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Research on solid polymer electrolytes (SPEs) is now moving beyond the realm of polyethers that have dominated the field for several decades. A promising alternative group of candidates for SPE host materials is carbonyl-containing polymers. In this work, SPE properties of three different types of carbonyl-coordinating polymers are compared: polycarbonates, polyesters, and polyketones. The investigated polymers were chosen to be as structurally similar as possible, with only the functional group being different, thereby giving direct insights into the role of the noncoordinating main-chain oxygens. As revealed by experimental measurements as well as molecular dynamics simulations, the polyketone possesses the lowest glass transition temperature, but the ion transport is limited by a high degree of crystallinity. The polycarbonate, on the other hand, displays a relatively low coordination strength but is instead limited by its low molecular flexibility. The polyester performs generally as an intermediate between the other two, which is reasonable when considering its structural relation to the alternatives. This work demonstrates that local changes in the coordinating environment of carbonyl-containing polymers can have a large effect on the overall ion conduction, thereby also showing that desired transport properties can be achieved by fine-tuning the polymer chemistry of carbonyl-containing systems.

Thiolated polymers are widely used in hydrogels for drug delivery, tissue engineering, and biofabrication. The oxidation of thiols is spontaneous, resulting in the formation of disulfide bridges and cross linking of polymers. The cross-linking process is, however, difficult to control and is initiated directly when the thiolated components are exposed to ambient conditions, which significantly complicates handling of the materials. Here, we show a fully bioorthogonal enzyme-mediated thiol-based chemistry for dynamic covalent cross-linking of carbohydrate-based hydrogels that circumvents the problems with uncontrolled thiol oxidation. Alginate was modified with cysteine residues, protected by an enzyme-labile thiol-protecting group (Phacm). Releasing the Phacm group by penicillin G acylase generates free thiols that oxidize under physiological conditions, resulting in a reversible cross-linking and formation of hydrogels with tunable stiffness. Prior to deprotection, the components can be exposed to ambient conditions. The enzyme-triggered deprotection and subsequent gelation allows for encapsulation of cells and 3D bioprinting of cell-laden hydrogel structures. Remaining deprotected thiols enabled postprinting modifications and hydrogel self-healing. The proposed hydrogel synthesis strategy significantly increases the versatility of thiol-based cross-linking chemistries and provides new possibilities to generate dynamic covalent hydrogels for a broad range of biomedical applications. Funding Agencies|Swedish Foundation for Strategic Research (SFF) [FFL15-0026]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; Carl Tryggers Foundation; Knut and Alice Wallenberg Foundation [KAW 2016.0231, 2021.0186]

Potentially high-performance lithium metal cells in extreme high-temperature electrochemical environments is a challenging but attractive battery concept that requires stable and robust electrolytes to avoid severely limiting lifetimes of the cells. Here, the properties of tailored polyester and polycarbonate diols as the soft segments in polyurethanes are investigated and electrochemically evaluated for use as solid polymer electrolytes in lithium metal batteries. The polyurethanes demonstrate high mechanical stability against deformation at low flow rates and moreover at temperatures up above 100 degrees C, enabled by the hard urethane segments. The results further indicate transferrable ion transport properties of the pure polymers when incorporated as the soft segments in the polyurethanes, offering designing opportunities of the polyurethane by tuning the soft segment ratio and composition. Long-term electrochemical cycling of polyurethane-containing cells in lithium metal batteries at 80 degrees C proves the stability at elevated temperatures as well as the compatibility with lithium metal with stable cycling maintained after 2000 cycles.

Nowadays, there is an urgent need to decrease our dependence on fossilresources and shift towards the use of renewable resources for advancingsustainable development. Utilizing renewable and bio-based raw materials,such as lignocellulosic biomass, for designing new materials is a promisingapproach to promote this objective. The main components of lignocellulosicbiomass are cellulose, hemicellulose, and lignin. Lignin is the most abundantaromatic biopolymer in nature and it is produced on a large scale fromchemical pulping processes as technical lignin. Lignin has the potential as asustainable and renewable alternative to fossil-based aromatics in variousapplications, e.g. thermosetting resins. Technical lignin has a complex and heterogeneous structure, with arelatively low chemical reactivity. It is characterized by a high dispersity, thepresence of various functional groups that are unevenly distributed along thelignin chains, and various interunit linkages between the monoaromatics. Toovercome the challenges associated with lignin heterogeneity, technicallignin can be fractionated and/or chemically modified. In this work, LignoBoost Kraft lignin was used as a starting material toproduce lignin-based thiol-ene thermosets. Firstly, lignin was fractionatedusing two approaches: 1) sequential solvent fractionation, and 2) microwaveassistedextraction. These fractionation approaches enabled access to ligninfractions with unique and tunable properties. Subsequently, lignin waschemically modified, in particular through allylation. Two allylation reagentswere used: allyl chloride and diallyl carbonate. The use of allyl chlorideenables a selective allylation of the phenolic OH groups, leaving the aliphaticand carboxylic acid OH groups unmodified. On the other hand, diallylcarbonate can react with all the aforementioned OH groups, leading to ahigher degree of allylation. Subsequently, allylated lignin was thermallycross-linked with various polyfunctional thiols, leading to thiol-enethermosets. The structure-property relationships of the thermosets wereinvestigated by varying several parameters, including the lignin source,fractionation approach, chemical modification, and thiol cross-linker. Byadjusting these parameters, various thermosets with tunable mechanical andmorphological properties were produced. Understanding the structurepropertyrelationships of these bio-based materials is crucial for identifyingpotential applications. Nuförtiden finns det ett akut behov av att minska vårt beroende av fossilaresurser och övergå till användningen av förnybara resurser och därmedavancera den hållbara utvecklingen. Att använda förnybara och biobaseraderåvaror, såsom lignocellulosabiomassa, för att designa nya material är ettlovande tillvägagångssätt för att uppnå detta mål. Huvudkomponenterna ilignocellulosabiomassa är cellulosa, hemicellulosa och lignin. Lignin ärnaturens vanligaste aromatiska biopolymer och den produceras i stor skalafrån kemiska massaprocesser som tekniskt lignin. Lignin kan fungera som etthållbart och förnybart alternativ till fossilbaserade aromater i olikatillämpningar, t.ex. g. värmehärdande hartser. Tekniskt lignin har en komplex och heterogen struktur, med en relativt lågkemisk reaktivitet. Det kännetecknas av en hög dispersitet, närvaron av olikafunktionella grupper som är ojämnt fördelade längs ligninkedjorna, och olikatyper av enhetsbindningar mellan monoaromaterna. För att övervinna deutmaningar som är förknippade med ligninets heterogenitet kan ligninfraktioneras och/eller kemiskt modifieras. I detta arbete användes LignoBoost Kraft-lignin som utgångsmaterial föratt tillverka ligninbaserade tiol-en-härdplaster. Först har lignin fraktioneratsmed hjälp av två olika metoder: 1) sekventiell lösningsmedelsfraktionering,och 2) mikrovågsassisterad extraktion. Dessa fraktioneringsmetoder gjordedet möjligt att erhålla ligninfraktioner med unika och skräddarsyddaegenskaper. Därefter modifierades ligninet kemiskt genom allylering. Tvåallyleringsreagens användes: allylklorid och diallylkarbonat. Användningenav allylklorid möjliggör selektiv allylering av de fenoliska OH-grupperna,samtidigt som de alifatiska och karboxylsyra-OH-grupperna lämnasomodifierade. Diallylkarbonat kan å andra sidan reagera med alla de tidigarenämnda OH-grupperna, vilket leder till en högre grad av allylering. Däreftertvärbands härdades allylerat lignin termiskt med olika polyfunktionellatioler, för att ge härdplast med tiol-en-tvärbindingar. Strukturegenskapsförhållandenaför härdplasterna undersöktes genom att varieraflera parametrar, inklusive ligninkällan, fraktioneringsmetod, kemiskmodifiering och tioltvärbindare. Genom att justera dessa parametrarproducerades olika härdplaster med skräddarsydda mekaniska ochmorfologiska egenskaper. Att förstå relationerna mellan struktur ochegenskaper av dessa biobaserade material är avgörande för att identifierapotentiella tillämpningar. QC 2023-05-23

Polyester dendrimers based on 2,2 bis(hydroxymethyl)propionic acid have been reported to be degradable, non-toxic, and exhibit good antimicrobial activity when decorated with cationic charges. However, these systems exhibit rapid depolymerization, from the outer layer inwards in physiological neutral pHs, which potentially restricts their use in biomedical applications. In this study, we present a new generation of amine functional bis-MPA polyester dendrimers with increased hydrolytic stability as well as antibacterial activity for Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) planktonic bacteria strains. These new derivatives show generally good cytocompatibility for the concentrations they are active toward bacteria, in monocyte/macrophage-like cells (Raw 264.7), and human dermal fibroblasts. Fluoride - promoted esterification chemistry, anhydride chemistry, and click reactions were utilized to produce a library from generations 1–3 and with cationic peripheral groups ranging from 6 to 24 groups, respectively. The dendrimers were successfully purified using conventional purification techniques as well as characterized by matrix-assisted laser desorption ionization time-of-flight mass spectroscopy, nuclear magnetic resonance, and size exclusion chromatography. As proof of synthetic versatility, dendritic-linear-dendritic block copolymer were successfully synthesized to display cysteamine peripheral functionalities as well as the scaffolding ability with biomedically relevant lipoic acid and methoxy polyethylene glycol. QC 20230526

The self-assembly of nanocellulose in the form of cellulose nanofibers (CNFs) can be accomplished via hydrogen-bonding assistance into completely bio-based hydrogels. This study aimed to use the intrinsic properties of CNFs, such as their ability to form strong networks and high absorption capacity and exploit them in the sustainable development of effective wound dressing materials. First, TEMPO-oxidized CNFs were separated directly from wood (W-CNFs) and compared with CNFs separated from wood pulp (P-CNFs). Second, two approaches were evaluated for hydrogel self-assembly from W-CNFs, where water was removed from the suspensions via evaporation through suspension casting (SC) or vacuum-assisted filtration (VF). Third, the W-CNF-VF hydrogel was compared to commercial bacterial cellulose (BC). The study demonstrates that the self-assembly via VF of nanocellulose hydrogels from wood was the most promising material as wound dressing and displayed comparable properties to that of BC and strength to that of soft tissue. Validerad;2023;Nivå 2;2023-05-17 (hanlid);Licens full text: CC-BY: This license allows reusers to distribute, remix, adapt, and build upon the material in any medium or format, so long as attribution is given to the creator. The license allows for commercial use. Credit must be given to the creator.

