic heavy metals, for instance, lead ions (Pb2+), using electrochemical-based methods with a limit of detection (LOD) of 8 mu M. The electrochemical measurements may advance 'Lab-onCelloZIFPaper' technologies for label-free detection of heavy metal ions.

Utilizing renewable recourses and waste recycling are necessary for reaching a circular resource society. The concept of this thesis was to set up a sustainable recycling route, suitable even for low quality biopolymer and plastic waste for production of functional carbon materials. Carbonaceous materials were prepared by mild hydrothermal carbonizations of cellulose and polypropylene (PP) under acidic conditions. The carbonization of cellulose resulted mainly in micro-/nanometer sized carbon spheres (CS) with polar functionalities. After carbonization of PP, products were found in solid and liquid phase. Completely carbonized solid carbons products were obtained from PP at 250 °C after 60 min. The liquid products from the same process displayed aromatics and exhibited fluorescence properties. In addition, new carbon materials were prepared by acid, base and thermal treatments of the carbonized products at low temperatures. Thermally resistant carbon products and antibacterial CS towards both Staphylococcus aureus and Pseudomonas aeruginosa were demonstrated as possible applications for these products. The minimum inhibitory concentrations of CS were 200-400 µg mL-1 depending on the bacteria strain and reached after only 3 h. Furthermore, nanometer sized carbon nanodots with high oxygenation degree and fluorescence properties were derived together with carbon flakes (CF) from the carbonized products. The CF with flat and micrometer sized morphology and polar groups were utilized for coating of cationized cellulose filters, applied as adsorbents and then subsequently as surfaces for SALDI-MS analysis of environmental contaminants. This work contributes with new routes to and applications for functional carbon materials.

Carbon spheres (CS) are interesting materials for antibacterial applications. Herein, CS are produced by a green process utilizing microwave-assisted hydrothermal treatment of cellulose. The CS are then postmodified in acidic and basic solutions to evaluate the influence of different functionalities on antibacterial properties. CS contain OH/COOH, C Symbol of the Klingon Empire C, and C Symbol of the Klingon Empire O functionalities, while O-CS produced by acid treatment of CS have additional COOH, and NH/NH2 groups, resulting in carbon spheres with negatively and positively charged groups in dispersion. Treatment with base (Na-CS) removes low molecular weight species with oxygen and results in carbon spheres with the highest C/O ratio. CS, O-CS, and Na-CS have nonporous morphology and are in micro/nanometer sizes, although, smaller sized spheres, hollow spheres, and fragments are also attained in the case of O-CS. O-CS show antibacterial activity toward both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Pseudomonas aeruginosa (P. aeruginosa). The minimum inhibitory concentration is 200 and 400 mu g mL(-1) for S. aureus and P. aeruginosa, respectively, and is achieved only after 3 h of incubation. Neither CS nor Na-CS exhibit antibacterial activity. The antibacterial activity is suggested to originate from electrostatic interactions between O-CS and the bacteria.

Persistent free radicals (PFR) in carbonized particles may play a role in degradation of environmental compounds. The influence of PFR is evaluated in various carbonized particles on their radical scavenging efficiency upon the common radical indicator 2-2-diphenyl-1-picrylhydrazyl (DPPH). Carbonized particles are derived by hydrothermal carbonization of glucose (C-W) or glucose and urea (NC-W) and ionothermal carbonization of glucose and urea ionic liquid (IL) (NC-IL). The carbonized materials contain OH/COOH, C=C, and C-O functionalities. The addition of urea introduces NH/NH2 functionalities. The content of polar surface groups is lower in IL-processed NC-IL. The scavenging ability, measured as DPPH UV–vis absorption decline, increases with concentration and time for all particles, while the efficiency changes are in the order of C-W > NC-W > NC-IL. Electron paramagnetic resonance analysis reveals similar radical concentration in all carbonized materials studied. The difference in efficiency is, thus, not directly related to the PFR concentration but rather to the type of PFR, surface functionalities and/or scavenging mechanism. According to the g-values, radicals in these particles are carbon-centered. The minor variation in g-values suggests interactions between the radicals and their environmental functional groups. This provides insights into the influence of PFR in carbonized materials on their radical scavenging efficiency.

Functional carbon materials produced through a hydrothermal treatment of waste products have gained interest. Particularly, the method is considered more facile and green compared to conventional decomposition methods. Here, we demonstrated an upcycling of polypropylene (PP) waste to carbon materials by a microwave assisted hydro thermal treatment. The solid product obtained from the hydrothermal treatment was analyzed by multiple techniques to reveal the structure and the influence of processing conditions on PP degradation and hydrothermal carbonization. Chemical analyses showed the presence of carbonaceous material independent of acid amount (20 and 30 mL), temperature (210 and 250 degrees C), and time (20-80 min). A complete transformation of PP content to amorphous carbon required 60 min at 250 degrees C. The mass yield of the solid product decreased as a function of harsher processing conditions. At the same time, thermogravimetric analysis illustrated products with increasing thermal stability and a larger amount of remaining residue at 600 degrees C. The solid products consisted of irregular fragments and sheet-like structures. A solid state microwave process in air atmosphere was performed on a product with incomplete carbonization. The modification resulted in a decreased C/O ratio, and TGA analysis in nitrogen showed high thermal stability and degree of carbonization as indicated by the remaining residue of 86.4% at 600 degrees C. The new insights provided on the hydrothermal carbonization, and postmodification in air atmosphere, can catalyze effective handling of plastic waste by enabling transformation of low quality waste into functional carbon materials.

