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The work in this licentiate thesis examines the adsorption of polyelectrolyte multilayers (PEM) onto wood fibres as a new way to influence the properties of the fibre surfaces and hence the fibres. Fundamental aspects of PEM formation on wood fibres have been studied, and discussed in terms of paper strength and wood fibre wettability. PEMs have been formed from three different polymer systems: 1) two strong polyelectrolytes (i.e., fully charged over a wide pH range), polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulphonate (PSS); 2) polyethylene oxide (PEO) and polyacrylic acid (PAA), formed at low pH and held together by hydrogen bonding; and 3) two weak polyelectrolytes, polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA). The PEMs formed from PDADMAC/PSS and PEO/PAA were studied using Stagnation Point Adsorption Reflectometry (SPAR), with SiO2 as the substrate. This was done to establish the formation of PEMs and, using PDADMAC/PSS, also to predict the influence of salt concentration during PEM formation. The amount of PDADMAC/PSS adsorbed was found to increase with salt concentration up to approximately 0.1 M NaCl. The formation of PEMs from PAH/PAA has already been studied in terms of structure; amount adsorbed, and influence on paper strength. Sheets were formed from fibres treated with either PDADMAC/PSS or PEO/PAA PEMs and tested to determine paper tensile strength. Both PEM systems increased the tensile index and strain at break in the range of 100% when approximately 10 layers had been adsorbed. After several PEM layers had been adsorbed, the sheets made of fibres treated with PDADMAC/PSS differed in tensile strength depending on the polymer adsorbed in the outermost layer. A higher tensile strength was detected when PDADMAC rather than PSS was adsorbed in the outermost layer. Sheets made of fibres treated with PEO/PAA displayed a linear increase in strength, independent of which polymer that was adsorbed in the outermost layer. The amount of adsorbed PDADMAC/PSS, as analysed using nitrogen and sulphur analysis, respectively, increased linearly, but with a higher amount adsorbed in the first layer. A comparison of the adsorption onto the SiO2-surfaces (SPAR-measurements) and fibres shows some differences. This is apparent both regarding the adsorption in the first layer and in the change in adsorbed amount with salt concentration. Despite this, one can conclude that SiO2 and wood fibres show very similar trends, and that SiO2 can be used as a convenient model surface in predicting PEM formation on wood fibres. Individual fibres were also partially treated using a Dynamic Contact Angle Analyser, and the treated and untreated parts were analysed in terms of wettability and surface structure. The differences in wettability are significant, depending on the polymer system used and, with PAH/PAA PEMs, the pH strategy show a large influence in wettability. PDADMAC/PSS and PAH/PAA PEMs both had a large influence on wettability, depending on the polymer adsorbed in the outermost layer, wettability being lower when the cationic polymer was adsorbed in the outermost layer. With the PEO/PAA system, however, the polymer adsorbed in the outermost layer caused no detectable difference. These results, when compared against the paper strength results, indicate that the strongest sheets are formed of the fibres with the lowest wettability. This may be explained in terms of wet adhesion: since the fibre networks are formed in water, lower wettability would give a stronger force between the fibres during consolidation, resulting in a greater contact area and thus probably a stronger dry adhesion between the fibres in the formed sheet. This is furthermore also supported by wet adhesion measurements using Atomic Force Microscopy where PEMs formed from PAH/PAA, show that the pull-off force is increased when PAH is adsorbed in the outermost layer, compared to when PAA is adsorbed in the outermost layer. / Denna licentiatavhandling behandlar adsorption av polyelektrolytmultiskikt (multiskikt) på cellulosafibrer som ett nytt sätt att påverka en fibers ytegenskaper. Grundläggande förutsättningar för bildandet av multiskikt på fibrer diskuteras i termer av pappersstyrka och fibervätning. Multiskikt har bildats med hjälp av tre olika polymerkombinationer; 1.) två starka polyelektrolyter, polydiallyldimetylammoniumklorid (PDADMAC) och polystyrensulfanat (PSS), 2.) polyetylenoxid (PEO) och polyakrylsyra (PAA), adsorberade vid lågt pH och sammanhållna av icke elektrostatiska vätebindningar, och 3.) två svaga polyelektrolyter, polyallylaminhydroklorid (PAH) och PAA. Uppbyggnaden av multiskikt bestående av PDADMAC/PSS och PEO/PAA på kiseloxid studerades med Stagnationspunktsreflektometri (SPAR) för att undersöka att uppbyggnad av PEM skett, samt att studera hur uppbyggnaden påverkas av koncentrationen NaCl i polymerlösningen. Försöken visade att den adsorberade mängden PDADMAC/PSS ökade med