<p>The ability to create surfaces with well-defined chemical properties is a major research field. One possibility to do this is to design peptides that bind with a specific secondary structure to silica nanoparticles. The peptides discussed in this thesis are constructed to be random coil in solution, but are “forced” to become helical when adsorbed to the particles. The positively charged side-chains on the peptides strongly disfavor an ordered structure in solution due to electrostatic repulsion. When the peptides are introduced to the particles these charges will strongly favor the structure because of ion pair bonding between the peptide and the negatively charged nanoparticles. The peptide-nanoparticle system has been thoroughly investigated by systematic variations of the side-chains. In order to determine which factors that contributes to the induced structure, several peptides with different amino acid sequences have been synthesized. Factors that have been investigated include 1) the positive charge density, 2) distribution of positive charges, 3) negative charge density, 4) increasing hydrophobicity, 5) peptide length, and 6) by incorporating amino acids with different helix propensities. Moreover, pH dependence and the effect of different nanoparticle curvature have also been investigated. It will also be shown that the system can be modified to incorporate a catalytic site that is only active when the helix is formed. This research will increase our understanding of peptide-surface interactions and might be of importance for both nanotechnology and medicine.</p>

<p>Hiphop och Rap är en kultur med stark genomslagskraft över hela världen och även bland ungdomar i Sverige.  Syftet med detta examensarbete är att, genom kvalitativa forskningsintervjuer med fem stycken respondenter, undersöka hur ungdomarna som ägnar sig åt Rap i sitt musikskapande kan skildra sin omvärld samt att undersöka hur de beskriver att deras skildringar behandlas i skolan. För att operationalisera syftet valde jag att ha en grupp högstadie- och gymnasieelever som ägnar sig åt Rap som undersökningspersoner. Resultatet visar på att ungdomarna via sitt musikskapande skildrar en ambivalent inställning till det egna bostadsområdet, där interaktioner med polisen, droger och våldsamheter kan vara en del av vardagen. Samtidigt skildras även förorten som en kärleksfull plats där barndomsminnen och de närmaste vännerna även beskrivs. Återkommande teman i respondenternas musikskapande är genomgående livet i förorten.  Vidare visar resultatet att uppfattningen om hur skolan behandlar den värld som skildras genom musiken skiljer sig mellan respondenterna beroende på vilket stadie de studerar vid.  Slutsatserna visar på att olika socialisations processer spelar en stor roll i valen av teman hos respondenterna. Samt att högstadieskolorna på ett mer användbart sätt behandlar den omvärld som respondenterna skildrar i sin musik.</p> / <p>Hip Hop and Rap is a culture with a strong appeal worldwide and also among young people in Sweden. The purpose of this thesis is that, through qualitative research interviews with five respondents, to examine how young people that are engaged in the RAP in its music creation can depict the world around them and to examine how they describe their depictions are treated in school. To meet the purpose of this essay, I chose to have a group of junior high school students and high school students that are engaged in RAP as study subjects. The results show that the respondent through their music creation depicts an ambivalent attitude towards their own neighborhood, where interactions with police, drugs and violence can be a part of everyday life. At the same time also depicted suburbia as a loving place where childhood memories and closest friends are also described. Recurring themes in respondents' music-making is consistently the life in the suburbs. Furthermore, the results show that the perception of how the school treats the world as depicted through the music is different between respondents depending on which stage they are studying at. The findings suggest that different socialization processes play a major role in the choice of themes among respondents. And that secondary schools in a more useful way deals with the outside world as respondents depict in their music.</p>

The ability to create surfaces with well-defined chemical properties is a major research field. One possibility to do this is to design peptides that bind with a specific secondary structure to silica nanoparticles. The peptides discussed in this thesis are constructed to be random coil in solution, but are “forced” to become helical when adsorbed to the particles. The positively charged side-chains on the peptides strongly disfavor an ordered structure in solution due to electrostatic repulsion. When the peptides are introduced to the particles these charges will strongly favor the structure because of ion pair bonding between the peptide and the negatively charged nanoparticles. The peptide-nanoparticle system has been thoroughly investigated by systematic variations of the side-chains. In order to determine which factors that contributes to the induced structure, several peptides with different amino acid sequences have been synthesized. Factors that have been investigated include 1) the positive charge density, 2) distribution of positive charges, 3) negative charge density, 4) increasing hydrophobicity, 5) peptide length, and 6) by incorporating amino acids with different helix propensities. Moreover, pH dependence and the effect of different nanoparticle curvature have also been investigated. It will also be shown that the system can be modified to incorporate a catalytic site that is only active when the helix is formed. This research will increase our understanding of peptide-surface interactions and might be of importance for both nanotechnology and medicine.