Semitransparent organic solar cells (ST-OSCs) are promising candidates for applications in building-integrated photovoltaics (BIPV) as windows and facades. The challenge to achieve highly efficient ST-OSCs is the trade-off between power conversion efficiency (PCE) and average visible transmittance (AVT). Herein, solution-processed ST-OSCs are demonstrated on the basis a polymer donor, PM6, and a small molecule acceptor, Y6; lowering the visible-absorbing PM6 contents in blends could increase AVT and maintain PCE. Additionally, conductive polymer PEDOT:PSS is used as the top electrode due to its high transparency, good conductivity, and solution processability. Efficient ST-OSCs with 20 wt % PM6 achieve high PCE of 7.46% and AVT of 36.4%. The light utilization efficiency (LUE) of 2.72% is among the best reported values for solution-processed ST-OSCs. This work provides a straightforward approach for solution-processed ST-OSCs by combining a low fraction of visible-wavelength-selective polymer donors with near-infrared nonfullerene acceptors to achieve high PCE and AVT simultaneously. Funding agencies: Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation [2016.0059]; Swedish Government Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; China Scholarship Council (CSC)China Scholarship Council [201708370115]

Double-layer solid polymer electrolytes (DLSPEs) comprising one layer that is stable toward lithium metal and one which is stable against a high-voltage cathode are commonly suggested as a promising strategy to achieve high-energy-density lithium batteries. Through in-depth EIS analysis, it is here concluded that the polymer–polymer interface is the primary contributor to electrolyte resistance in such DLSPEs consisting of polyether-, polyester-, or polycarbonate-bad SPEs. In comparison to the bulk ionic resistance, the polymer–polymer interface resistance is approximately 10-fold higher. Nevertheless, the interfacial resistance was successfully lowered by doubling the salt concentration from 25 to 50 wt % LiTFSI owing to improved miscibility at the interface of the two polymer layers.

Diketopyrrolopyrroles (DPP) have been recognized as a promising acceptor unit for construction of semiconducting donor-acceptor (D-A) polymers, which are typically flanked by spacers such as thiophene rings via a carbon-carbon single bond formation. It may suffer from a decrease in the coplanarity of the molecules especially when bulky side chains are installed. In this work, the two N atoms in the DPP unit are further fused with C-3 of the two flanking thiophene rings, yielding a p-expanded, very planar fused-ring building block (DPPFu). A novel DPPFu-based D-A copolymer (PBDTT-DPPFu) was successfully synthesized, consisting of a benzo[1,2-b:4,5-b]dithiophene (BDTT) unit as a donor and a DPPFu unit as an acceptor. For comparison, the unfused DPP-based counterpart PBDTT-DPP was also synthesized. Two dodecyl alkyl chains were attached to thiophene rings of DPP moieties to ensure good solubility of the DPPFu-based polymer. The influence of the ring-fusion effect on their structure, photophysical properties, electronic properties, molecular packing, and charge transport properties is investigated. Ring-fusion enhances the intermolecular interactions of PBDTT-DPPFu polymer chains as indicated by density functional theory calculation and analysis of electrostatic potential and van der Waals potential and results in significantly improved molecular packing for both the in-plane and out-of-plane directions as suggested by X-ray measurements. Finally, we correlate the molecular packing to the device performance by fabricating field-effect transistors based on these two polymers. The charge carrier mobility of the ring-fused polymer PBDTT-DPPFu is significantly higher as compared to the PBDTT-DPP polymer without ring-fusion, although PBDTT-DPPFu exhibited a much lower number-average molecular weight of 17 kDa as compared to PBDTT-DPP with a molecular weight of 108 kDa. The results from our comparative study provide a robust way to increase the interchain interaction by ring-fusion-promoted coplanarity. Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2015-04853, 2016-06146, 2019-04683]; Swedish Research Council FormasSwedish Research CouncilSwedish Research Council Formas; NSFCNational Natural Science Foundation of China (NSFC) [21504006, 21534003, 11272093]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [2017.0186, 2016.0059]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research; China Scholarship CouncilChina Scholarship Council [201908440047]; Guangzhou Municipal Science and Technology Bureau [201804010501, 201904010381, 202002030362]; Department of Education of Guangdong ProvinceNational Natural Science Foundation of Guangdong Province [2018GKTSCX041, 2017GKQNCX005]; Department of Science and Technology of Guangdong Province [2016A010103046]; Open Fund of the State Key Laboratory of Luminescent Materials and Devices (South China University of Technology) [2020-skllmd-07]; Natural Science Foundation of Hunan ProvinceNatural Science Foundation of Hunan Province [2018JJ3098]; Office of Science, Office of Basic Energy Sciences, of the U.S. Department of EnergyUnited States Department of Energy (DOE) [DE-AC02-05CH11231]

Highly porous, strong aerogels with anisotropicstructural properties are of great interest for multifunctionalmaterials for applications including insulators in buildings,filters for oil cleanup, electrical storage devices,etc. Contem-porary aerogels are mostly extracted from fossil resources andsynthesized from bottom-up techniques, often requiring addi-tional strategies to obtain high anisotropy. In this work, auniversal approach to prepare porous, strong, anisotropicaerogels is presented through exploiting the natural hierarchicaland anisotropic structure of wood. The preparation comprisesnanoscale removal of lignin, followed by dissolution−regener-ation of nanofibers, leading to enhanced cell wall porosity with nanofibrillated networks occupying the pore space in thecellular wood structure. The aerogels retain structural anisotropy of natural wood, exhibit specific surface areas up to 247 m2/g, and show high compression strength at 95% porosity. This is a record specific area value for wood aerogels/foams and evenhigher than most cellulose-based aerogels for its assigned strength. The aerogel can serve as a platform for multifunctionalcomposites including scaffolds for catalysis, gas separation, or liquid purification due to its porous matrix or as binder-freeelectrodes in electronics. To demonstrate the multifunctionality, the aerogels are successfully decorated with metalnanoparticles (Ag) and metal oxide nanoparticles (TiO2)byin situsynthesis, coated by the conductive polymer(PEDOT:PSS), and carbonized to yield conductive aerogels. This approach is found to be a universal way to prepare highlyporous anisotropic aerogels. QC 20200918

An environmentally benign synthesis of a magnetically responsive carboxymethylated cellulose nanofibril-based material is reported. Applied experimental conditions lead to the in-situ formation of magnetite nanoparticles with primary particle sizes of 2.0-4.0 nm or secondary particles of 3.6-16.4 nm depending on whether nucleation occurred between individual carboxymethylated cellulose nanofibrils, or on exposed fibril surfaces. The increase in magnetite particle size on the cellulose fibril surfaces was attributed to Ostwald ripening, while the small particles formed within the carboxymethyl cellulose aggregates were presumably due to steric interactions. The magnetite nanoparticles were capable of coordinating to carboxymethylated cellulose nanofibrils to form large "fibre-like" assemblies. The confinement of small particles within aggregates of reductive cellulose molecules was most likely responsible for excellent conservation of magnetic characteristics on storage of this material. The possibility for using the material in drug delivery applications with release rate controlled by daylight illumination is presented.

The interphase properties in nanocomposites indicate the interaction between filler and matrix, which is dependent on the preparation method, shape, and size of filler and the chemical interaction between two phases. Local chemical environment in polymer matrix give rise to the different dielectric properties compared to that of bulk material. These properties allow the understanding of their effects on the dielectric properties and glass transition (T-g) of the nanocomposites. In this study, interphase power law model was used to predict the interphase properties based on the experimental dielectric constant of polyimide (PI) with BaTiO3, TiO2, and ZrO2 nanocomposites. They were prepared via in situ polymerization of PI whose dielectric constant were increased at interphase filler volume fraction of BaTiO3, TiO2, and ZrO2 at 3.8, 2.05, and 1.7, respectively. These results indicate that PI/ceramics nanocomposites had poor dispersion and weak interphase interaction between the filler and the matrix, as an evidence of scanning electron microscopy and Fourier transform infrared spectroscopy results. However, PI incorporated with high aspect ratio of BaTiO3 nanofiber shows better dispersion than nanocomposites of TiO2 and ZrO2 filled PI; therefore provide higher dielectric constant and T-g. Funding Agencies|AUN/SEED-Net [6050315]; RU (I) [814242]

Artificial photosynthesis requires catalysts for efficient and selective conversions of small molecules. Molecular catalysts are advantageous to use in these instances as they offer precise control over chemical reactivity. They are synthetically tuneable, and their catalytic mechanisms are often well documented and more readily understood than those of solid-state catalysts. In this thesis, the synthetic incorporation of molecular catalysts into heterogenised molecular anodes for water oxidation are evaluated. The catalysts are incorporated as structural linkers into porous metal-organic framework (MOF) structures, and as coordination oligomers stacked onto graphitic surfaces. The preparation of MOF/molecular catalyst hybrid materials of two topologies, UiO (UiO = Universitet i Oslo) and NU-1000 (NU = Northwestern University), were investigated. Multiple synthetic methods for the incorporation of molecular ruthenium-based catalysts into MOFs were examined in papers I and II. In paper III of this thesis, a Ru-bda type molecular complex was successfully used in the solvothermal synthesis of a new MOF. The resulting material is the first of its kind that is built exclusively from molecular water oxidation catalyst linkers. It is shown that MOF incorporation greatly enhances the structural stability of the catalyst linker in chemical water oxidation experiments, giving rise to higher turnover numbers compared to that of a homogenous reference system. Finally, paper IV describes a stable and inert molecular ruthenium complex, which possesses a flexible adaptative multidentate equatorial (FAME) type equatorial ligand with a carbanion on the equatorial ligand that forms a C-Ru bond. This molecular complex is studied in homogeneous phase, and subsequently incorporated into a coordination oligomer, which can be activated for water oxidation catalysis. This finding broadens the field of molecular catalysis significantly, and proves that supramolecular interactions can be used to promote electrocatalysis in complexes which are otherwise too inert and stable to engage in electrocatalytic reactions.