Cationized cellulose filters with coating of oxidized carbonized cellulose (OCC) were successfully fabricated. The OCC-coated filter was demonstrated as a combined surface for adsorption of environmental contaminants and their detection on the filter by surface-assisted desorption ionization-mass spectrometry (SALDI-MS). The cellulose filters were cationized by utilizing 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHTAC) and sodium hydroxide. It was shown that the degree of substitution increased with the CHTAC feed. OCC, synthesized by hydrothermal carbonization of cellulose with subsequent oxidation and dialysis, was attached onto the cationized filters by electrostatic interactions. The filters adsorbed the model contaminant methylene blue (MB) from aqueous solution, and the MB could subsequently be detected on the filter surfaces by SALDI-MS as [M](+) adduct. The OCC coating further improved the relative peak intensity of [M](+) with little background interferences. This work indicates great potential for the OCC-coated filters as a combined surface for rapid monitoring of environmental contaminants.

A resorbable 3D printed polydioxanone (PDO) device is manufactured to facilitate ligation of vascular tissue during surgery. The device must provide sufficient mechanical performance throughout the healing period. Therefore, degradation and mechanical performance of the device are investigated as a function of in vivo and in vitro aging. During aging the PDO device released cyclic and linear water-soluble products. In vivo aging resulted in higher relative number of linear oligomers in comparison to in vitro aging. A major loss of mechanical performance is observed after only 10 days in vivo and the Young’s modulus (E) and tensile strength at break (σb) decreased by 28% and 54%, respectively. This is in contrast to in vitro aging, where no loss of mechanical properties is observed during the same period. The in vivo aged devices exhibit clear holes in the matrices after 28 days, while apparent cracks are observed first after 140 days in vitro. These results highlight the sensitivity of the degradation process of resorbable devices with regards to the interactions of the device with the surrounding environment (tissues) and demonstrate the importance of in vivo testing as compliment to in vitro testing before clinical use of devices.

Hydrothermally carbonized cellulose and its further modifications are intriguing materials for a wide range of potential applications. Hydrothermal carbonization is a sustainable process for converting biopolymers or other biomass sources into carbonaceous materials under mild conditions in water and at relatively low temperatures. This review presents the latest progress in modification and utilization of hydrothermally carbonized cellulose and related materials in environmental, biomedical, and energy applications. Further applications presented include evaluation of cellulose-derived carbon spheres or carbon dots as catalysts, antibacterial materials, flame retardants, and functional fillers in bioplastic composites. The wide range of applications highlights the great potential and multifunctionality of hydrothermally carbonized cellulose and its derivatives. The field is expected to further expand and increase in importance as we move toward circular bioeconomy.

The production and engineering of sustainable materials through green chemistry will have a major role in our mission of transitioning to a more sustainable society. Here, combined catalysis, which is the integration of two or more catalytic cycles or activation modes, provides innovative chemical reactions and material properties efficiently, whereas the single catalytic cycle or activation mode alone fails in promoting a successful reaction. Polyphenolic lignin with its distinctive structural functions acts as an important template to create materials with versatile properties, such as being tough, antimicrobial, self-healing, adhesive, and environmentally adaptable. Sustainable lignin-based materials are generated by merging the catalytic cycle of the quinone-catechol redox reaction with free radical polymerization or oxidative decarboxylation reaction, which explores a wide range of metallic nanoparticles and metal ions as the catalysts. In this review, we present the recent work on engineering lignin-based multifunctional materials devised through combined catalysis. Despite the fruitful employment of this concept to material design and the fact that engineering has provided multifaceted materials able to solve a broad spectrum of challenges, we envision further exploration and expansion of this important concept in material science beyond the catalytic processes mentioned above. This could be accomplished by taking inspiration from organic synthesis where this concept has been successfully developed and implemented.

The sustainable production of polymers and materials derived from renewable feedstocks such as biomass is vital to addressing the current climate and environmental challenges. In particular, finding a replacement for current widely used curable resins containing undesired components with both health and environmental issues, such as bisphenol-A and styrene, is of great interest and vital for a sustainable society. In this work, we disclose the preparation and fabrication of an all-biobased curable resin. The devised resin consists of a polyester component based on fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and reactive diluents acting as both solvents and viscosity enhancers. Importantly, the complete process was performed solvent-free, thus promoting its industrial applications. The cured biobased resin demonstrates very good thermal properties (stable up to 415 °C), the ability to resist deformation based on the high Young’s modulus of ∼775 MPa, and chemical resistance based on the swelling index and gel content. We envision the disclosed biobased resin having tailorable properties suitable for industrial applications.