This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II. The redox properties of these complexes have been investigated with electro chemical methods and the structure of the complexes has been investigated with different X-ray techniques. Structural aspects and the effect of water on the redox properties have been shown. One of the manganese complexes has been covalently linked in a triad donor-photosensitizer-acceptor (D–P–A) system. The kinetics of this triad has been investigated in detail after photo excitation with both optical and EPR spectroscopy. The formed charge separated state (D––P–A+) showed an unusual long lifetime for triad based on ruthenium photosensitizers. The thesis also includes a study of manganese-salen epoxidation reactions that we believe can give an insight in the oxygen transfer mechanism in the water oxidising complex in photosystem II.

This thesis describes the development of new catalytic methods for the synthesis and application of organometallic reagents, mainly focusing on allylboronic acid derivatives. Thus, palladium pincer-complex catalysis has been applied for extending the scope of palladiumcatalyzed borylation reactions in the synthesis of regio- and stereodefined functionalized allylboronic acid derivatives. These novel allylboronic acids were also employed as substrates in palladium catalyzed regioselective coupling reactions with iodobenzenes. We have also developed a new one-pot sequence based on preparation of allyl- and vinylboronates via catalytic carbon-hydrogen bond activation/borylation reactions. The synthetic scope of the reaction as well as mechanistic studies on the borylation process are presented. Finally, the synthesis of new chiral palladium pincer-complexes is described. These species were employed as catalysts in asymmetric electrophilic allyation of imines.

This thesis is mainly focused on the reactions of oxo-pyrimidines and oxo-imidazoles with nitric acid in sulfuric acid and properties of the gem-dinitro products formed in this process. Low temperature nitrations of 2-methylimidazoles produced – in addition to the known 2-methyl-5(4)-nitroimidazole – 2-(dinitromethylene)-5,5-dinitro-4-imidazolidinone and parabanic acid. This tetranitro compound was also obtained via nitration of 2-methyl-4,4-dihydro-(1H)-5- imidazolone. Thermal decomposition of 2-(dinitromethylene)-5,5-dinitro-4-imidazolidinone yielded 2-(dinitromethylene)-4,5-imidazolidinedione, which also was the product from the nitration of the new compound 2-methoxy-2-methyl-4,5-imidazolidienedione. Treatment of 2- (dinitromethylene)-5,5-dinitro-4-imidazolidinone with aqueous ammonia resulted in the previously unknown 1,1-diamino-2,2-dinitroethylene (Paper I). The nitration of some 2-substituted pyrimidine-4,6-diones in sulfuric acid, which afforded previously unknown 5,5-gem-dinitro-pyrimidine-4,6-diones in high yields, was studied. Alloxane was prepared in a one-step procedure by thermal decomposition of 5,5-dinitrobarbituric acid in hot acetic acid. The gem-dinitro products were found to be easily attacked by nucleophiles with concomitant formation of gem-dinitroacetyl derivatives, which in turn could be further hydrolysed to salts of dinitromethane and triureas (Papers II and III). Nitration of 4,6-dihydroxypyrimidine in sulfuric acid yielded nitroform as the sole product. This behaviour was tentatively explained by the formation of an intermediate, 5,5-dinitro-4,6- dihydroxypyrimidine, which underwent hydrolysis in the nitrating acid into gem-dinitroacetyl formamidine. This compound was further nitrated in the same reaction mixture into trinitroacetylformamidine, which finally underwent hydrolytic cleavage into nitroform. It was also demonstrated that gem-dinitroacetylureas could produce nitroform upon nitration. The structures of the proposed trinitroacetylureas were confirmed by the isolation of one of their derivatives (Paper IV). / QC 20100907