The approach of using polyether, aka glycol, side chains to afford amphiphilicity to conducting polymers has recently emerged as a powerful technique for next-generation materials for bioelectronics and electrochemical devices. Herein we apply this synthetic logic to the archetypical conducting polymer poly(3,4-ethylenedioxythiophene), PEDOT, to generate a glycolated PEDOT analogue, G-PEDOT. We report on the electropolymerization of this material, and its electrochemical properties: including spectroelectrochemistry, electrochemical capacitance, and operation of microelectrodes and electrochemical transistors. While in many respects performing like PEDOT, G-PEDOT has electrochemical switching within lower potentials with complete de-doping at lower potentials, affording transistors with higher on/off ratios than PEDOT, and electrochromic switching within a smaller electrochemical window. Overall, G-PEDOT emerges as a useful, functional alternative to other PEDOT derivatives, and could be a building block in copolymers. Funding Agencies|National Science Centre, Poland [2019/33/B/ST5/01212]; European Research Council (ERC) under the European Union [949191]; city council of Brno, Czech Republic; MEYS CR [LM2018110]

The interplay between the nanostructure of a doped polythiophene with oligoether side chains and its electrical as well as mechanical properties is investigated. The degree of order of the polymer is found to strongly vary when co-processed with bistriflimidic acid (H-TFSI). The neat polythiophene as well as strongly oxidized material are largely disordered while intermediate concentrations of H-TFSI give rise to a high degree of pi-stacking. The structural disorder of strongly oxidized material correlates with a decrease in the kinetic fragility with H-TFSI concentration, suggesting that positive interactions between TFSI anions and the polymer reduce the ability to crystallize. The electrical conductivity as well as the Youngs modulus first increase upon the addition of 4-10 mol% of H-TFSI, while the loss of pi-stacking observed for strongly oxidized material more significantly affects the latter. As a result, material comprising 25 mol% H-TFSI displays an electrical conductivity of 58 S cm(-1) but features a relatively low Youngs modulus of only 80 MPa. Decoupling of the electrical and mechanical properties of doped conjugated polymers may allow the design of soft conductors that are in high demand for wearable electronics and bioelectronics. Funding Agencies|Swedish Research Council [2016-05990, 2018-03824]; European Union [955837]; Knut and Alice Wallenberg Foundation through a Wallenberg Academy Fellowship Prolongation grant

Injectable bioelectronics could become an alternative or a complement to traditional drug treatments. To this end, a new self-doped p- type conducting PEDOT-S copolymer (A5) was synthesized. This copolymer formed highly water-dispersed nanoparticles and aggregated into a mixed ion-electron conducting hydrogel when injected into a tissue model. First, we synthetically repeated most of the published methods for PEDOT-S at the lab scale. Surprisingly, analysis using high-resolution matrix-assisted laser desorption ionization-mass spectroscopy showed that almost all the methods generated PEDOT-S derivatives with the same polymer lengths (i.e., oligomers, seven to eight monomers in average); thus, the polymer length cannot account for the differences in the conductivities reported earlier. The main difference, however, was that some methods generated an unintentional copolymer P(EDOT-S/EDOT-OH) that is more prone to aggregate and display higher conductivities in general than the PEDOT-S homopolymer. Based on this, we synthesized the PEDOT-S derivative A5, that displayed the highest film conductivity (33 S cm(-1)) among all PEDOT-S derivatives synthesized. Injecting A5 nanoparticles into the agarose gel cast with a physiological buffer generated a stable and highly conductive hydrogel (1-5 S cm(-1)), where no conductive structures were seen in agarose with the other PEDOT-S derivatives. Furthermore, the ion-treated A5 hydrogel remained stable and maintained initial conductivities for 7 months (the longest period tested) in pure water, and A5 mixed with Fe3O4 nanoparticles generated a magnetoconductive relay device in water. Thus, we have successfully synthesized a water-processable, syringe-injectable, and self-doped PEDOT-S polymer capable of forming a conductive hydrogel in tissue mimics, thereby paving a way for future applications within in vivo electronics. Funding Agencies|Swedish Research Council [2018-05258, 2018-06197]; Swedish Foundation for Strategic Research (e-NeuroPharmacology) [RMX18-0083]; European Research Council (ERC) project [e-NeuroPharma 834677]

Aqueous sodium hydroxide solutions are extensively used as solvents for lignin in kraft pulping. These are also appealing systems for cellulose dissolution due to their inexpensiveness, ease to recycle and low toxicity. Cellulose dissolution occurs in a narrow concentration region and at low temperatures. Dissolution is often incomplete but additives, such as zinc oxide or urea, have been found to significantly improve cellulose dissolution. In this work, lignin was explored as a possible beneficial additive for cellulose dissolution. Lignin was found to improve cellulose dissolution in cold alkali, extending the NaOH concentration range to lower values. The regenerated cellulose material from the NaOH-lignin solvents was found to have a lower crystallinity and crystallite size than the samples prepared in the neat NaOH and NaOH-urea solvents. Beneficial lignin-cellulose interactions in solution state appear to be preserved under coagulation and regeneration, reducing the tendency of crystallization of cellulose. info:eu-repo/semantics/publishedVersion

Strukturella batterier är multifunktionella; de tillhandahåller lagring av elektrokemisk energi samtidigt som de bidrar med en lastbärande funktion. Tillsammans möjliggör detta att batteriet kan integreras i karossen hos ett elektriskt fordon eller apparat. Denna multifunktionalitet möjliggör således en avsevärd reducering i fordonets vikt. Kompositmaterialet är förstärkt av kolfiberelektroder, innesluten i en elektrolytstruktur. För att förverkliga detta koncept måste batteriets elektrolyt kunna motstå mekanisk belastning, samtidigt som den transporterar joner mellan batteriets elektroder. Denna studie syftar till att bygga vidare på konceptet av fas-separerade polymerelektrolyter, skapade från polymerisationsinducerad fasseparation via termisk härdning, vilket är en teknik utvecklad av Schneider et al. och Ihrner et al. Vidare undersöks effekten av att dels använda en elektrolytlösning baserad på EC:PC, men även att inkorporera tioler till polymernätverket. Tvärbindningsmolekylerna som användes i denna studie inkluderade trimetylolpropan tris(3-merkaptopropionat) (3TMP), pentaerythritol tetrakis(3-merkaptopropionat) (4PER), och dipentaerythritol hexakis-(3-merkaptopropionat) (6DPER). Dessa skiljer sig i antal funktionella tiolgrupper. Konduktivitet, termo-mekanisk prestanda och strukturberoende egenskaper undersöktes genom tre laborativa faser. Den första fasen behandlade inverkan på elektrolytsystemet av ändrat lösningsmedel, tiol-funktionalitet samt tiolgruppförhållandet gentemot allyl gruppen på den primära monomeren. Sampolymeren innehållandes 6DPER uppvisade bäst multifunktionalitet, varpå denna utvecklades vidare i fas två där en optimal sammansättning fastställdes som bestod utav 45 viktprocent jonlösning. I den slutliga fasen konstruerades en halv-cell baserat på den tidigare optimerade elektrolytkompositionen; den uppmätta kapaciteten visar tydlig förbättring jämfört med tidigare forskning. Resultatet som erhölls i denna studie bidrar till förståendet av strukturella batteri-elektrolyter samt den forskning som en dag kan komma att förverkliga strukturella batterier och dess tillämpningskrav. Structural batteries are multifunctional; providing electrochemical energy storage synergistically with a load-bearing function that enables their integration into the body panels of electric devices and vehicles. Thus, massless energy can be achieved. As a composite material, it is composed of reinforcing carbon fibre electrodes embedded in an electrolyte matrix. To realize this concept, the electrolyte must simultaneously transfer mechanical load and transport ions between electrodes. The following study builds on a phase-separated polymer electrolyte, created using polymerization-induced phase separation via thermal curing, formulated by Schneider et al. and Ihrner et al.. The impact of the incorporation of thiols for copolymerization and as cross-linking agents for the polymer network was researched along with use of an EC:PC-based solvent. The three thiols studied were: trimethylolpropane tris(3-mercaptopropionate) (3TMP), pentaerythritol tetrakis(3-mercaptopropionate) (4PER), and dipentaerythritol hexakis-(3-mercaptopropionate) (6DPER). These differed in regard to the amount of thiol functional groups present. Ionic conductivity, thermo-mechanical performance and structure-property relationships were studied across 3 laboratory phases. The first phase concerned the effect of thiol-functionality, the thiol functional group ratio relative to the allyl group present in the primary monomer, and the solvent interaction. 6DPER was concluded to be the most promising cross-linking agent. During the second phase, the effect of electrolyte content was evaluated with an optimum of 45 weight% determined. The third phase concluded the study, wherein a half-cell was assembled with the optimized electrolyte formulation showing improved capacity relative to previous studies. The results developed here contribute to the understanding of structural battery electrolyte systems and their continued research to meet application demands.

The purpose of this study was to investigate the influence of aging on the properties of high-density polyethylene (HDPE) reinforced with multi-wall carbon nanotubes (MWCNTs). Nanocomposites were prepared with nanotubes at 0, 1, 3, and 5 wt%. The long-term durability of the prepared materials was evaluated by thermo-oxidative aging test. Test bodies were aged at 110°C for up to 10 weeks. The nanocomposites were characterized by differential scanning calometry, thermogravimetric analysis (TGA), 13C-NMR, elongation at break, and transmission electron microscopy. The aging mainly occurred on the surface of the samples and the neat HDPE showed a strong yellowing after the aging. A strong reduction in elongation at break was seen. For neat HDPE, the elongation at break was reduced from roughly 1400–25%. When HDPE was reinforced with the nanotubes, the reduction was less dramatic