This article presents a waterborne nanocellulose coating process to change the surface characteristics and mitigate fouling of commercially available polyethersulfone (PES) microfiltration membranes. An extensive comparative study between nanoporous and nano-textured layers composed of cellulose nanocrystals (CNC) or TEMPO-oxidized cellulose nanofibrils (T-CNF), which were coated on the PES membrane by taking advantage of the electrostatic interactions between the PES substrate, a polyallylamine hydrochloride (PAHC1) anchoring layer, and the nanocellulose functional layer. Coated PES membranes exhibited decreased surface roughness and pore sizes as well as rejection of compounds with a M-w above 150 kDa, while the water permeability and mechanical properties of remained largely unaffected. The coatings improved the wettability as confirmed by a reduction of the contact angle by up to 52% and exhibited a higher negative surface charge compared to the uncoated membranes over a pH range of 4-8. A significant reduction in organic fouling was observed for the coated membranes demonstrated by bovine serum albumin (BSA) adsorption studies on T-CNF and CNC surfaces using Quartz Crystal Microbalance with Dissipation monitoring (QCM-D), UV-vis spectroscopy and FTIR mapping after exposing the membranes to dynamic adsorption of BSA. The T-CNF coating exhibited effective antibacterial action against Escherichia coli (E. coli) attributed to the pH reduction effect induced by the carboxyl groups; while CNC coatings did not show this property. This work demonstrates a simple, green, and easy-to-scale layer-by-layer coating process to tune the membrane rejection and to improve antifouling and antibacterial properties of commercially available membranes.

Pharmaceuticals, designed for treating diseases, ironically endanger humans and aquatic ecosystems as pollutants. Adsorption-based wastewater treatment could address this problem, however, creating efficient adsorbents remains a challenge. Recent efforts have shifted towards sustainable bio-based adsorbents. Here, cryogels from lignin-containing cellulose nanofibrils (LCNF) and lignin nanoparticles (LNPs) were explored as pharmaceuticals adsorbents. An enzyme-based approach using laccase was used for crosslinking instead of fossil-based chemical modification. The impact of laccase treatment on LNPs alone produced surface-crosslinked water-insoluble LNPs with preserved morphology and a hemicellulose-rich, water-soluble LNP fraction. The water-insoluble LNPs displayed a significant increase in adsorption capacity, up to 140 % and 400 % for neutral and cationic drugs, respectively. The crosslinked cryogel prepared by one-pot incubation of LNPs, LCNF and laccase showed significantly higher adsorption capacities for various pharmaceuticals in a multi-component system than pure LCNF or unmodified cryogels. The crosslinking minimized the leaching of LNPs in water, signifying enhanced binding between LNPs and LCNF. In real wastewater, the laccase-modified cryogel displayed 8–44 % removal for cationic pharmaceuticals. Overall, laccase treatment facilitated the production of bio-based adsorbents by improving the deposition of LNPs to LCNF. Finally, this work introduces a sustainable approach for engineering adsorbents, while aligning with global sustainability goals.

Adsorption is a relatively simple wastewater treatment method that has the potential to mitigate the impacts of pharmaceutical pollution. This requires the development of reusable adsorbents that can simultaneously remove pharmaceuticals of varying chemical structure and properties. Here, the adsorption potential of nanostructured wood-based adsorbents towards different pharmaceuticals in a multi-component system was investigated. The adsorbents in the form of macroporous cryogels were prepared by anchoring lignin nanoparticles (LNPs) to the nanocellulose network via electrostatic attraction. The naturally anionic LNPs were anchored to cationic cellulose nanofibrils (cCNF) and the cationic LNPs (cLNPs) were combined with anionic TEMPO-oxidized CNF (TCNF), producing two sets of nanocellulose-based cryogels that also differed in their overall surface charge density. The cryogels, prepared by freeze-drying, showed layered cellulosic sheets randomly decorated with spherical lignin on the surface. They exhibited varying selectivity and efficiency in removing pharmaceuticals with differing aromaticity, polarity and ionic characters. Their adsorption potential was also affected by the type (unmodified or cationic), amount and morphology of the lignin nanomaterials, as well as the pH of the pharmaceutical solution. Overall, the findings revealed that LNPs or cLNPs can act as functionalizing and crosslinking agents to nanocellulose-based cryogels. Despite the decrease in the overall positive surface charge, the addition of LNPs to the cCNF-based cryogels showed enhanced adsorption, not only towards the anionic aromatic pharmaceutical diclofenac but also towards the aromatic cationic metoprolol (MPL) and tramadol (TRA) and neutral aromatic carbamazepine. The addition of cLNPs to TCNF-based cryogels improved the adsorption of MPL and TRA despite the decrease in the net negative surface charge. The improved adsorption was attributed to modes of removal other than electrostatic attraction, and they could be 7C-7C aromatic ring or hydrophobic interactions brought by the addition of LNPs or cLNPs. However, significant improvement was only found if the ratio of LNPs or cLNPs to nanocellulose was 0.6:1 or higher and with spherical lignin nanomaterials. As crosslinking agents, the LNPs or cLNPs affected the rheological behavior of the gels, and increased the firmness and decreased the water holding capacity of the corresponding cryogels. The resistance of the cryogels towards disintegration with exposure to water also improved with crosslinking, which eventually enabled the cryogels, especially the TCNF-based one, to be regenerated and reused for five cycles of adsorption-desorption experiment for the model pharmaceutical MPL. Thus, this study opened new opportunities to utilize LNPs in providing nanocellulose-based adsorbents with additional functional groups, which were otherwise often achieved by rigorous chemical modifications, at the same time, crosslinking the nanocellulose network.

