Diss. (sammanfattning) Uppsala : Uppsala universitet, 2005. / Härtill 7 uppsatser.

Diss. (sammanfattning) Uppsala : Uppsala universitet, 2005. / Härtill 5 uppsatser.

In this thesis, density functional theory (DFT) is used to investigate the mechanisms and reactivities of electrophilic and nucleophilic aromatic substitution reactions (SEAr and SNAr respectively). For SEAr, the σ-complex intermediate is preceded by one (halogenation) or two (nitration) π-complex intermediates. Whereas the rate-determining transition state (TS) for nitration resembles the second π-complex, the corresponding chlorination TS is much closer to the σ-complex. The last step, the expulsion of the proton, is modeled with an explicit solvent molecule in combination with PCM and confirmed to be a nearly barrierless process for nitration/chlorination and involves a substantial energy barrier for iodination. It is also shown for nitration that the gas phase structures and energetics are very different from those in polar solvent. The potential energy surface for SNAr reactions differs greatly depending on leaving group; the σ-complex intermediate exist for F-/HF, but for Cl-/HCl or Br-/HBr the calculations indicate a concerted mechanism. These mechanistic results form a basis for the investigations of predictive reactivity models for aromatic substitution reactions. For SEAr reactions, the free energy of the rate-determining TS reproduces both local (regioselectivity) and global reactivity (substrate selectivity) with good to excellent accuracy. For SNAr reactions good accuracies are obtained for Cl-/HCl or Br-/HBr as leaving group, using TS structures representing a one-step concerted mechanism. The σ-complex intermediate can be used as a reactivity indicator for the TS energy, and for SEAr the accuracy of this method varies in a way that can be rationalized with the Hammond postulate. It is more accurate the later the rate-determining TS, that is the more deactivated the reaction. For SNAr reactions with F-/HF as leaving group, the same method gives excellent accuracy for both local and global reactivity irrespective of the degree of activation. / <p>QC 20170510</p>

Abstract The solubility of polymers depends on how well the parameters of the polymers and solvents used resemble each other. The more similar the parameters are, the more likely the polymers are to be dissolved. Hansen´s solubility parameters (HSP) tells us how dispersion forces, polar forces and hydrogen bonding influences the structure of the polymers and thereby their solubility. To be able to manufacture effective organic polymer solar cells in the future, we need more knowledge of how polymers and organic solvents interact with each other. This is an essay on how you could gather more knowledge of how primarily the polymer Poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} , (N2200), but also the polymer Poly[2,3-bis-(3-octyloxyphenyl) quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl], (TQ1) dissolves in different organic solvent blends. It is also a test on using the computer software Hansen´s Solubility Parameters in Practice (HSPiP), to estimate the HSP:s for the polymers and the polymer blend. The HSPiP was good at estimating the Hansen solubility parameters for the solubility test on N2200. The software´s drawing tool in the do it yourself- part (DIY) that is used to create a structure code-string (SMILES) for the polymer, did not work as well in this project. The Optimizer in HSPiP made good suggestions of organic solvent blends for N2200 and TQ1, that dissolved the polymers. o-Xylene and tetrahydronaphthalene were the solvents that dissolved N2200 in the solubility test in 24 h and 50 ֯C and among the organic solvent blends it was toluene/1-methylnaphthalene, tetrahydronaphthalene/methyl acetate, tetrahydronaphthalene/o-Xylene and tetrahydronaphthalene/2-methyltetrahydrofuran that were able to dissolve the polymers in the concentrations of 10.0 mg/ml. N2200 dissolved very well up to 10.0 mg/ml in the calculated solvent blends but on the other hand, the samples became very viscous at that concentration and hardly fluent, if fluent at all. It was more difficult to find organic solvent blends that could dissolve N2200 than it was for TQ1. TQ1 dissolved in all solvent ratios that dissolved N2200. / Sammanfattning   Löslighet hos polymerer beror på hur löslighetsparametrarna hos polymeren och det lösningsmedel man använder, liknar varandra. Ju mer löslighetsparametrarna liknar varandra, desto bättre löser sig polymeren i lösningsmedlet. Hansen´s löslighetsparametrar (HSP) talar om hur dispersionskrafter, polära krafter och vätebindningar påverkar strukturer hos polymerer och därigenom deras löslighet. För att kunna tillverka effektiva organiska polymera solceller i framtiden, behöver vi mer kunskap i hur polymerer och organiska lösningsmedel interagerar med varandra. Detta är en uppsats i hur man kan gå tillväga för att ta reda på mer om hur främst polymeren Poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} , (N2200), men också polymeren Poly[2,3-bis-(3-octyloxyphenyl) quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl], (TQ1) löser sig i olika blandningar av organiska lösningsmedel. Det är också ett försök till att använda dataprogrammet, Hansen´s Solubility Parameters in Practice (HSPiP), för att estimera löslighet hos polymererna och polymerblandningen. Det visade sig att HSPiP, var bra på att estimera Hansens löslighetsparametrar för löslighetstestet på N2200. Programmets ritverktyg i DIY (do it yourself/gör det själv), för att skapa SMILES-kod (kod för den ritade molekylens struktur) för polymeren, visade sig vara mindre bra. Optimeraren i HSPiP visade sig kunna föreslå organiska lösningsmedelsblandningar för N2200 och TQ1 som kunde lösa polymererna. o-Xylene och tetrahydronaftalen var de som löste N2200 i löslighetstestet på 24 h med 50 ֯C och av blandningarna var det toluen/1-methylnaftalen, tetrahydronaftalen/metylacetat, tetrahydronaftalen/o-Xylene och tetrahydronaftalene/2-metyltetrahydrofuran som kunde lösa polymererna i koncentrationer av 10.0 mg/ml. N2200 löste sig bra ända upp till 10.0 mg/ml för de beräknade lösningsmedelsblandningarna men däremot blev proverna väldigt viskösa i den koncentrationen och knappt flytande, om alls flytande. Det var svårare att hitta organiska lösningsmedelsblandningar som fungerade för N2200 medan TQ1 kunde lösa sig i allt som fungerade för N2200.