Executive summary Today, packaging has gained a significant role in the food industry as well as other industries. Paper substrates that have been coated in some ways are typically used to make packaging. The amount and type of pigment used in the formulation determine whether this coating is a pigment coating or a barrier coating. Critical pigment volume concentration (CPVC) is the optimum spot when the pigments are packed as densely as possible, and the binder fills the air gaps. When the amount of pigment in a coating is less than CPVC, a barrier coating is formed, although when the amount of pigment in the coating is greater than CPVC, a pigment coating is formed. Pigment coating adds optical properties to a package, such as improved printability. And chemical protection is primarily provided for water, water vapour, fats, and gases in the case of the barrier coating. Chemical protection against these substances means, for food packaging, that the shelf life of the product will be extended, among other things. The role of packaging in society is expected to grow as barrier coatings on packaging continue to improve. The use of nanoclay in barrier coatings is investigated in this laboratory study. Two latexes are tested with nanoclay, with latex chosen based on its glass transition temperature (Tg). The hypothesis was that a latex with a higher Tg would have more properties like brittleness and orderly structure in its amorphous structure than the other latex. Latex with a lower Tg, on the other hand, would have more elasticity, be more ductile, and have a lower degree of ordered structure in its amorphous structure. Latex with a higher Tg was referred to as Hard latex and was composed of Styrene-butadiene, while latex with a lower Tg was referred to as Soft latex and was composed of Polyolefin dispersion, although it is unorthodox to call it latex. Previous research has found that the addition of Bentonite nanoclay can improve the mechanical and barrier properties of barrier coatings. Bentonite was therefore chosen as the nanoclay for this study due to having a higher aspect ratio, is flaky and can improve desired properties. The coating was applied as a dispersion coating using a lab-scale rod coater. The substrate for this study was BillerudKorsnäs FibreForm with a grammage of 150 g/m2.In order to find the optimum rod for the coating, three different rods were tested during screening test 1. The rods tested were based on the desired coating weight and thickness, a red rod with a wet film thickness of 12 μm was chosen. The nanoclay content of the latex formulation was investigated to determine the optimal level for improved barrier properties. In screening test 2, the concentrations examined were 2/4/8 w/w% nanoclay in each latex, and 0 w/w% to compare the difference with Hard/Soft latex to see if there are any benefits of nanoclay. For both latexes, the addition of 2/4 w/w% nanoclay resulted in more pinholes as well as a poor water vapour transmission rate and permeability. The results of screening test 2 showed that adding 8 w/w% nanoclay to both latexes improved the water vapour transmission rate, water vapour permeability, and pinholes test when compared to the other concentrations of nanoclay. In the water vapour transmission rate and pinholes test, however, 0 percent nanoclay performed similarly 8 w/w% for each latex formulation. The selected formulation for further study was 8 w/w% nanoclay with Hard/Soft latex. Water vapour was the most important barrier property to investigate since barrier coatings were intended for food packaging. For the intended food packaging, it was sought that the barrier could be stretched with 3.8/6.7/10.4%-stretch and then characterized by water vapour transmission rate to be able to see the differences before and after stretching. Stretching with tensile tester were performed on a barrier coated FibreForm, first in the machine direction (MD), then in cross-direction (CD). Hydroforming with shaped bubbles was used for the second method of stretching with various bubbles. Stretching in MD + CD, and hydroforming bubbles were done according to the desired %-stretching. Characterization of the coating was done by water vapour transmission rate (WVTR) for all coatings, pinholes test for hydroformed coatings, water vapour permeability (WVP) and scanning electron microscopy (SEM) on tensile-stretched coatings. The performance of Soft latex with an 8 w/w% formulation stretched in MD then CD and characterized by water vapour transmission rate was significantly unchanged despite stretching up to 10.4%. This is thought to be because nanoclay, as the literature suggests, has created a better barrier against water vapour. The mean WVTR of 10.4%-stretching in MD then CD was 5.5 g/m2/day, compared to 5.5 g/m2/day for the unstretched barrier. SEM images of both stretched and non-stretched coatings show that the dispersion of nanoclay is poor, as there are islands of polymer and nanoclay bulk. The poor dispersion of nanoclay in the matrix was due to the lack of polar groups in the backbone of Soft latex (Polyolefin) and also being hydrophobic, as opposed to Bentonite, which is hydrophilic. Despite poor nanoclay dispersion and a stretch of 10.4% in MD + CD, resulting in reduced barrier thickness, WVP improved from 289 g* /m2/day (pre-stress) to 191 g* /m2/day (10.4%-stretch), giving the impression of some reorientation of nanoclay in the polymer matrix. A crack was also visible in SEM images, near the boundary layer between the barrier and the substrate, on an unstretched coating, which is thought to be caused by the difference in the boundary layer and adhesive forces, that has occurred during drying. Cracks are not visible on the stretched barriers, even though it was expected. With increased stretching of hydroforming substrates coated with Soft latex formulation, the performance of water vapour transmission rate was significantly worse. The reason for this is thought to be that the barrier was damaged during hydroforming due to friction during pressing and shaping, as the hydroforming was done on the barrier side. The pinhole test revealed clearly degraded performance with a large number of pinholes. This could indicate that the barrier has been stretched beyond its capacity or has been damaged. There was no correlation found between stretching in tensile tester and hydroforming. Hard latex with an 8 w/w% formulation stretched in MD then CD and characterized by water vapour transmission rate could be stated to have significantly improved performance despite stretching up to 10.4%. The mean-WVTR of 10.4%-stretching in MD then CD was 11.3 g/m2/day, compared to 16.4 g/m2/day for the unstretched barrier. According to SEM images, the reason for this is that nanoclay was very well dispersed in the matrix and that there has seemingly been a slight reorientation of nanoclay with increased stretch. Furthermore, SEM images show that the thickness was reduced, yet despite this, mean-WVP improved from 1094 g* /m2/day (pre-stress) to 419 g* /m2/day (10.4%-stretch), indicating reorientation of nanoclay and thus improved stretchability.These SEM images show cracks at the boundary layer between the barrier and the substrate for both unstretched and 10.4%-stretched barriers in the Hard latex formulation. The cracks are seemingly stopped by nanoclay in the matrix, according to the stress concentration effect, where the crack moves around nanoclay and not through nanoclay. Hydroforming of barrier coated Hard latex formulation showed a deterioration of water vapour transmission rate with increased stretching. The mean WVTR of hydroforming with 10.4%-stretching was 30.6 g/m2/day. It is not thought that pressing during hydroforming damaged the Hard latex barrier as much, which can be confirmed by the pinholes test. Pinholes test demonstrated good performance and comparable to an unstretched barrier. Because comparisons between the different polymers were impractical, it was not possible to state if the glass transition temperature was important for the improvement seen by stretching in the tensile tester. But it can be argued that Hard latex has a more structured and rigid structure, allowing for a greater degree of reorientation. Soft latex, on the other hand, has less stiffness and thus less reorientation. The result of this study is that when stretching is done in both tensile testing and hydroforming, 8 w/w% nanoclay (bentonite) with Hard latex (styrene-butadiene) can be used advantageously in FibreForm packaging if stretchability is desired while maintaining barrier properties against water vapor. Sammanfattning Idag har förpackningar fått en betydande roll i matindustrin såväl som andra industrier. Vid bestrykning på förpackningar och papperssubstrat så är det vanligt med pigment- eller barriärbestrykning. Vid pigmentbestrykning så tillförs optiska egenskaper till förpackningen, såsom exempelvis förbättrad tryckbarhet. Vid barriärbestrykning tillförs huvudsakligen kemisk skydd mot exempelvis vatten, vattenånga, fetter eller gaser, och innebär för matförpackningar bland annat att hållbarheten blir längre för livsmedlet. Genom fortsatt utveckling av barriärbestrykningar på förpackningar så förväntas även förpackningens roll i samhället att bli större. I denna laborativa studie undersöks möjligheterna kring töjbara barriärer på papperssubstrat, med fokus på vattenångaresistans. De formuleringar som togs fram bestod av en latex med låg glasövergångstemperatur (Tg), kallad Soft latex med implementerad nanolera samt en latex med en Tg kallad Hard latex med implementerad nanolera. Soft latex var en Polyolefin dispersion med Tg -30°C, och Hard latex var en Styren-butadien latex med Tg = 0°C. 8 w/w% nanolera var den halt som bedömdes ge förbättringar i de mekaniska samt barriäregenskaper som eftersöktes för de båda latex. För denna studie valdes Bentonit som nanolera, på grund av dess plana samt dess fjälliga (flaky) struktur. Töjbarheten hos de framtagna barriärformuleringarna testades med töjning i dragprov först i maskin-riktning (MD) och sedan tvär-riktning (CD) samt töjning med hydroforming, med töjning på 3,8/6,7/10,4% för respektive metod. Efter töjning av respektive metod bestämdes överföringshastigheten av vattenångpermabilitet (WVTR) genom barriären. En jämförelse gjordes mellan töjning i dragprov och hydroforming för att få en ökad förståelse kring WVTR-prestationen beroende på metod av töjning. Soft latex visade en oförändrad vattenångaresistans efter 10,4%-töjning i dragprovaren. Detta tros bero på att nanoleran försvårar vattenångan att genomträngas trots töjning. Vid elektronmikroskop (SEM) kunde det ses att dispersionen av nanolera med Soft latex inte var bra, och därför var inte förbättringarna lika tydliga. Den sämre dispersionen av nanolera i matrisen beror på att Polyolefin saknar polära grupper i dess ryggrad (backbone) samt är väldigt hydrofobt, till skillnad från Bentonit som är hydrofilt. Trots sämre dispersion av nanolera och en töjning på 10,4% i MD + CD, så förbättrades vattenånga permeabiliteten (WVP).För hydroforming var prestationen av Soft latexformuleringen gällande WVTR dåliga, och vid Pinholes test fanns det uppenbara pinholes. Hard latex visade en tydlig förbättring av WVTR efter 10,4%-töjning i dragprovaren, som tros bero på en omorientering av nanoleran i polymer matrisen vid töjning, vilket kan bekräftas av elektronmikroskop (SEM) där viss omorientering är synlig. Dessutom sågs en tydlig förbättring i WVP trots en lägre barriärtjocklek.För hydroforming var WVTR-värdena liknande till endast Hard latex och 0% nanolera. Vid töjning var jämförelser beroende på de olika glasövergångstemperaturerna hos polymererna inte möjlig, och därför inte heller möjligt att konstatera ifall glasövergångstemperaturen var viktig för den förbättring som setts trots töjning i dragprovare. Men det kan hävdas att Hard latex har en mer strukturerad och stel struktur, vilket möjliggör en större grad av omorientering. Soft latex däremot, är mindre styvt och mindre ordnat, därav åstadkoms en mindre omorientering. Resultaten av denna studie är att när stretching görs i både dragprovning och hydroformning, kan 8 w/w% nanoclay (bentonit) med Hard latex (styren-butadien) vara fördelaktig i FibreForm-förpackning om töjbarhet önskas samtidigt som barriäregenskaperna mot vattenånga bibehålls.

Development of functional and stable solid polymer electrolytes SPEs for battery applications is an important step towards both safer batteries and for the realization of lithium based or anode less batteries. The interface between the lithium and the solid polymer electrolyte is one of the bottlenecks, where severe degradation is expected. Here, the stability of three different SPEs poly ethylene oxide PEO , poly amp; 949; caprolactone PCL and poly trimethylene carbonate PTMC together with lithium bis trifluoromethanesulfonyl imide LiTFSI salt, is investigated after they have been exposed to lithium metal under UHV conditions. Degradation compounds, e.g. Li O R, LiF and LixSyOz, are identified for all SPEs using soft X ray photoelectron spectroscopy. A competing degradation between polymer and salt is identified in the outermost surface region lt;7 nm , and is dependent on the polymer host. PTMC LiTFSI shows the most severe decomposition of both polymer and salt followed by PCL LiTFSI and PEO LiTFSI. In addition, the movement of lithium species through the decomposed interface shows large variation depending on the polymer electrolyte system

Under flera månaders tid har ett kandidatexamensarbete utförts med syftet att optimera produktionen av protein-nanofibrer av vassleproteinisolat. Vassleproteinisolat består till stor del av proteinet β-laktoglobulin. Detta protein kan under upphettning bilda nanofibrer i sur miljö. Det var därför med avseende på parametrarna värme, koncentration och inkubationstid som processen optimerades eftersom det redan existerar ett pH-optimum vid pH-värdet 2. Lösningar av vassleproteinisolat med olika koncentrationer inkuberades under 24 timmar vid fyra olika temperaturer. Samtliga lösningar hade pH-värdet 2. För varje temperatur och inkubering togs proverna ut en åt gången för att sedan analyseras. De olika proverna analyserades sedan med Thioflavin T fluorescens för att se indikationer på fibrillering. De erhållna ThT spektrumen visade på fibrillbildning och resultaten för detta experiment visar på att utbytet av fibrilleringsreaktionen blir högre i takt med att hydrolysens hastighetskonstant blir lägre samt att lägre temperaturer kan gynna fibrillbildning . Ytterligare försök, tid och resurser bör läggas ner på detta område för att med säkerhet kunna optimera produktionen av nanofibrer av vassleproteinisolat. This bachelor’s degree project’s aim was to optimize the production of protein nanofibrils originating from whey protein isolate. Whey protein isolate largely consists of the protein β-lactoglobulin, which can form nanofibrils while immersed in an acidic environment when heated. Therefore, the process was attempted to be optimized with regards to the yield of the final product of protein nanofibrils by varying parameters such as incubation time, initial concentration and temperature, with a constant pH-value of 2. Solutions of the whey protein isolate at different concentrations were incubated during a time interval of 24 hours and at different temperatures. For every temperature and time period of incubation, one sample at a time was taken out to be measured and analyzed, a total of four samples per initial concentration. The samples were analyzed with Thioflavin T fluorescence to see indications of the existence of fibrillation. The obtained ThT spectra showed intensity diagrams that can be related to the amount of formed nanofibrils, and this experiment shows that the yield of fibrils increases while the rate constant of the hydrolysis decreases, and that the fibrillation is favoured by lower temperatures. To optimize the production of nanofibrils of whey protein with certainty, further experiments, time and resources should be invested in this area.