Nanocellulose is very hydrophilic, preventing interactions with the oil phase in Pickering emulsions. This limitation is herein addressed by incorporating lignin nanoparticles (LNPs) as co-stabilizers of nanocellulose-based Pickering emulsions. LNP addition decreases the oil droplet size and slows creaming at pH 5 and 8 and with increasing LNP content. Emulsification at pH 3 and LNP cationization lead to droplet flocculation and rapid creaming. LNP application for emulsification, prior or simultaneously with nanocellulose, favors stability given the improved interactions with the oil phase. The Pickering emulsions can be freeze–dried, enabling the recovery of a solid macroporous foam that can act as adsorbent for pharmaceutical pollutants. Overall, the properties of nanocellulose-based Pickering emulsions and foams can be tailored by LNP addition. This strategy offers a unique, green approach to stabilize biphasic systems using bio-based nanomaterials without tedious and costly modification procedures.

In tissue engineering, the production of well-defined scaffolds with a porous architecture from degradable polymers is of great interest. Detailed designs have become feasible through the development of additive manufacturing. A small nozzle size is needed to obtain detailed scaffold structures, and careful control of the rheological properties is therefore required during production. A lower viscosity of the melt allows for easier printability, but a high molar mass is required to produce scaffolds that can retain mechanical properties over the time needed for tissue regeneration. An additional challenge of using degradable polymers with high molar mass in any melt-based processing is that thermal degradation can reduce the molar mass during the production stage. To utilise medical grade degradable polymers whilst limiting the thermal degradation a rheological analysis of the most commonly used commercial medical-grade degradable synthetic polymers was performed. Their rheological behaviours aided in setting process parameters for two different melt-based additive manufacturing routes. The variation in thermal degradation in the two routes was assessed, and the parameters were adjusted to minimise it.

A nondegradative additive manufacturing method was designed, and knowledge regarding printability was developed based on rheological analysis and polymer characterisation methods. This knowledge was applied to the copolymer poly(e-caprolactone-co-p-dioxanone) developed within the group to fabricate pliable scaffolds for tissue engineering with an increased rate of hydrolysis in comparison to poly(e-caprolactone). In addition to the selection of the polymer and process parameters, the mechanical properties were also controlled through the structural design. Poly(e-caprolactone) was used as a model material to show how the mechanical properties of scaffolds could be controlled based on the design solely. The results showed that the stiffness could be reduced by more than a factor of 10 through tuning of the design, resulting in soft pliable scaffold structures.

Additive manufacturing is suitable for producing complex geometries; however, variation in thermo-mechanical properties are observed during one batch cycle when degradable aliphatic polyesters of medical grade are used in melt extrusion-based methods. This is one important reason for why additive manufacturing has not yet been fully utilised to produce degradable medical implants. Herein, the internal variation has been minimised during one batch cycle by assessing the effect of different processing parameters when using commercially available medical grade copolymers. To minimise the molar mass, thermal and mechanical variation within one batch cycle, the rheological fingerprint of the commercially available medical grade poly(L-lactide-co-ε-caprolactone) and poly(L-lactide-co-trimethylene carbonate) has been correlated to the process parameters of the ARBURG Plastic Freeforming. An increase in the temperature up to 220°C and the associated increase in pressure are beneficial for the viscoelastic and thermally stable poly(L-lactide-co-ε-caprolactone). In contrast, a temperature below 220°C should be used for the poly(L-lactide-co-trimethylene carbonate) to reduce the variation in strain at break during one batch cycle. The residence time is decreased through the increase of the discharge parameter. An increase in temperature is however required to reduce the viscosity of the polymer and allow the pressure to stay within the machine limitations at higher discharge parameters. The results are highly relevant to the development of additive manufacturing for the production of degradable medical devices with identical properties. In fact, Food and Drug Administration guidelines for additive manufacturing of medical implants specify the need to control changes in material properties during the process.

Rheological measurements have shown that lactide-based copolymers with L-lactide content between 50 and 100 mol% with varying comonomers, as well as polydioxanone (PDX), can be used in additive manufacturing analogously to poly(L-lactide) (PLLA) if their melt behaviour are balanced. The results indicate that copolymers can be melt processed if the temperature is adjusted according to the melting point, and parameters such as the speed are tuned to conteract the elastic response. Small amplitude oscillatory shear (SAOS) rheology, thermal and chemical characterisation allowed us to map the combined effect of temperature and frequency on the behaviour of six degradable polymers and their melt stability. Values of complex viscosity and Tan delta obtained through nine time sweeps by varying temperature and frequency showed that the molecular structure and the number of methylene units influenced the results, copolymers of L-lactide with D-Lactide (PDLLA) or glycolide (PLGA) had an increased elastic response, while copolymers with trimethylene carbonate (PLATMC) or epsilon-caprolactone (PCLA) had a more viscous behaviour than PLLA, with respect to their relative melting points. PDLLA and PLGA require an increased temperature or lower speed when processed, while PLATMC and PCLA can be used at a lower temperature and/or higher speed than PLLA. PDX showed an increased viscosity compared to PLLA but a similar melt behaviour. Negligible chain degradation were observed, apart from PLGA.

Although additive manufacturing through melt extrusion has become increasingly popular as a route to design scaffolds with complex geometries the technique if often limited by the reduction in molecular weight and the viscoelastic response when degradable aliphatic polyesters of high molecular weight are used. Here we use a melt extruder and fused filament fabrication printer to produce a reliable nondegradative route for scaffold fabrication of medical grade copolymers of L-lactide, poly(epsilon-caprolactone-co-L-lactide), and poly(L-lactide-co-trimethylene carbonate). We show that degradation is avoided using filament extrusion and fused filament fabrication if the process parameters are deliberately chosen based upon the rheological behavior, mechanical properties, and polymer composition. Structural, mechanical, and thermal properties were assessed throughout the process to obtain comprehension of the relationship between the rheological properties and the behavior of the medical grade copolymers in the extruder and printer. Scaffolds with a controlled architecture were achieved using high-molecular-weight polyesters exhibiting a large range in the elastic response causing negligible degradation of the polymers.