saltkoncentrationen upp till 0,05-0,1 M NaCl. Uppbyggnaden av multiskikt bestående av PAH/PAA är sedan tidigare studerad undersöks därför inte specifikt i detta arbete. Laboratorieark tillverkades av fibrer som behandlats med multiskikt bestående av PDADMAC/PSS, respektive PAH/PAA. Fysikalisk pappersprovning av arken visade för båda systemen en ökning med cirka 100 % i dragindex för ark som tillverkats av fibrer som behandlats med cirka tio lager, jämfört med ark som tillverkats av icke-behandlade fibrer. Ark tillverkade från PDADMAC/PSS-behandlade fibrer visade att när 5-7 lager adsorberats, ett högre dragindex då PDADMAC adsorberats i det yttersta lagret, jämfört med då PSS adsorberats i det yttersta lagret. Ark tillverkade från fibrer behandlade med PEO/PAA visade ingen skillnad i dragindex beroende av vilken polymer som adsorberats i det yttersta lagret. Den adsorberade mängden PDADMAC/PSS på fibrerna bestämdes med hjälp av kväve- respektive svavelanalys. Den adsorberade mängden polymer ökad linjärt som en funktion av antalet adsorberade lager, men med en högre adsorberad mängd i det första lagret. Dessa resultat har jämförts med den adsorberade mängden för multiskikt uppbyggda med SPAR på kiseloxid. Jämförelsen visade att det finns skillnader i uppbyggnaden mellan skikt byggda på kiseloxid och fibrer, men att kiseloxid med god tillförlitlighet kan användas som modellyta för att förutsäga generella trender för adsorptionen av samma polymersystem på cellulosafibrer. Multiskikt har också bildats på enskilda fibrer med hjälp av en dynamisk kontaktvinkelmätare (DCA). Genom att behandla en del av en fiber, och jämföra den behandlade delen med den obehandlade delen på samma, kan ett multiskikts inverkan på fiberns ytstruktur och vätningsegenskaper studeras. De olika polymersystemen visade en avsevärd skillnad i förmågan att påverka en fibers vätningsegenskaper. För fibrer behandlade med PAH/PAA är också pH av stor betydelse för graden inverkan på fiberns vätningsegenskaper. Fibrer behandlade med PDADMAC/PSS och PAH/PAA, visade en sämre vätningsförmåga då den katjoniska polymeren adsorberats i det yttersta lagret, och vice versa. För enskilda fibrer behandlade med PEO/PAA, kunde inte konstateras någon skillnad beroende av vilken polymer som adsorberats i det yttersta lagret. Vid en jämförelse mellan vätningsförmåga och pappersstyrka kan konstateras att de ark som visade den högsta styrkan tillverkats av fibrer där den lägsta vätningsförmågan har kunnat konstateras. Denna skillnad kan diskuteras med utgångspunkten i att en lägre vätningsförmåga resulterar i en högre våt adhesion och därmed en starkare interaktion mellan de polymerbehandlade ytorna i vått tillstånd. Det föreslås i avhandlingen att den ökade kraft som detta resulterar i vid bildandet av en fiber-fiberfog ger upphov till en högre kontaktarea och därmed, förmodligen, också en högre torr adhesion. Kraftmätningar i vått tillstånd för behandlade kiselmodellytor med hjälp av atomkraftsmikroskopi (AFM) har för PAH/PAA visat att den våta adhesionen är högre då PAH är adsorberats i det yttersta lagret, jämfört med då PAA adsorberats i det yttersta lagret. Detta stödjer hypotesen att en lägre vätning gynnar uppkomsten av en stark fiber-fiberfog. / QC 20101118

Integration of living cells with novel microdevices requires the development of innovative technologies for manipulating cells. Chemical surface patterning has been proven as an effective method to control the attachment and growth of diverse cell populations. Patterning polyelectrolyte multilayers through the combination of layer-by-layer self-assembly technique and photolithography offers a simple, versatile and silicon compatible approach that overcomes chemical surface patterning limitations, such as short-term stability and low protein adsorption resistance. In this study, direct photolithographic patterning of PAA/PAAm and PAA/PAH polyelectrolyte multilayers was developed to pattern mammalian neuronal, skeletal and cardiac muscle cells. For all studied cell types, PAA/PAAm multilayers behaved as a negative surface, completely preventing cell attachment. In contrast, PAA/PAH multilayers have shown a cell-selective behavior, promoting the attachment and growth of neuronal cells (embryonic rat hippocampal and NG108-15 cells) to a greater extent, while providing a little attachment for neonatal rat cardiac and skeletal muscle cells (C2C12 cell line). PAA/PAAm multilayer cellular patterns have also shown a remarkable protein adsorption resistance. Protein adsorption protocols commonly used for surface treatment in cell culture did not compromise the cell attachment inhibiting feature of the PAA/PAAm multilayer patterns. The combination of polyelectrolyte multilayer patterns with different adsorbed proteins could expand the applicability of this technology to cell types that require specific proteins either on the surface or in the medium for attachment or differentiation, and could not be patterned using the traditional methods.