An important factor in the development of sodium-ion batteries (SIBs) is the use of cheap and sustainable materials. Sodium lignosulfonate, a lignin derivative, is demonstrated here as an attractive, “green”, water-soluble, and potentially cost-effective binder for use in hard carbon anodes for SIBs. A comparison of its battery cycling performance is made against other binders including sodium carboxymethyl cellulose and lignin, obtained from the kraft process, as well as sodium alginate, derived from algae. Apart from lignin, which requires processing in N-methyl-2-pyrrolidone, the other three binders are water-soluble. Lignosulfonate shows comparable or better performance, with high capacity retention and stability, when using 1 M NaPF6 in propylene carbonate or ethylene carbonate:diethyl carbonate electrolytes for both half- and full-cells (against a Prussian white cathode). Further improvements are observed when including styrene-butadiene rubber as a co-binder. X-ray photoelectron spectroscopy demonstrates similar solid electrolyte interphase compositions after the initial sodium insertion for both lignosulfonate and carboxymethyl cellulose binders. However, after subsequent cycling, the surface layer composition and thickness are found to be dependent on the binder. For the lignosulfonate-based electrode, the layer appears thicker but comprises a smaller fraction of carbon–oxygen species.

A composite electrolyte based on a garnet electrolyte (LLZO) and polyester-based co-polymer (80:20 epsilon-caprolactone (CL)-trimethylene carbonate, PCL-PTMC with LiTFSI salt) is prepared. Integrating the merits of both ceramic and co-polymer electrolytes is expected to address the poor ionic conductivity and high interfacial resistance in solid-state lithium-ion batteries. The composite electrolyte with 80 wt % LLZO and 20 wt % polymer (PCL-PTMC and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) at 72:28 wt %) exhibited a Li-ion conductivity of 1.31 X 10(-4) S/cm and a transference number (t(Li+)) of 0.84 at 60 degrees C, notably higher than those of the pristine PCL-PTMC electrolyte. The prepared composite electrolyte also exhibited an electrochemical stability of up to 5.4 V vs Li+/Li. The interface between the composite electrolyte and a LiFePO4 (LFP) cathode was also improved by direct incorporation of the polymer electrolyte as a binder in the cathode coating. A Li/composite electrolyte/LFP solid-state cell provided a discharge capacity of ca. 140 mAh/g and suitable cycling stability at 55 degrees C after 40 cycles. This study clearly suggests that this type of amorphous polyester-based polymers can be applied in polymer-in-ceramic composite electrolytes for the realization of advanced all-solid-state lithium-ion batteries.

We study composites of cellulose nanocrystals (CNCs) in an ionomer matrix of poly(ethylene-stat-sodium acrylate) and find that direct cellulose/cellulose interactions in the composite are not a requirement for achieving reinforcement. While isotropic composites only show a slightly enhanced stiffness compared to the neat ionomer, a more substantial increase in Youngs modulus by a factor of up to 5 is achieved by uniaxial alignment of the composites through melt spinning. The orientation of CNC in melt-spun composites reduces the probability of cellulose/cellulose interactions, which suggests that cellulose/polymer interactions must be present that lead to the observed reinforcement. Molecular dynamics simulations confirm strong cellulose/polymer interactions in the form of ionic interactions as well as hydrogen bonding. These cellulose/polymer interactions facilitate efficient stress transfer, leading to the high reinforcing effect of CNC, while cellulose/cellulose interactions play a minor role in the mechanical response of the composite. Funding Agencies|Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RMA15-0052]; Swedish Research Council FormasSwedish Research CouncilSwedish Research Council Formas [FR-2018/0010]; Treesearch; Chalmers University of Technology Foundation; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2018-06487 RFI NanoSPAM]

Polymer-based ion exchange membranes (IEMs) are utilized for many applications such as in water desalination, energy storage, fuel cells and in electrophoretic drug delivery devices, exemplified by the organic electronic ion pump (OEIP). The bulk of current research is primarily focused on finding highly conductive and stable IEM materials. Even though great progress has been made, a lack of fundamental understanding of how specific polymer properties affect ionic transport capabilities still remains. This leads to uncertainty in how to proceed with synthetic approaches for designing better IEM materials. In this study, an investigation of the structure-property relationship between polymer size and ionic conductivity was performed by comparing a series of membranes, based on ionically charged hyperbranched polyglycerol of different polymer sizes. Observing an increase in ionic conductivity associated with increasing polymer size and greater electrolyte exclusion, indi-cating an ionic transportation phenomenon not exclusively based on membrane electrolyte uptake. These findings further our understanding of ion transport phenomena in semi-permeable membranes and indicate a strong starting point for future design and synthesis of IEM polymers to achieve broader capabilities for a variety of ion transport-based applications. Funding Agencies|Swiss Society for Biomaterials and Regenerative Medicine, SSB + RM; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research; Swedish Research CouncilSwedish Research CouncilEuropean Commission; European UnionEuropean Commission [834677]

Attaching hydrogels to soft internal tissues is crucial for the development of various biomedical devices. Tough sticky hydrogel patches present high adhesion, yet with lack of injectability and the need for treatment of contacting surface. On the contrary, injectable and photo-curable hydrogels are highly attractive owing to their ease of use, flexibility of filling any shape, and their minimally invasive character, compared to their conventional preformed counterparts. Despite recent advances in material developments, a hydrogel that exhibits both proper injectability and sufficient intrinsic adhesion is yet to be demonstrated. Herein, a paradigm shift is proposed toward the design of intrinsically adhesive networks for injectable and photo-curable hydrogels. The bioinspired design strategy not only provides strong adhesive contact, but also results in a wide window of physicochemical properties. The adhesive networks are based on a family of polymeric backbones where chains are modified to be intrinsically adhesive to host tissue and simultaneously form a hydrogel network via a hybrid cross-linking mechanism. With this strategy, adhesion is achieved through a controlled synergy between the interfacial chemistry and bulk mechanical properties. The functionalities of the bioadhesives are demonstrated for various applications, such as tissue adhesives, surgical sealants, or injectable scaffolds.

Hard carbons are the most promising negative active materials for sodium ion storage. In this work, a simple synthesis approach is proposed to produce hard carbon microspheres (CMSs) (with a mean diameter of ~1.3 μm) from resorcinol-formaldehyde precursors produced via acid-catalyzed polycondensation reaction. Samples prepared at 1200, 1400, and 1500 oC showed different electrochemical behavior in terms of reversible capacity, initial coulombic efficiency (iCE), and the mechanism of sodium ion storage. The specific capacity contributions from the flat voltage profile (

Increasing the ionic conductivity has for decades been an overriding goal in the development of solid polymer electrolytes. According to fundamental theories on ion transport mechanisms in polymers, the ionic conductivity is strongly correlated to free volume and segmental mobility of the polymer for the conventional transport processes. Therefore, incorporating plasticizing side chains onto the main chain of the polymer host often appears as a clear-cut strategy to improve the ionic conductivity of the system through lowering of the glass transition temperature (T-g) This intended correlation between Tg and ionic conductivity is, however, not consistently observed in practice. The aim of this study is therefore to elucidate this interplay between segmental mobility and polymer structure in polymer electrolyte systems comprising plasticizing side chains. To this end, we utilize the synthetic versatility of the ion-conductive poly(trimethylene carbonate) (PTMC) platform. Two types of host polymers with side chains added to a PTMC backbone are employed, and the resulting electrolytes are investigated together with the side chain-free analogue both by experiment and with molecular dynamics (MD) simulations. The results show that while added side chains do indeed lead to a lower Tg, the total ionic conductivity is highest in the host matrix without side chains. It was seen in the MD simulations that while side chains promote ionic mobility associated with the polymer chain, the more efficient interchain hopping transport mechanism occurs with a higher probability in the system without side chains. This is connected to a significantly higher solvation site diversity for the Li+ ions in the side-chain-free system, providing better conduction paths. These results strongly indicate that the side chains in fact restrict the mobility of the Li+ ions in the polymer hosts.

Over the past decades, concerns for the environment have increased and efforts to achieve a sustainable society have intensified. One particular challenge is to replace fossil-based plastics with biodegradable materials produced from renewable resources. Cellulose nanofibril (CNF)-based materials are strong candidates due to their excellent mechanical properties, nano-dimensions and molecular structure, which is suitable for modification. CNFs can be obtained from wood and are elongated, often charged, particles which are usually handled in aqueous dispersions. The colloidal stability is sensitive, and instability results in aggregation or transition to an arrested state. Since the properties of CNF-based materials rely on dispersion of the CNFs, an understanding of the colloidal behaviour is crucial. This work has focused on the interactions and dynamics of CNFs in different colloidal states. Arrested states of CNFs were studied in detail and it was found that two types of arrested state exist, with different colloidal interactions and mechanisms governing their formation. The dynamics in arrested and dispersed states were studied by tracer diffusion measurements, and it was found that small amounts of CNFs can constitute an excellent stabiliser for other particle dispersions according to a so far unexplored mechanism. The effects of altering the colloidal interactions using different strategies were also evaluated. The counterions of CNFs were exchanged and the impact on the swelling behaviour was measured. Based on the results, different contributions to the counterion-dependent interactions are discussed. Two strategies for using polymers to alter the interactions were furthermore studied. Polyethylene glycol (PEG) was grafted to CNFs in order to increase the arrested state threshold concentration. PEG, carboxymethyl cellulose and lignin, were also used as additives which improved the redispersion of dried CNF, especially in the case of samples containing lignin. Under de senaste decennierna har oron för miljön ökat och strävan mot ett hållbart samhälle har intensifierats. En del i utmaningen är att ersätta fossilbaserad plast med bionedbrytbara material producerade från förnyelsebara råvaror. Cellulosa nanofibrill (CNF)-baserade material är starka kandidater för detta tack vare deras nanostorlek, utmärkta mekaniska egenskaper och gynnsamma molekylära struktur för kemisk modifiering. CNF kan utvinnas från träd och är avlånga, ofta laddade, partiklar som oftast hanteras i vattendispersioner. Den kolloidala stabiliteten styrs av subtila växelverkningar, och instabilitet leder till aggregering eller övergång till ett volymsomfattande låst tillstånd. Egenskaperna hos CNF-baserade material påverkas av hur väl dispergerade fibrillerna är, därmed är det viktigt att förstå de faktorer som styr det kolloidala beteendet. Detta arbete har fokuserat på interaktionerna och dynamiken hos CNF i olika kolloidala tillstånd. Låsta tillstånd av CNF undersöktes och resultaten visade att det finns två typer av låsta tillstånd, med olika interaktioner och mekanismer som ligger bakom hur de genereras. Dynamiken i olika kolloidala tillstånd undersöktes genom att mäta diffusionen av sfäriska partiklar i systemen, och det påvisades att små mängder CNF kan skapa en stabilitet hos andra partiklar via en ny, ännu inte helt utredd, mekanism. De kolloidala interaktionerna modifierades på olika sätt för att klarlägga effekterna på CNFs associationstillstånd. I en serie försök undersöktes hur ett byte av motjoner till ytladdningarna påverkade växelverkan genom att mäta svällningen av nanopapper. Vidare undersöktes två strategier där polymerer användes för att öka repulsionen mellan CNFs. Polyetylenglykol (PEG) kopplades kovalent till CNF för att förhöja koncentrationen för övergången till ett låst tillstånd. PEG, karboximetylcellulosa och lignin användes även som additiv vilket förbättrade återdispergeringen av torkad CNF, speciellt när lignin användes. QC 2020-10-27