Plastics provide incredible opportunities in the form of great versatility for material usage. However, this comes at the cost of environmental issues as they accumulate in the environment. Therefore a compromise between sustainability and continued plastic usage is to use biomass as a filler material in plastic composites instead of virgin plastics. This would in turn reduce the amount of plastic and increase the usage of renewable raw materials. Of course the mechanical and thermal properties must also be of acceptable quality for material applications and preferably even offer some form of improvement to the preexisting material. One potential biomass filler material is Woodmer, a LCC (lignin carbohydrate complex) produced by Ecohelix. The viability of Woodmer as a thermoplastic composite material was analysed and compared to virgin thermoplastics. Three different plastics were used as basis for the composites and these plastics were Acrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) and low density polyethylene (LDPE).

The results show that it is possible to create homogenous Woodmer/thermoplastic composites. As for the thermal properties, while the UL 94 provided no flame classification on the materials some positive effects were observed in TGA and the results from the DSC were similar to the virgin plastics. The tensile test on the other hand showed that the mechanical properties were negatively affected by increasing Woodmer additions but the effect varied substantially between the different plastics as LDPE was the least affected and PLA the most affected. Future research should focus on making the materials through twin screw extrusion as there were unfortunately issues with the mixing from single screw extruders. Further research regarding the materials morphology, solubility and so forth are also required to see if the composites are suitable materials or if there are any unforeseen issues.

Spruce Bark contains several fundamental main substances; lignin, non-cellulose polysaccharides, cellulose and extractives. This undergraduate study focuses on developing a process to extract each of these components from spruce bark using a biorefinery concept, with a main focus on extracting lignin without degradation. The purpose of the Bark biorefinery concept is to contribute to a circular bioeconomy, by making use of natural resources. With extended research on the area, it will be possible to produce polymers, green chemicals and biofuel from the components in bark. 

This report covers the extraction of the bark components with soxhlet extraction, Hot-water extraction, organosolv extraction and peracetic acid delignification. The extraction was made on two samples, matchstick-sized bark (MS) and 20 mesh-sized bark with a diameter of 0.8 mm (20M). The purpose was to be able to compare the efficiency of the extraction between the two samples. Afterwards, the characterisation of extracts and residue was executed with carbohydrate analysis, 2D HSQC-NMR and FTIR-analysis. 

The results showed that a smaller particle size led to more efficient extractions of all components as well as more pure extract solutions. Lignin concentration determinations of samples at each step showed that a significant amount of lignin was lost prior to the organosolv extraction. Future research should look into ways to reduce this loss in order to increase the lignin yield. The findings in the FTIR and NMR analyses correlates with what could be seen in other reports, discussing similar subjects. For upscaling of this process, future research should go toward optimization of all extraction methods in order to make an upscaling of the process economically viable.  

This thesis explores the optimization of thermal efficiency in 3D-printed walls, employing a variety of materials and wall geometries. A total of 25 walls were fabricated using mortar in four distinct geometries: frame, zigzag, three-void, and S-geometry. Initial plans included experimenting with a wide range of infill materials such as geopolymer (GP), geopolymer foam (GPF) with different concentrations of aluminum (Al) powder (0.25%, 0.5%, 0.75%, and 1%), geopolymer incorporating phase change materials (GPPCM), geopolymer foam incorporating phase change materials (GPPCMF) with varying Al powder concentrations, and polyurethane foam (PUF). Due to time constraints, the study was initiated with the frame wall geometry using six types of infills: mortar, GP, GPF with 1% Al powder, GPPCM, GPPCMF with 1% Al powder, and PUF. Material characterizations were conducted for each infill, assessing density, thermal conductivity, and specific heat capacity to support simulation inputs. Although practical experiments in a custom-built thermal chamber were planned to simulate external temperature variations from 17°C to 32°C, technical challenges resulted in the exclusive use of simulation techniques with COMSOL Multiphysics software. Separate simulation models were developed for each wall geometry to evaluate thermal performance, with one side maintained at a constant room temperature of 22°C and the other side was set to the external temperature conditions, both assigned as convection. Energy losses were quantified using the formula 𝑄 = ∑(ℎ𝑟𝑜𝑜𝑚𝐴∆𝑇𝑖) ∆𝑡𝑖 and compared against a baseline of walls filled solely with mortar. The analysis highlighted that the frame, zigzag and three-void geometries exhibited superior thermal performance when filled with GPPCM. In contrast, GPPCMF with 0.25% Al powder demonstrated the poorest thermal performance due to having the highest thermal diffusivity among the PCM-based materials tested. Notably, the S-geometry wall filled with air and PUF achieved the best thermal performance among all cases, characterized by minimal energy loss. This was due to a sandwich structure with low conductivity and proper heat capacity due to having mortar in between. These findings provide promising insights into future research directions for developing building materials that enhance energy efficiency in architectural applications.