When making paper, fibers and additives are suspended in water to a fiber suspension. The sheet is formed by draining a specific amount of suspension through a wire-cloth. The procedure is well known, but the underlying mechanisms are not fully understood. To understand how the different particles such as fines, fibers, retention aids and other additives interact with each other, further research is needed. This knowledge is important because in the production of paper, the retention and the distribution of fines and additives within a paper structure are vital parameters for the properties and also for the profitability of the final product. In this study fluorescence microscopy was used to study fines from bleached kraft pulp which were labeled with fluorophores. When the fines exhibit fluorescence we can study their individual trajectories and understand more about the interactions between fibers, fines and additives in different chemical environments. Fines from bleached kraft pulp have no fluorescent properties and therefore it is necessary to bind a fluorophore to the material. It was difficult to find a suitable fluorophore which binds covalently to the cellulose, the dominating part of fines. The result from this study was that the labeled fines did exhibited fluorescence. As the fines were aggregated no individual trajectories could be analyzed with fluorescence microscopy. Further development of the technique for labeling fines must be carried out to avoid aggregation of fines. / Vid tillverkning av papper, blandas fibrer och tillsatser i vatten till en fibersuspension. Arket bildas genom att avvattna suspensionen genom en vira. Förfarandet är välkänt men för att förstå mekanismerna måste vi förstå hur olika partiklar som fines, fibrer, retentionsmedel och andra tillsatser interagerar med varandra. Denna kunskap är viktigt eftersom i produktionen av papper är retention och distribution av fines och tillsatser i en pappersstruktur avgörande parametrar för de egenskaper, och även för lönsamheten, som erhålls i den slutliga produkten. I denna studie används fluorescensmikroskopi för att kunna studera fines av blekt sulfatmassa som blivit märkta med fluoroforer. När materialet uppvisar fluorescens kan deras individuella rörelsemönster studeras och därmed kan interaktionen som sker mellan fibrer, fines och tillsatser i olika kemiska miljöer förstås. Fines av blekt sulfatmassa har inga fluorescerande egenskaper och därför är det nödvändigt att binda en fluorfor till materialet. Det var svårt att hitta en lämplig fluorofor som binder kovalent till cellulosa, den dominerande delen av fines. Resultatet från denna studie visar att lösningarna med fluorescentmärkta fines uppvisade fluorescens. Eftersom det skedde en aggregering av fines kunde inte deras individuella rörelsemönster analyseras med fluorescensmikroskopi. Modifiering av märkningen måste göras för att kunna undvika aggregeringen av fines.

The main focus of this thesis is on the effects caused by α-helical peptides on liposome structure, the impact of cholesterol on the peptide-membrane interactions, and the effect of aggregate curvature on the peptide affinity. Results of the studies show that the membrane destabilizing effect of the cationic α-helical peptide melittin is modulated by cholesterol. Melittin induces leakage from pure phospholipid liposomes in a manner that is compatible with the presence of small pores. In the case of cholesterol-supplemented liposomes leakage coincides, however, with major structural transformations and rupture of the liposomes. Cholesterol decreases the affinity of melittin for phospholipid bilayers, but once the peptide has adsorbed to the membrane the presence of cholesterol does not offer any resistance against melittin-induced membrane destabilization. Our investigations indicate that cholesterol affects the alamethicin-lipid bilayer interactions in a similar way. PEG-stabilized bilayer disks are formed upon addition of polyethylene glycol (PEG)-lipids to lipid mixtures with high bending rigidity. The partial segregation of components within the bilayer disk, suggested by theoretical calculations and experimental observations, was verified by small angle neutron scattering. By means of a novel competitive binding assay it was shown that the three α-helical peptides melittin, alamethicin, and magainin have high affinity for the curved rim of PEG-stabilized bilayer disks. The bilayer disks have structural, and other properties, that make them interesting for the formulation of peptides and membrane-associated proteins. For stability reasons dry formulations are often preferred. The PEG-stabilized bilayer disks were shown to retain their structure in rehydrated samples that had been freeze- or spray-dried in the presence of lactose.