We report a side group modification strategy to tailor the structure of a polymer of intrinsic microporosity (PIM-1). PIM-1 with an average of ∼50% of the repeat units converted to tetrazole is prepared, and a subsequent reaction then introduces three types of pseudo-ionic liquid tetrazole-like structures (PIM-1-ILx). The presence of pseudo-ionic liquid functional groups in the PIM-1 structure increases gas selectivities for O2/N2 and CO2/N2, while it decreases pure-gas permeabilities. The overall gas separation performance of PIM-1-ILx is close to the 2008 Robeson upper bound. Since the tetrazoles are versatile groups for building a wide variety of ionic liquids, the modification method can be expanded to explore a broad spectrum of functional groups.

The last decades have been overshadowed by reports about the seemingly endless increase use of fossil-based resources. With the development of new products, our mindset is changing so that we more and more need to consider sustainability in our daily lives. Furthermore, smarter devices are indispensable in our world and daily life, and these are expected to be smaller and smaller in size. To support the transition from fossil-based to sustainable materials, we need to develop knowledge of new materials. Within this thesis project, the aim has been to understand the thin-film properties of sustainable materials and to develop methodologies to measure these. As sustainable template material wood-based nanocellulose was chosen as a bio-degradable representative with favourable favourable physical properties, such as lightweight, transparency, and flexibility. These properties make nanocellulose a perfect candidate for future advanced applications in thin-film organic solar cells, supercapacitors, or sensors. Nanocellulose comprises only a part of such a device, and hence the relevant functional materials and their combinations have to be studied to reveal the interaction between multiple material components on the final device performance. As the nanoscale, or even Ångstrom scale, governs the macroscopic physical properties, it is crucial to understand the materials in detail. Ergo, neutron and X-ray surface-sensitive scattering methods were applied to study nanoparticle deposition layering kinetics and the effects of environmental changes, which revealed the morphology of the resulting nanoporous nanocellulose thin films. The knowledge was used to infiltrate water-soluble intrinsic conductive polymers into these nanopores, which serves as a model for transparent but conductive templates for organic electronics. By changing the environment of the films through humidity cycling, the impact of the environment during a real-life application could be illustrated. Neutron scattering experiments also showed that the cellulose-conductive polymer composite (or hybridmaterial) changes irreversibly during humidity cycling while the pure nanocellulose films show fully reversible properties. Furthermore, the thermal decomposition of silver nitrate deposited on nanocellulose was studied to understand the nanofibrils' impact on the synthesis of nanoparticles. The transparency allowed in situ studies of the synthesis process, the spectroscopic properties as well as the plasmonic effect, which demonstrated routes for minimal material usage concepts for surface synthesis processes. It was also discovered that the process allows for band-gap tuning, which can be directly be applied in organic solar cells to tailor the band-gap to be adapted and hence increasing the efficiency.The morphological properties, as studied using X-rays and neutrons, were correlated to macroscopic properties by measuring wettability, surface topography, spectroscopy, or conductivity to examine the full materials application possibilities. Neutron and X-ray scattering methods are complementary and wisely combined, thus allowed pioneering studies of bio-based sustainable nanocomposites leading to advanced functional material concepts that support the development of devices using less fossil-based materials. Den ökande användningen av fossilbaserade resurser representerar en global samhällsutmaning som kan mötas genom utveckling av nya materialkoncept. Vårt samhälle fylls även av smarta produkter, vilka både förväntas bidra till ökad hållbarhet och att kontinuerligt bli mindre i storlek. För att möjliggöra denna utveckling och samtidigt minska användningen av fossilbaserade material behöver vi öka vår kunskap om nya biobaserade material och deras användning. Målet med denna avhandling är en ökad insikt i egenskaperna hos tunna biobaserade filmer, och att utveckla metoder för att karakterisera dessa egenskaper. Utgångspunkten har varit att använda vedbaserad nanocellulosa, en biobaserad och förnyelsebar råvara som är biologiskt nedbrytbar, har mycket goda mekaniska egenskaper, och kan användas för framställningen av materialkoncept med låg densitet, transparens och flexibilitet. Detta gör nanocellulosa till en perfekt grundkomponent i framtida avancerade biobaserade tunnfilmsapplikationer såsom organiska solceller, superkondensatorer eller sensorer, vilket möjliggörs genom inblandning av komponenter som ger önskad funktion. Olika materialkoncept har därför studerats med syftet att öka förståelsen för interaktionerna mellan olika komponenter och hur dessa påverkar prestanda och funktion. De makroskopiska egenskaperna av ett material ges av dess hierarkiska struktur, från ångströms- och nanometerskalan och upp till variationer på mikrometer och millimeterskalan. Ergo har fokus varit på att studera kinetik relaterat till framställning av filmer uppbyggda genom ytdeponering av nanopartiklar, inkluderande studier av effekter av omgivande atmosfär. Dessa studier har genomförts med hjälp av ytselektiva neutron- och röntgenspridningsmetoder och har resulterat i goda insikter i morfologin hos tunna nanoporösa nanocellulosafilmer. Vidare har även effekter av att fylla dessa nanoporer med vattenlösliga ledande polymerer studerats, då detta är en intressant funktionaliseringsväg som möjliggör tillverkning av transparenta och ledande templat för organisk elektronik. I detta sammanhang studerades även effekter av fuktvariationer i omgivningen, vilket är en viktig frågeställning för många biobaserade material och cellulosabaserade material i synnerhet. Med hjälp av neutronspridningsexperiment kunde skillnader mellan rena nanocellulosafilmer och filmer fyllda med ledande polymerer studeras, där strukturen hos de rena filmerna förändras reversibelt under fuktcykling, till skillnad från filmerna med ledande polymerer, vars struktur förändrades irreversibelt. Slutligen studerades även temperaturens inverkan på syntesen av nanopartiklar som initieras genom deponering av silvernitrat på nanocellulosafilmer, där materialens transparens tillät in-situ studier av processen, spektroskopiska egenskaper samt plasmoniska effekter. Detta visade att nanocellulosafilmer är ett lovande templat för ytsyntesprocesser, där det särskilt observerades att de olika processparametrarna direkt kan kopplas till det observerade bandgapet, kunskaper som kan användas för att skräddarsy organiska solceller så att dessa blir effektivare. QC 201117

Nickel(II)-aryl complexes [(L-2)Ni(Ar)Br] bearing either chiral phosphine ligands (L-2=RR- orSS-DIPAMP, Ar =ortho-anisyl), or a chiral aryl-group have been prepared, and their structural optical an chiroptical properties have been characterized. Enantiomeric pairs of both catalysts have been used for the asymmetric polymerization of different isocyanides (M1,M2,M3), to give well defined polyisocyanides (P1,P2,P3). Their polymerization behavior has been studied, which confirmed chain-growth polymerization in all cases. The asymmetric induction has been verified by circular dichroism spectroscopy on enantiomeric pairs of all three polymers.

Solid polymer electrolytes (SPEs) are promising candidates for solid-state lithium-ion batteries. Potentially, they can be used with lithium metal anodes and high-voltage cathodes, provided that their electrochemical stability is sufficient. Thus far, the oxidative stability has largely been asserted based on results obtained with sweep voltammetry, which are often determined and reliant on arbitrary assessments that are highly dependent on the experimental conditions and do not take the interaction between the electrolyte and the electrode material into account. In this study, alternative techniques are introduced to address the pitfalls of sweep voltammetry for determining the oxidative stability of SPEs. Staircase voltammetry involves static conditions and eliminates the kinetic aspects of sweep voltammetry, and coupled with impedance spectroscopy provides information of changes in resistance and interphase layer formation. Synthetic charge–discharge profile voltammetry applies the real voltage profile of the active material of interest. The added effect of the electrode active material is investigated with a cut-off increase cell cycling method where the upper cut-off voltage during galvanostatic cycling is gradually increased. The feasibility of these techniques has been tested with both poly(ethylene oxide) and poly(trimethylene carbonate) combined with LiTFSI, thereby showing the applicability for several categories of SPEs.

Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low-cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi-metallic conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm2/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X-ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer-based devices, The authors acknowledge the European Research Council (ERC-starting-grant 307596), the Swedish foundation for strategic research (project: “Nano-material and Scalable TE materials”), the Knut and Alice Wallenberg foundation (project “Power Paper” and “Tail of the Sun”), The Swedish Energy Agency (3833221), the Swedish Research Council via “Research Environment grant” on “Disposable paper fuel cells” (2016205990), and the Advanced Functional Materials Center at Linköping University. The authors thank Masatsugu Yamashita from the THz Sensing & Imaging Lab at RIKEN in Japan for conducting the THz reflectance spectroscopy experiments. D.R. Evans acknowledges the support of the Australian Research Council through the Future Fellowship scheme (FT160100300). J.W. Andreasen acknowledges the support of the European Research Council (ERC-consolidator-grant 681881). The computations were performed on resources provided by the Swedish National Infrastructure for Computing (SNIC) at NSC.