To meet the future need for clean and sustainable energies, there has been considerable interest in the development of triboelectric nanogenerators (TENGs) that scavenge waste mechanical energies. The performance of a TENG at the macroscale is determined by the multifaceted role of surface and interface properties at the nanoscale, whose understanding is critical for the future development of TENGs. Therefore, various protocols from the atomic to the macrolevel for fabrication and tuning of surfaces and interfaces are required to obtain the desired TENG performance. These protocols branch out into three categories: chemical engineering, physical engineering, and structural engineering. Chemical engineering is an affordable and optimal strategy for introducing more surface polarities and higher work functions for the improvement of charge transfer. Physical engineering includes the utilization of surface morphology control, and interlayer interactions, which can enhance the active interfacial area and electron transfer capacity. Structural engineering at the macroscale, which includes device and electrode design/modifications has a considerable effect on the performance of TENGs. Future challenges and promising research directions related to the construction of next-generation TENG devices, taking into consideration “interfaces” are also presented.

Hydrogel-based localised drug delivery minimises systemic side effects and a linear release profile ensuring a sustained drug release over time, crucial for long-term therapy. The current paper describes the use of the Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAc) to append azidified Dexamethasone (Dex) onto dendrons of first- and second-generation PEGs. Crosslinking with thiolated PEGs using either thiol-acrylate or nucleophilic addition reactions yielded gels containing β-thio-ether ester groups that imparted enhanced hydrolytic susceptibility. In vitro gel degradation was followed gravimetrically and expressed as swelling ratios. Thiol-acrylate crosslinked hydrogels exhibited zero-order Dex release kinetics over 11, 27, and 16 days (G1, G1-star, and G2). Crosslinking the G1-gels by nucleophilic addition also resulted in linear release and the end point was reached in 5 days. Hydrolysis was accounted as the main release mechanism for covalently bound Dex, while physically incorporated Dex showed undefined rapid burst or first-order release, with most of the drug released in the initial 1–3 days. Eluates from covalently bound Dex maintained high activity, whereas Trap-Dex gels lost activity over time, as detected by the upregulation of luciferase expression from a transformed cell line. This novel chemistry combination offers precise drug release control applicable beyond Dex to drugs with suitable nucleophilic groups.

Highly conductive silver-nanowire (Ag-NW) networks are used in composite materials as conductive channels. Their resistance tuning can be accomplished by changing the Ag-NW concentration, and, therefore, changing the network structure. In this study, an alternative pathway to resistance engineering of conductive Ag-NW networks by local atmospheric plasma treatment is employed. The corresponding changes in nanowire network morphology and crystallinity as a function of plasma etching time are investigated by time-resolved grazingincidence X-ray scattering, field-effect scanning electron microscopy, and X-ray photoelectron spectroscopy. Three characteristic etching phases are identified. The first two phases enable the controlled engineering of the electrical properties with different rates of resistance change, which results from changes in nanowire shape, network morphology, and different oxidation rates. Phase III is characterized by pronounced fragmentation and destruction of the Ag-NW networks. These results show the feasibility of atmospheric plasma treatments to tune the local electrical properties of conductive Ag-NW networks. Furthermore, we present a physical Monte Carlo model explaining the electrical network properties as a function of plasma etching time based on the network connectivity and a constant plasma etching rate of 570 ng s-1 cm-2.

In the world’s transformation towards a bioeconomy, lignocellulosic biomass plays a key role as a substitute for fossil-based resources. Lignin is the most abundant source of renewable and naturally occurring aromatics and it constitutes 15-30% of lignocellulosic biomass. The technical lignin currently available on the market is limited in its applications because of its complex and poorly understood chemical structure. To contribute to the lignin-first biorefinery concept, this work investigates the effect of urea and carboxymethylation pretreatments on the yield as well as the chemical and physical properties of lignin. Characterization techniques such as Fourier-transform infra-red and nuclear magnetic resonance spectroscopy were utilized to analyze the molecular structure of the lignin product after extraction. It was shown that both pretreatment methods resulted in higher yields between 1% and 16%. The urea pretreatment had no effect on the chemical structure of the fibers nor the lignin. However, carboxymethylation altered the chemical structure of the lignin by adding carboxymethyl groups in both the aliphatic and phenolic regions. While increasing the pretreatment time increased the yield for both pretreatment methods, in the case of carboxymethylation it reduced the amount of quantifiable inter-unit linkages. Overall, the pretreatment methods discussed have potential use for lignin valorization.

A novel and facile method to produce inexpensive protein biofoams suitable for sponge applications is presented. The protein used in the study was wheat gluten (WG), readily available as a by/co-product, but the method is expected to work for other cross-linkable proteins. The foams were obtained by high-speed stirring of pristine WG powder in water at room temperature followed by drying. Glutaraldehyde was used to crosslink the foam material in order to stabilize the dispersion, reduce its tackiness and improve the strength of the final foam. The foams were of medium to high density and absorbed readily both hydrophobic and hydrophilic liquids. The foam structure, consisting primarily of an open pore/channel system, led to a remarkably fast capillary-driven (pore-filling only) uptake of a hydrophobic liquid (limonene). Essentially all uptake occurred within the first second (to ca. 90% of the dry weight). In a polar liquid (water), the rapid pore-filling occurred in parallel with a more time-dependent swelling of the foam matrix material. Further improvement in the foam strength was achieved by making a denser foam or adding TEMPO-oxidized cellulose nanofibres. Soft foams were obtained by adding glycerol.