This Thesis presents studies of phase transitions ocurring in porous media. The investigated phase transitions include melting/crystallization, surface pre-melting and liquid-liquid phase separation of binary mixtures. A combination of NMR techniques, already existing and newly developed and ranging from cryoporometry to elaborate self-diffusion and spin-relaxation experiments, was applied in order to detect and quantify the effect of finite size constraints on those phase transitions. By relating the results to physico-chemical models, the difference in behaviour with respect to that of bulk was exploited and related to pore morphology and surface properties in diverse porous systems. NMR cryoporometry is based on the detection of the melting/freezing temperature shifts with respect to those in the bulk state to obtain mean pore size and pore size distribution. We extended the size range in which this can be done in porous matrices of both hydrophilic and hydrophobic nature to a 1 μm-600 nm upper limit. This was achieved by introducing two new probe liquids namely octamethylcyclotetrasiloxane (OMCTS) and zinc nitrate hexahydrate Zn(NO)3•H2O. The thickness of the pre-molten surface layer that appears at the interface of frozen octamethylcyclotetrasiloxane (OMCTS) to the matrix in controlled porous glasses was quantified and modeled including its temperature and wall-curvature dependence. The results reveal that the layer thickness depends logarithmically on the deviation from the pore melting point, while for the largest pore investigated this turns into a power law with the exponent of –1/2. Diverse NMR techniques were used not only to detect solely the surface layer and the evolution of the surface melting, but also to distinguish the latter from the volume melting transition within the pores. The morphologies of two nanostructured materials, sintered films of TiO2 nanoparticles and a mesoporous foam obtained by surfactant-templated synthesis, were investigated. These two porous matrices have very different structures but fall into the size range accessible by NMR cryopormetry and their characterization plays an important role in their future applications. They were studied by exploiting the difference between melting and freezing temperature shifts ΔTm and ΔTf, respectively, with respect to that of bulk. NMR cryoporometry was shown to be a suitable alternative and an excellent complement to other porosimetry techniques, namely mercury intrusion and gas sorption porosimetries to analyze the pore structure and pore size distribution because of the unique and model-independent access to information about pore shape. By combining NMR cryoporometry with NMR diffusion experiments holds great potential for accessing information about pore interconnectivity. By diverse NMR techniques we provided experimental evidence that corroborate that liquid-liquid phase separation of a binary mixture imbibed in porous media actually occurs within the individual pores. The size distribution of the phase-separated domains was measured. / QC 20100927

This thesis deals with the influence of molecular adhesion on paper strength. By combining the use of high-resolution techniques and silica/cellulose surfaces, with various fibre–fibre and sheet testing techniques, new information regarding the molecular mechanisms responsible for paper strength has been obtained. Large parts of this research were devoted to the polyelectrolyte multilayer (PEM) technique, i.e. a charged surface is consecutively treated with oppositely charged polyelectrolytes. Application of PEMs incorporating polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) onto dried, fully bleached softwood fibres, prior to sheet preparation, increased tensile strength. No linear relationship was detected between the amounts of PAH and PAA adsorbed onto the fibres and the developed tensile strength, which suggests that the adsorbed amount is not the only important factor determining the tensile strength. Closer examination of PEM formation on silica indicated that both exponential PEM film growth and the occurrence of a PEM film in which the polyelectrolytes are highly mobile, favour the strength-enhancing properties of sheets containing PEM-treated fibres. This indicates that a water-rich, soft PEM film allows the polyelectrolytes to diffuse into each other, creating a stronger fibre–fibre joint during consolidation, pressing, and drying of the paper. In addition, when PAH capped the PEM film, the paper strength was higher than when PAA capped the film; this could be related to the structure of the adsorbed layer. Further analysis of the sheets revealed that the increase in tensile strength can also be linked to an increase in the degree of contact within a fibre–fibre joint, the number of efficient joints, and the formation of covalent bonds. The relative bonded area (RBA) in the sheets, as determined using light-scattering measurements, indicated no significant change until a certain tensile strength was obtained. The RBA, as determined using nitrogen adsorption via BET analysis, did show significant changes over the whole investigated tensile strength range. From this it can be concluded that light scattering cannot give any direct information regarding molecular interactions within a sheet. Furthermore, it was shown that PEMs involving cationic and anionic starch display an almost linear relationship with out-of-plane strength properties regarding the amount of starch in the sheets, whereas the tensile strength was more dependent on the physical properties of the starch, as was the case with PAH and PAA. Cationic dextran (DEX) and hydrophobically modified cationic dextran (HDEX) were used to test the importance of having compatible surface layers in order to obtain strong adhesive joints. DEX and HDEX phase separated in solution, however, this incompatibility of HDEX:DEX mixtures was not reflected in wet or dry joint strength. For both wet and dry measurements, adhesion between DEX and HDEX coated surfaces was intermediate to the adhesion of DEX:DEX and HDEX:HDEX surfaces. In addition, various types of cellulose surfaces, different regarding their crystallinity, were investigated. Depending on the preparation techniques and solution conditions used, i.e. pH and salt concentration, steric, electrostatic, and van der Waals interactions were obtained between the surfaces in aqueous solutions. The adhesion forces between polydimethylsiloxane and cellulose surfaces, measured under ambient conditions, were influenced by the degree of crystallinity. This suggests that amorphous cellulose offers more possibilities for surface groups to arrange themselves to participate in molecular interactions in the joint. Higher relative humidity could increase this adhesion force further, water probably acting as a plasticizer during joint formation. / QC 20110125