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) has been reported as a successful functional material in a broad variety of applications. One of the most important advantages of PEDOT:PSS is its water-solubility, which enables simple and environmental friendly manufacturing processes. Unfortunately, this also implies that pristine PEDOT:PSS films are unsuitable for applications in aqueous environments. To reach stability in polar solvents, (3-glycidyloxypropyl)trimethoxysilane (GOPS) is typically used to cross-link PEDOT:PSS. Although this strategy is widely used, its mechanism and effect on PEDOT:PSS performance have not been articulated yet. Here, we present a broad study that provides a better understanding of the effect of GOPS on the electrical and electronic properties of PEDOT:PSS. We show that the GOPS reacts with the sulfonic acid group of the excess PSS, causing a change in the PEDOT:PSS film morphology, while the oxidation level of PEDOT remains unaffected. This is at the origin of the observed conductivity changes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 814–820

Small interfering RNAs (siRNAs) are powerful tools for post-transcriptional gene silencing, which offers enormous opportunities for tissue engineering applications. However, poor serum stability, inefficient intracellular delivery, and inevitable toxicity of transfection reagents are the key barriers for their clinical translation. Thus, innovative strategies that allow safe and efficient intracellular delivery of the nucleic acid drugs at the desired site is urgently needed for a smooth clinical translation of therapeutically appealing siRNA-based technology. In this regard, we have developed an innovative siRNA transfection protocol that employs a short incubation time of just 5 min. This allows easy transfection in suspension followed by transplantation of the cells in a hyaluronic acid (HA) hydrogel system. We also report here the unique ability of siRNA to bind HA that was quantified by siRNA release and rheological characterization of the HA-hydrogel. Such interactions also showed promising results to deliver functional siRNA in suspension transfection conditions within 30 min using native HA, although removal of excess HA by centrifugation seem to be essential. In the 2D experiments, suspension transfection of hMSCs with RNAiMAX resulted in ≈90% gene silencing (with or without removal of the excess reagent by centrifugation), while HA demonstrated a modest ≈40% gene silencing after removal of excess reagent after 30 min. Transplantation of such transfected cells in the HA-hydrogel system demonstrated an improved knockdown (≈90% and ≈60% with RNAiMAX and HA respectively after 48 h), with lower cytotoxicity (up to 5-days) as determined by PrestoBlue assay. The gene silencing efficiency in the 2D and 3D conditions were also confirmed at the protein levels by Western blot analysis. We postulate this novel transfection method could be applied for in vivo applications as it allows minimal manipulation of cells that are to be transplanted and reduce toxicity.

Currently, there are limited approaches to tailor 3D scaffolds cross-linked with a stable covalent C-C bond that does not require any catalysts or initiators. We present here the first hydrogels employing aldol condensation chemistry that exhibit exceptional physicochemical properties. We investigated the aldol-cross-linking chemistry using two types of aldehyde-modified hyaluronic acid (HA) derivatives, namely, an enolizable HA-aldehyde (HA-Eal) and a non-enolizable HA-aldehyde (HA-Nal). Hydrogels formed using HA-Eal demonstrate inferior cross-linking efficiency (due to intramolecular loop formation), when compared with hydrogels formed by mixing HA-Eal and HA-NaI leading to a cross-aldol product. The change in mechanical properties as a result of cross-linking at different pH values is determined using rheological measurements and is interpreted in terms of molecular weight between cross-links (Mc). The novel HA cross-aldol hydrogel demonstrate excellent hydrolytic stability and favorable mechanical properties but allow hyaluronidase-mediated enzymatic degradation. Interestingly, residual aldehyde functionality within the aldol product rendered the tissue-adhesive properties by bonding two bone tissues. The aldehyde functionality also facilitated facile post-synthetic modifications with nucleophilic reagents. Finally, we demonstrate that the novel hydrogel is biocompatible with encapsulated stem cells that show a linear rate of expansion in our 3-6 days of study.

Due to climate change and plastic pollution, there is an increasing demand for bio-based materials with similar properties to those of common plastics yet biodegradable. In this respect, cellulose is a strong candidate that is already being refined on a large industrial scale, but the properties differ significantly from those of common plastics in terms of shapeability and water-resilience. This thesis investigates how supramolecular interactions can be used to tailor the properties of cellulose-based materials by modifying cellulose surfaces or control the assembly of cellulose nanofibrils (CNFs). Most of the work is a fundamental study on interactions in aqueous environments, but some material concepts are presented and potential applications are discussed. The first part deals with the modification of cellulose by the spontaneous adsorption of xyloglucan or polyelectrolytes. The results indicate that xyloglucan adsorbs to cellulose due to the increased entropy of water released from the surfaces, which is similar to the increased entropy of released counter-ions that drives polyelectrolyte adsorption. The polyelectrolyte adsorption depends on the charge of the cellulose up to a limit after which the charge density affects only the first adsorbed layer in a multilayer formation. Latex nanoparticles with polyelectrolyte coronas can be adsorbed onto cellulose in order to prepare hydrophobic cellulose surfaces with strong and ductile wet adhesion, provided the glass transition of the core is below the ambient temperature. The second part of the thesis seeks to explain the interactions between different types of cellulose nanofibrils in the presence of different ions, using a model consisting of ion-ion correlation and specific ion effects, which can be employed to rationally design water-resilient and transparent nanocellulose films. The addition of small amounts of alginate also creates interpenetrating double networks, and these networks lead to a synergy which improves both the stiffness and the ductility of the films in water. A network model has been developed to understand these materials, with the aim to explain the properties of fibril networks, based on parameters such as the aspect ratio of the fibrils, the solidity of the network, and the ion-induced interactions that increase the friction between fibrils. With the help of this network model and the model for ion-induced interactions, we have created films with wet-strengths surpassing those of common plastics, or a ductility suitable for hygroplastic forming into water-resilient and biodegradable packages. Due to their transparency, water content, and the biocompatibility of cellulose, these materials are also suitable for biomaterial or bioelectronics applications. På grund av klimatförändringar och ständigt ökande plastföroreningar finns det en växande efterfrågan på biobaserade material med egenskaper som liknar dem hos vanliga plaster och som samtidigt är biologiskt nedbrytbara. I detta avseende är cellulosa är en stark kandidat som redan framställs i stor industriell skala, men egenskaperna skiljer sig markant från plasternas med avseende på formbarhet och vattentålighet. Denna avhandling undersöker hur supramolekylära interaktioner kan användas för att skräddarsy egenskaperna hos cellulosa-baserade material genom att modifiera cellulosaytor eller styra hur cellulosa nanofibriller (CNFs) sätts samman. Huvuddelen av arbetet berör grundläggande studier kring interaktioner i vatten, men några materialkoncept och potentiella tillämpningar diskuteras. Den första delen avhandlar hur spontan adsorption av xyloglukan eller polyelektrolyter kan användas för att modifiera cellulosa. Resultaten indikerar att xyloglukan adsorberar till cellulosa på grund av den ökade entropin hos vatten som frigörs från ytorna, vilket liknar den ökade entropin hos frigjorda motjoner som driver polyelektrolytadsorption. Adsorptionen av polyeletrolyter beror på cellulosans laddning upp till en viss gräns, varefter laddningstätheten endast påverkar adsorptionen i första lagret i en multilager formering. Adsorption av latexnanopartiklar med en korona av polyeletrolyter, ger hydrofoba cellulosaytor med stark och töjbar, våt vidhäftning, om kärnans glasövergång sker vid lägre temperatur än omgivningens. Syftet med den andra delen av avhandlingen är att förklara interaktioner mellan olika typer av cellulosa nanofibriller i närvaro av olika joner. Detta görs med en modell bestående av jon-jonkorrelation och specifika joneffekter, som kan användas för rationell design av vattentåliga och transparenta filmer av nanocellulosa. Tillsatsen av små mängder alginat skapar också interpenetrerande dubbla nätverk, och dessa nätverk leder till en synergi som förbättrar både styvheten och töjbarheten hos filmerna i vatten. En nätverksmodell utvecklades för att förstå dessa material. Modellen klarar av att förklara hur egenskaperna hos fibrillnätverk beror av parametrar som fibrillernas geometri, nätverkets soliditet och friktionen som induceras av specifika joner. Med hjälp av nätverksmodellen och modellen för joninducerade interaktioner kan vi skapa filmer med våtstyrka som överträffar den hos många plaster, eller med en töjbarhet som är lämplig för hygroplastisk formpressning till vattentåliga och biologiskt nedbrytbara förpackningar. Filmernas transparens och vatteninnehåll, samt biokompatibiliteten hos cellulosa, gör dem lämpliga som biomaterial eller för bioelektronikapplikationer. QC 20190411

Solid polymer electrolytes based on high-molecular-weight poly(trimethylene carbonate) (PTMC) in combination with NaFSI salt were investigated for application in sodium batteries. The polycarbonate host material proved to be able to dissolve large amounts of salt, at least up to a carbonate:Na+ ratio of 1:1. Combined DSC, conductivity, and FTIR data indicated the formation of a percolating network of salt clusters along with the transition to a percolation-type ion transport mechanism at the highest salt concentrations. While the highest total ionic conductivities were seen at the highest salt concentrations (up to a remarkable 5 x 10(-5) S cm(-1) at 25 degrees C at a 1:1 carbonate:Na+ ratio), the most stable battery performance was seen at a more moderate salt loading of 5:1 carbonate:Na+, reaching >80 cycles at a stable capacity of similar to 90 mAh g(-1) at 60 degrees C in a sodium metal/Prussian blue cell. The results highlight the importance of the choice of salt and salt concentration on electrolyte performance as well as demonstrate the potential of utilizing polycarbonate-based electrolytes in sodium-based energy storage systems.

Covalent cross-linking chemistry is currently exploited in the preparation of biomaterial for biomedical applications. Choice of these chemistries for the preparation of biomaterials and bioconjugates strongly influences the biological output of these materials. Therefore, this thesis aims to develop novel bioconjugation strategies understanding their advantages and drawbacks. Our results provide new insight to adapt these chemical transformations for a specific application. The first part of this thesis points out the relevance of tuning different properties of biomaterials with specific emphasis on the development of hyaluronic acid (HA) hydrogels. The second part of the thesis describes how different chemical transformations including hydrazone formation (Paper I), thiazolidine formation (Paper II), cross-aldol addition reaction (Paper III) and disulfide formation (Paper IV) dictate material properties. This thesis explores both basic organic reaction mechanism and application of these reactions to influence material characteristics. The detailed study of the reaction conditions, kinetics, and stability of the products will help to understand the mechanical properties, hydrolytic stability, and degradability of the materials described here. Additionally, we performed degradation studies of gadolinium labeled HA hydrogels using magnetic resonance imaging. Furthermore, we also explored post-synthetic modification of hydrogels to link model fluorescent moieties as well as explored the tissue adhesive properties using Schiff-base formation. In summary, this thesis presents a selection of different covalent chemistries for the design of advanced biomaterials. The advantages and disadvantages of these chemistries are rigorously investigated. We believe, such an investigation provides a better understanding of the bioconjugation strategies for the preparation of biomaterials with potential clinical translation.

The relatively new and still growing field of 3D-printing has opened up the possibilities to manufacture patient-specific medical devices with high geometrical accuracy in a precise and quick manner. Additionally, biocompatible materials are a demand for all medical applications while biodegradability is of importance when developing scaffolds for tissue growth for instance. With respect to this, this project consisted of developing biocompatible and bioresorbable polymer blend and composite filaments, for fused deposition modeling (FDM) printing. Poly(lactic acid) (PLA) and polycaprolactone (PCL) were used as supporting polymer matrix while hydroxyapatite (HA), a calcium phosphate with similar chemical composition to the mineral phase of human bone, was added to the composites to enhance the biological activity. PLA and PCL content was varied between 90–70 wt% and 10-30 wt%, respectively, while the HA content was 15 wt% in all composites. All materials were characterized in terms of mechanical properties, thermal stability, chemical composition and morphology. An accelerated degradation study of the materials was also executed in order to investigate the degradation behavior as well as the impact of the degradation on the above mentioned properties. The results showed that all processed materials exhibited higher mechanical properties compared to the human trabecular bone, even after degradation with a mass loss of around 30% for the polymer blends and 60% for the composites. It was also apparent that the mineral accelerated the polymer degradation significantly, which can be advantageous for injuries with faster healing time, requiring only support for a shorter time period.