Saccharina latissima biomass cultivated along the Swedish west coast was subjected to four different scalable preservation methods after harvest; freezing, sun-drying, oven-drying and ensiling. Freeze-drying and freezing at -80 ?C were also included to provide dry and wet references. The effects of the different preservation methods on the composition of Saccharina biomass (on dry weight, DW, basis), and the recovery as well as properties of high-quality protein, alginate and biogas were evaluated. Sun-drying significantly reduced protein, alginate and fatty acid content of the seaweeds and thereby concentrated ash in the biomass compared to the other methods. Protein/amino acids and fatty acids were significantly concentrated in ensiled biomass, while mannitol and laminarin were reduced compared to the other biomasses. Oven-drying and -20 ?C freezing affected the composition the least, with lower ash content and alterations in some specific amino and fatty acids. Sun-drying and ensiling resulted in significantly lower protein solubility at high pH compared to the other biomasses which translated into the lowest total seaweed protein recovery using the pH-shift process. Highest protein yield was obtained with the freeze-dried reference. Ensiling lead to a significant decrease in the molecular weight of alginate, while sun-drying caused a negative effect on alginate by inducing a shift in the guluronic and mannuronic acids composition of alginate. Sun-drying gave the lowest methane yield in the anaerobic digestion experiments while freezing at -80 ?C gave the highest yield, closely followed by freezing at -20 ?C and ensiling. To conclude, preservation methods must be carefully chosen to protect the valuable component in Saccharina latissima, and to achieve an efficient downstream processing ultimately yielding high quality products as part of a seaweed biorefinery.

High molar mass poly(lactic acid) (PLA) is obtained by either the polycondensation of lactic acid or ring-opening polymerization (ROP) of the cyclic dimer 2,6-dimethyl-1,4-dioxane-2,5-dione, commonly referred to as dilactide or lactide (LA). This chapter describes preparation of polymers and copolymers of LAs with different structures, using polycondensation and ROP. Typical comonomers and polymers which are used for lactic acid or LA copolymerization include glycolic acid or glycolide, poly(ethylene glycol) or poly(ethylene oxide), and so on. PLAs having amino, carboxyl, or other functional groups are well reported in the literature. These functional groups can be utilized for chemical modification or as binding sites for biomolecules to impart selective binding and adhesion. PLA and its copolymers especially when used for biological applications, besides requirement of optimization of mechanical properties by engineering at the molecular level, also demands a fast degradation polymer rate.

Plastic waste is a severe environmental problem in today's society which has been noticed and discussed during the last couple of years. A constant increase of production over the last decades hasled to a large amount of plastic waste ending up in oceans as microplastics. With harder restrictions of plastic use from the European Parliament, alternative plastics that are bio-based and therefore degradable have increased in demand. The aim of this project was therefore to synthesize alignocellulose-based material which contains the minimum amount of latex, the plastic component, while still satisfying the same requirements as a thermoplastic. The original idea was to create the latex with PISA-RAFT technique however, this was not possible since the needed materials could not be delivered due to COVID-19, therefore radical emulsion polymerization was carried out.

Two latexes were synthesized to create composites with wheat-straw, latex A and latex B. Both latexes consisted of 75% of monomer vinyl acetate (VAc) which was the main component but with different weight percentages of monomers methacrylic acid (MAA) and methyl methacrylate (MMA). Latex A consisted of 20 % MAA and 5% MMA and latex B consisted of 20% MMA and 5% MAA. Latex A and latex B were then mixed with wheat straw to create composites. Due to problems withthe wheat-straw composites one additional composite was created to be able to do all of the analyses. This composite was created by using filter paper as biofiber to mix with the two different latexes. Various characterization analyses including FE-SEM, DLS, DSC, FTIR, NMR, TGA and tensile tests were performed on the composites.

The NMR and DSC analyses indicated that the actual composition of monomers differs from the theoretical composition and demonstrates that the presence of MAA is hard to detect. This is due to the DSC value for latex A experimental Tg being lower than latex B experimental Tg when latex A consists of more MAA which has a higher detected Tg. During the NMR analysis MAA was also not detected in either latex A nor latex B. The analyses of FTIR contradicts the NMR and DSC analyses hence peaks believed to be from MAA are detected. When comparing the analysis for latex A and B, DLS analysis resulted in latex A having a low PDI and a bigger emulsion sphere size which is preferred when producing composites. The tensile test resulted in latex B achieving the higher values for Young’s modulus and max stress while latex A had a higher value for strain at break. The TGA and DSC analysis however resulted in latex B having a higher Tg and higher thermal stability. The overall analyses indicated that latex B was the most optimal choice for composite production with aslight difference.

The analysis of the composites indicated by FE-SEM that the interaction between latex and filter paper were higher than for latex and wheat straw. A total of four wheat-straw composites were created with the weight-ratio of wheat-straw:latex, 50:50 and 75:50 for both latex A and B. Due to not being able to grind the wheat straw to the minimum size needed to create composites only FE-SEM and FTIR analyses of the wheat-straw composites could be made. Because of this no conclusion could be made whether the 75:50 or 50:50 weight ratio was the most optimal.

Cellulosic materials are widely used in our everyday lives, ranging from paperand packaging to biomedical applications. However, in most applications, cellulose must coexist with hydrophobic polymers which can be challenging due to its hydrophilic character. This has encouraged the exploration of chemical and physical modifications of cellulose.