<p>This thesis deals with the influence of molecular adhesion on paper strength. By combining the use of high-resolution techniques and silica/cellulose surfaces, with various fibre–fibre and sheet testing techniques, new information regarding the molecular mechanisms responsible for paper strength has been obtained.</p><p>Large parts of this research were devoted to the polyelectrolyte multilayer (PEM) technique, i.e. a charged surface is consecutively treated with oppositely charged polyelectrolytes. Application of PEMs incorporating polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) onto dried, fully bleached softwood fibres, prior to sheet preparation, increased tensile strength. No linear relationship was detected between the amounts of PAH and PAA adsorbed onto the fibres and the developed tensile strength, which suggests that the adsorbed amount is not the only important factor determining the tensile strength. Closer examination of PEM formation on silica indicated that both exponential PEM film growth and the occurrence of a PEM film in which the polyelectrolytes are highly mobile, favour the strength-enhancing properties of sheets containing PEM-treated fibres. This indicates that a water-rich, soft PEM film allows the polyelectrolytes to diffuse into each other, creating a stronger fibre–fibre joint during consolidation, pressing, and drying of the paper. In addition, when PAH capped the PEM film, the paper strength was higher than when PAA capped the film; this could be related to the structure of the adsorbed layer. Further analysis of the sheets revealed that the increase in tensile strength can also be linked to an increase in the degree of contact within a fibre–fibre joint, the number of efficient joints, and the formation of covalent bonds. The relative bonded area (RBA) in the sheets, as determined using light-scattering measurements, indicated no significant change until a certain tensile strength was obtained. The RBA, as determined using nitrogen adsorption via BET analysis, did show significant changes over the whole investigated tensile strength range. From this it can be concluded that light scattering cannot give any direct information regarding molecular interactions within a sheet. Furthermore, it was shown that PEMs involving cationic and anionic starch display an almost linear relationship with out-of-plane strength properties regarding the amount of starch in the sheets, whereas the tensile strength was more dependent on the physical properties of the starch, as was the case with PAH and PAA.</p><p>Cationic dextran (DEX) and hydrophobically modified cationic dextran (HDEX) were used to test the importance of having compatible surface layers in order to obtain strong adhesive joints. DEX and HDEX phase separated in solution, however, this incompatibility of HDEX:DEX mixtures was not reflected in wet or dry joint strength. For both wet and dry measurements, adhesion between DEX and HDEX coated surfaces was intermediate to the adhesion of DEX:DEX and HDEX:HDEX surfaces.</p><p>In addition, various types of cellulose surfaces, different regarding their crystallinity, were investigated. Depending on the preparation techniques and solution conditions used, i.e. pH and salt concentration, steric, electrostatic, and van der Waals interactions were obtained between the surfaces in aqueous solutions. The adhesion forces between polydimethylsiloxane and cellulose surfaces, measured under ambient conditions, were influenced by the degree of crystallinity. This suggests that amorphous cellulose offers more possibilities for surface groups to arrange themselves to participate in molecular interactions in the joint. Higher relative humidity could increase this adhesion force further, water probably acting as a plasticizer during joint formation.</p>

Diss. (sammanfattning) Linköping : Univ., 2004. / Härtill 6 uppsatser.