The widespread use of renewable nanomaterials has been limited due to poor integration with conventional polymer matrices. Often, chemical and physical surface modifications are implemented to improve compatibility, however, this comes with environmental and economic cost. This work demonstrates that renewable nanomaterials, specifically cellulose nanocrystals (CNCs), can be utilized in their unmodified state and presents a simple and versatile, one-step method to produce polyamide/CNC nanocomposites with unique Janus-like properties. Nanocomposites in the form of films, fibers, and capsules are prepared by dispersing as-prepared CNCs in the aqueous phase prior to the interfacial polymerization of aromatic diamines and acyl chlorides. The diamines in the aqueous phase not only serve as a monomer for polymerization, but additionally, adsorb to and promote the incorporation of CNCs into the nanocomposite. Regardless of the architecture, CNCs are only present along the surface facing the aqueous phase, resulting in materials with unique, Janus-like wetting behavior and potential applications in filtration, separations, drug delivery, and advanced fibers. QC 20191119

Effective and economical carbon dioxide-methane separation (CO2/CH4) is highly desirable in several industries such as sweetening natural gases and renewable natural gas (RNG) from biogas and landfills. Among the different separation technologies, membrane separation has been shown to have lower cost of production and lower CH4 losses. In this study, Zeolitic Imidazole Frameworks (ZIF-8) crystals with sizes varying from 45 nm to 450 nm were synthesized and incorporated in the polymer of intrinsic microporosity, PIM-1, to form mixed matrix membranes (MMMs). The structure, morphology, and physicochemical properties of the MMMs were characterized by 1H NMR, FTIR, XRD, TGA, and SEM. ZIF-8 crystal size was controlled using the concentration of sodium formate. The influence of the ZIF-8 crystal size on MMMs was studied by sorption, gas permeability, and aging of the membranes. The MMMs with ZIF-8 crystals of 120 nm particle diameter yielded the greatest improvement in gas transport properties; the CO2/CH4 selectivity-CO2 permeability was 11.4 and 9700 Barrer compared to PIM-1 with 6.4 and 9300 Barrer respectively. The former is near the Robeson 2008 upper bound, while PIM-1 is on the 1991 upper bound. After 40 days of aging, selectivity increased and permeability decreased; the changes were parallel to the Robeson upper bounds indicating increased polymer packing and diffusivity selectivity.

Biodegradable aliphatic polyesters such as poly(lactide) and poly(ϵ-caprolactone), largely used in tissue engineering applications, lack suitable functional groups and biological cues to enable interactions with cells. Because of the ubiquity of thiol groups in the biological environment and the pliability of thiol chemistry, we aimed to design and synthesize poly(ester) chains bearing pendant thiol-protected groups. To achieve this, 3-methyl-6-(tritylthiomethyl)-1,4-dioxane-2,5-dione, a lactide-type monomer possessing a pendant thiol-protected group, was synthesized. This molecule, when used as a monomer in controlled ring-opening polymerization in combination with lactide and ϵ-caprolactone, appeared to be a convenient "building block" for the preparation of functionalized aliphatic copolyesters, which were easily modified further. A polymeric sample bearing pyridyl disulfide groups, able to bind a cysteine-containing peptide, was efficiently obtained from a two-step modification reaction. Porous scaffolds were then prepared by blending this latter copolymer sample with poly(l-lactide-co-ϵ-caprolactone) followed by salt leaching. A further disulfide exchange reaction performed in aqueous medium formed porous scaffolds with covalently linked arginine-glycine-aspartic acid sequences. The scaffolds were characterized by thermal and mechanical tests, and scanning electron microscopy surface images revealed a highly porous morphology. Moreover, a cytotoxicity test indicated good cell viability. QC 20160518

In this report, the crosslinking density of bupivacaine molecularly imprinted methacrylic acid (MAA)-ethylene glycol dimethacrylate (EGDMA) copolymers was investigated through replacement of EGDMA by methyl methacrylate (MMA). The effects were examined using a series of full-scale MD simulations of pre-polymerization mixtures, equilibrium rebinding studies on the corresponding synthesized polymers and morphology characterization through nitrogen sorption measurements. While the extent of hydrogen bonding between the functional monomer MAA and bupivacaine observed in the MD pre-polymerization mixtures was comparable in each of the systems studied, the decrease in degree of crosslinking impacted directly on polymer morphology as observed in BET and BJH studies of surface area and porosity. Further, decreases in the crosslinking density induced reductions in template rebinding capacity as seen from a series of radio-ligand binding studies, demonstrating the importance of crosslinking on the performance of molecularly imprinted MAA-EGDMA copolymers, the polymer system most commonly used in molecular imprinting science and technology.

A novel rapid method for bacterial differentiation is explored based on the specific adhesion pattern of bacterial strains to tunable polymer surfaces. Different types of counter ions were used to electrochemically fabricate dissimilar polypyrrole (PPy) films with diverse physicochemical properties such as hydrophobicity, thickness and roughness. These were then modulated into three different oxidation states in each case. The dissimilar sets of conducting polymers were exposed to five different bacterial strains, Deinococcus proteolyticus, Serratia marcescens, Pseudomonas fluorescens, Alcaligenes faecalis and Staphylococcus epidermidis. By analysis of the fluorescent microscope images, the number of bacterial cells adhered to each surface were evaluated. Generally, the number of cells of a particular bacterial strain that adhered varied when exposed to dissimilar polymer surfaces, due to the effects of the surface properties of the polymer on bacterial attachment. Similarly, the number of cells that adhered varied with different bacterial strains exposed to the same surface, reflecting the different surface properties of the bacteria. Principal component analysis showed that each strain of bacteria had its own specific adhesion pattern. Hence, they could be discriminated by this simple, label-free method based on tunable polymer arrays combined with pattern recognition. (C) 2015 Elsevier B.V. All rights reserved. Funding Agencies|Iranian Ministry of Science, Research and Technology; Linkoping University; Swedish Research Council [VR-2014-3079]

We describe the fast reaction kinetics between 1,2-aminothiols and aldehydes. Under physiological conditions such a click-type reaction afforded a thiazolidine product that remains stable and did not require any catalyst. This type of bioorthogonal reaction offers enormous potential for the coupling of biomolecules in an efficient and biocompatible manner.

Organic photovoltaics devices (OPV) have attracted attentions of scientist for their potential as inexpensive, lightweight, flexible and suitable for roll-to-roll production. In recent years, considerable attention has been focused on new acceptor materials, either polymeric or small molecules, to replace the once dominating fullerene derivatives. The emergence of numerous new non-fullerene materials has driven power conversion efficiency (PCE) up to 17%, attracting more and more interests of commercialization. Polymer acceptors with more morphology stability, more absorption and more desired energy levels has been intensively studied and show great potential for large area and low-cost production in the future. OPV at this moment is not yet competitive with inorganic solar cells in PCE but is more attractive in flexibility, low weight and semitransparency. In this thesis, some basic knowledges of OPV is introduced in the first few chapters, while the next chapters are focusing on polymer-polymer blends and investigating novel structures and techniques for large scale production of solar cells and photodetectors aiming at maximizing these advantages to compete with inorganic counterpart. Thermal annealing effects on polymer-polymer solar cells based is studied. Annealed devices show doubled power conversion efficiency compared to non-annealed devices. Based on the morphology—mobility examination, we conclude that the better charge transport is achieved by higher order and better interconnected networks of the bulk heterojunction in the annealed active layers. The annealing improves charge transport and extends the conjugation length of the polymers, which do help charge generation and meanwhile reduce recombination. The blend of an amorphous polymer and a semi-crystalline polymer can thus be modified by thermal annealing to double the power conversion efficiency. A novel concept of all-polymer organic photovoltaics device is demonstrated in this thesis where all the layers are made out of polymers. We use PEDOT:PSS as semitransparent anode and polyethyleneimine modified PEDOT:PSS as semitransparent cathode, both of which are slot-die printed on polyethylene terephthalate(PET). Active layers are deposited on cathode and anode surfaces by spin coating separately. These layers are then joined through a roll-to-roll compatible lamination process. This forms a semitransparent and flexible solar cell. By laminating a thin layer acceptor polymer to a thick polymer-polymer blend, we can further improve the performance by reducing traps comparing to laminating blend to blend. Flexible and semitransparent all-polymer photodiodes with different geometries can be fabricated through lamination. By choosing high band gap polymers and appropriate combination of two or more polymers, organic photodiode with low noise and high specific detectivity can be obtained. Comparison between bilayer and bulk heterojunction devices gives better understanding of the origin of noise and provides ways to improve the performance of photodiodes as detector. Noise level is a critical parameter for photodetectors. The difficulties of measuring the noise of photodetectors make some researchers prefer the estimated shot noise as the dominating one and ignore the thermal noise and 1/f noise. The latter two terms are sometimes several orders higher than the former, noting the importance of experimentally measuring noise. The use of semi-transparent photovoltaic devices causes an inevitable loss of photocurrent, as light transmitted has not been absorbed. This trivial effect also leads to a loss of photovoltage, an effect partially due to the lower photocurrent but also due to the geometry of the semitransparent photovoltaic device. We here demonstrate and evaluate this photovoltage loss in semi-transparent organic photovoltaic devices, compared with non-transparent solar cells of the same material. Semi-transparent solar cells in addition introduce photovoltage loss when formed by lamination. We document and analyze these effects for a number of polymer blends in the form of bulk heterojunctions.

Textile actuators are an emerging technology to develop biomimetic actuators with synergetic actuation. They are composed of a passive fabric coated with an electroactive polymer providing with mechanical motion. Here we used different conducting yarns (polyamide + carbon, silicon + carbon, polyamide + silver coated, cellulose + carbon, polyester + 2 x INOX 50µm, polyester + 2 x Cu/Sn and polyester + gold coated) to develop such textile actuators. It was possible to coat them through direct electrochemical methods, which should provide with an easier and more cost-effective fabrication process. The conductivity and the electrochemical properties of the yarns were sufficient to allow the electropolymerization of the conducting polymer polypyrrole on the yarns. The electropolymerization was carried out and both the linear and angular the actuation of the yarns was investigated. These yarns may be incorporated into textile actuators for assistive prosthetic devices easier and cheaper to get and at the same time with good mechanical performance are envisaged. Funding agencies: Carl Tryggers Stifelsen [CTS16:207]; Swedish Research Council [VR-2014-3079]; Erling-Persson Family Foundation [2017-10-09]; Promobilia Foundation [F17603]