<p dir="ltr">The goal of this thesis is to design nature-inspired biomimetic materials that recapitulate essential features of tissues for biomedical applications including tissue modeling of drug transport and surgical adhesion.</p><p dir="ltr">The first part of this thesis utilizes collagen and glycosaminoglycans to mimic tissues for preclinical modeling of large-molecule drug transport. We first utilize hydrazone crosslinking chemistry with hyaluronic acid to form interpenetrating networks with collagen at different concentrations. The interpenetrating networks enabled a wide range of mechanical properties, including stiffness and swellability, and microstructures, such as pore morphology and size, that can better recapitulate diverse tissues. The mechanical and microstructural differences translated into differences in transport of the macromolecules of different sizes and charges from these matrices. Large macromolecules were impacted by mesh size, whereas small macromolecules were influenced primarily by electrostatic forces. The tunable properties demonstrated by the collagen and crosslinked hyaluronic acid hydrogels can be used to mimic different tissues for early-stage assays to understand drug transport and its relationship to matrix properties.</p><p dir="ltr">We then explore how the glycosaminoglycans hyaluronic acid, chondroitin sulfate, and heparin in collagen hydrogels influence drug transport via glycosaminoglycan-drug interactions and network development. Incorporating different types and concentrations of glycosaminoglycans led to glycosaminoglycan-collagen hydrogels with a range of collagen networks and negative charge densities to recapitulate different tissue compositions. Hyaluronic acid increased the overall viscosity of the hydrogel matrix, and chondroitin sulfate and heparin altered collagen fibrillogenesis. All three GAGs formed concentration-dependent polyelectrolyte complexes with positively charged macromolecules. Transport of positively charged macromolecules through collagen gels with chondroitin sulfate and high concentrations of heparin was inhibited due to complexation and charge effects. Conversely, collagen with low concentrations of heparin hastened the transport of macromolecules due to the limited collagen network resulting from fibrillogenesis inhibition. Overall, the addition of different GAGs into tissue models can better recapitulate native tissue to accurately predict therapeutics transport through a variety of tissues.</p><p>17</p><p dir="ltr">The second part of this thesis investigates the impact of pH and oxidation on an elastin- and mussel-inspired surgical sealant. We combined sodium periodate, an oxidizer, with an L-3,4-dihydroxyphenylalanine-modified elastin-like polypeptide to elucidate how the crosslinking mechanism and intermediate formation impacted adhesion, cure time, and stiffness. Formulations resisted burst pressures greater than physiological internal pressures. They did not swell and had stiffnesses similar to those of soft tissues, and their gelation times varied from seconds to hours. Small increases in the formulation pH led to the formation of α,β-dehydrodopamine intermediates which facilitated the development of multiple crosslinking networks. The mussel-inspired elastin-like adhesive can serve as a model of mussel proteins to further improve our understanding of mussel chemistry. This study exemplifies the importance of pH and oxidation on the performance of mussel-inspired adhesives in surgical sealing within physiological environments.</p><p dir="ltr">The final part of this thesis explores using biomimetic designs in an outreach activity aimed at engaging high school women in chemical engineering. The design and application of the activity led to increased interest in chemical engineering among the participants. There was greater alignment between students' aspirations and the field of chemical engineering, highlighting the potential for such outreach initiatives to inspire future generations of chemical engineers.</p>