The projects included in this thesis focus on the physical modification of cellulosic materials with tailor-made, highly versatile colloidal nanoparticles synthesized in water, called nanolatexes. Their synthesis is based on the combination of the reversible addition-fragmentation chain transfer (RAFT) polymerization with polymerization-induced self-assembly (PISA). The bridging of these techniques results in the formation of amphiphilic diblock copolymers which self-assemble in water forming a variety of morphologies. Spheres, worms and vesicles with pH-responsive shell polymers were prepared to investigate the parameters that tune these morphological transitions. Less investigated parameters such as the chemical composition of the RAFT agent were studied which resulted in the formation of bimodal nanolatexes with opal-like characteristics in a reproducible manner. 

A fundamental investigation of the parameters that govern the adsorption of cationically charged nanolatexes onto silica and regenerated TEMPO-oxidized cellulose model surfaces was also performed. The combination of gravimetric and a reflectometric techniques revealed the complexity of that model surface. Both the size and the charge density of the nanolatexes were found to influence their adsorption. The information gained from this study was implemented in the preparation of cellulose nanofibril (CNF)-nanocomposites with low contents of nanolatexes. It was found that when the nanolatex content was below 1 wt% the mechanical profile of the CNF-nanocomposites was improved. 

Finally, wood-based components were used to replace fossil-based monomers in nanolatexes. They were readily adsorbed onto cellulose filter papers and annealed, thus demonstrating their film formation capacity. Nanolatexes comprised of a wood-based shell polymer have a promising high-end application profile, as showcased by their interactions with Cu(II) ions, where nanolatexes prevented the formation of Cu(II) ion aggregates. 

The results summarized in this thesis add to the understanding on physical modification of cellulose and are envisaged to further promote the utilization of wood-based monomers in the production of the polymers for high-end applications.

To address the increasing demand for biobased materials, lignin-derived ferulic acid (FA) is a promising candidate. In this study, an FA-derived styrene-like monomer, referred to as 2-methoxy-4-vinylphenol (MVP), was used as the platform to prepare functional monomers for radical polymerizations. Hydrophobic biobased monomers derived from MVP were polymerized via solution and emulsion polymerization resulting in homo- and copolymers with a wide range of thermal properties, thus showcasing their potential in thermoplastic applications. Moreover, divinylbenzene (DVB)-like monomers were prepared from MVP by varying the aliphatic chain length between the MVP units. These biobased monomers were thermally crosslinked with thiol-bearing reagents to produce thermosets with different crosslinking densities in order to demonstrate their thermosetting applications. The results of this study expand the scope of MVP-derived monomers that can be used in free-radical polymerizations toward the preparation of new biobased and functional materials from lignin.

The polymerization of a bio-based terpene-derived monomer, sobrerol methacrylate (SobMA), was evaluated in the design of polymeric nanoparticles (nanolatexes). Their synthesis was accomplished by using emulsion polymerization, either by free-radical polymerization in the presence of a cationic surfactant or a cationic macroRAFT agent by employing RAFT-mediated polymerization-induced self-assembly (PISA). By tuning the length of the hydrophobic polymer, it was possible to control the nanoparticle size between 70 and 110 nm. The average size of the latexes in both wet and dry state were investigated by microscopy imaging and dynamic light scattering (DLS). Additionally, SobMA was successfully copolymerized with butyl methacrylate (BMA) targeting soft-core nanolatexes. The comparison of the kinetic profile of the cationically stabilized nanolatexes highlighted the differences of both processes. The SobMA-based nanolatexes yielded high T-g similar to 120 degrees C, while the copolymer sample exhibited a lower T-g similar to 50 degrees C, as assessed by Differential Scanning Calorimetry (DSC). Thereafter, the nanolatexes were adsorbed onto cellulose (filter paper), where they were annealed at elevated temperatures to result in polymeric coatings. Their morphologies were analysed by Field Emission Scanning Electron Microscopy (FE-SEM) and compared to a commercial sulfate polystyrene latex (PS latex). By microscopic investigation the film formation mechanism could be unravelled. Water contact angle (CA) measurements verified the transition from a hydrophilic to a hydrophobic surface after film formation had occured. The obtained results are promising for the toolbox of bio-based building blocks, focused on sobrerol-based monomers, to be used in emulsion polymerizations either for tailored PISA-latexes or facile conventional latex formation, in order to replace methyl methacrylate or other high T-g-monomers.

Cellulose nanofibril (CNF)-networks are modified by the addition of small amounts (below 10 wt%) of well-defined cationic nanolatexes synthesized through reversible addition–fragmentation chain-transfer-mediated polymerization-induced self-assembly (PISA). Minute amounts of nanolatex inclusions lead to increased tensile and shear moduli, indicating that nanolatexes can act as bridging-points between CNFs. At higher nanolatex content, this stiffening effect is lost, likely due to interactions between nanolatexes leading to plasticization. The influence of nanolatex content and size on interparticle distance is discussed and is used as a tool to understand the effects observed in macroscopic properties. Upon annealing, the stiffening effect is lost due to the softening of the nanolatexes, indicating that the core–shell morphology is a prerequisite for this effect. These systems form a versatile platform to develop fundamental insights into complex condensed colloidal systems, to ultimately aid in the development of new sustainable material concepts.