In the last decades several new nanostructures of carbon have been discovered, including carbon nanotubes (CNTs), and the recently discovered 2-dimensional graphene. These new materials exhibit extraordinary and unique properties—making them extremely interesting both for fundamental science and for future applications. It is, however, of crucial importance to develop new and improved fabrication and processing methods for these carbon nanomaterials. In this thesis the concept of applying solution chemistry and solution-based techniques to fabricate and to deposit graphene and other carbon nanomaterials is explored. An area-selective deposition method was developed for CNT and carbon-coated iron nanoparticles. By utilizing organic functionalization the properties of the nanomaterials were tuned, with the purpose to make them soluble in a liquid solvent and also enable them to selectively adsorb to non-polar surfaces. The first step of the functionalization process was an acid treatment, to introduce defects in the materials. This method was also used to create defects in so-called carbon nanosheets (CNS). The effect of the defect formation on the electric properties of the graphene-like CNS was studied; it was found that the resistance of the CNS could be reduced to 1/50 by acid treating of the sample. Also, the effect of the created defects on gas adsorption to the surface of the CNS has been investigated. This was done using atomic layer deposition (ALD) of TiO2 on the CNS, and a clear change in nucleation be-havior was seen due to the acid-treatment. Furthermore, a solution-based new method for fabrication of graphene was developed; this method combines intercalation of bromine into graphite with ultrasonic treatment to exfoliate flakes into a solvent. From the solvent the flakes can be deposited onto an arbitrary substrate. Several important parameters in the method were investigated in order to optimize the process. One important parameter proved to be the choice of solvent in all steps of the procedure; it was shown to influence sonication yield, flake size, and deposition results. Toluene was identified as a suitable solvent. A mild heat-treatment of the starting material was also identified as a way to increase the exfoliation yield. Using this method, fabrication of few-layer graphene sheets was achieved and areas down to 3 layers in thickness were identified—this is in the very forefront of current solution-based graphene fabrication techniques.

The secondary structure of peptides is of pivotal importance for their biological function. The introduction of photoswitchable moieties into the backbones of peptides provides a unique way of regulating their conformation using an external stimulus, i.e., light. This thesis addresses the design, synthesis, and conformational analysis of photoswitchable peptidomimetics (PSPM). Examples of photomodulation of their functional properties are given. PSPM were prepared by incorporation of stilbene and thioaurone chromophores (switches) into dipeptides. Synthetic schemes for preparing these chromophores have been developed. Their suitability for incorporation into peptidomimetics has been demonstrated, and the resulting PSPM have been subjected to photoisomerization as well as computational and spectroscopic conformational analysis. The chromophore’s potential as a β-hairpin inducer was particularly interesting. To investigate the factors that govern the formation of β-hairpins, a series of decapeptides were prepared. Turn regions consisting of amino acids or chromophores were combined with antiparallel peptide strands with hydrophobic side chains. Linear tryptophan zipper peptidomimetics and cyclic peptidomimetics with a second, hairpin-inducing turn region were particularly promising. Comparison between switches revealed that the more flexible stilbene is a better choice for upholding the β-hairpin conformation than the thioaurone. The catalytic properties of an artificial hydrolase with a helix-loop-helix structure can be improved by introducing a stilbene photoswitch into the loop region. Photoisomerization regulates the catalytic activity of this peptidomimetic, and provides a means to control its aggregation state. The activity of the enzyme Mycobacterium tuberculosis ribonucleotide reductase was realized by incorporating a stilbene moiety into a linear peptide. Here, one photoisomer proved to be an inhibitor at nM concentrations. A significantly lower effect was observed for the other isomer. Finally, the decomposition of thioaurones, mainly to thioflavonols and thiaindenes, under conditions used for solid-phase peptide synthesis has been mapped. These findings are expected to have implications for future use of this chromophore.

Electric current is known to flow through the π-bonds in oligothiophenes. In order to use them as molecular wires it is important to use a technique where the potential gradients can be generated and maintained in supramolecular networks. A solution to this problem can be the use of metal complexes as junction points within such a network.  In this project pathways to synthesize 2-thia-7,8-diaza-cyclopenta[l]phenanthrene (1) and 1-thia-7,8-diaza-cyclopenta[l]phenanthrene (2) for use in molecular electronic devices have been investigated. 4-(5-Bromo-thiophen-2-yl)2,2’-bipyridine (3) was prepared via Kröhnke reaction from 3-(5-bromothiophene-2-yl)acrolein and 1-(2-Oxo-2-pyridine-2-yl-ethyl)-pyridinium iodide in an overall yield of 14 %.    Several routes towards 2-thia-7,8-diaza-cyclopenta[l]phenanthrene (1) and 1-thia-7,8-diaza-cyclopenta[l]phenanthrene (2) were tested. Since the original planned pathway did not work, lack of time made it impossible to complete the series of experiments that were needed. The synthesis of 2-thia-7,8-diaza-cyclopenta[l]phenanthrene (1) is almost finished. Due to the solvation problems, after the decarboxylation step, the product could not be analyzed by 1H-NMR in a satisfactory manner. The product was sent for analysis.  A number of experiments towards 1-thia-7,8-diaza-cyclopenta[l]phenanthrene (2) were tested but few of them worked as planned. There is a lot of work left to be done in the synthesis of this compound but the lack of time made it impossible.  The chemistry that has been achieved is the synthesis of 1,10-phenanthroline-5,6-dione in the synthesis of 2-thia-7,8-diaza-cyclopenta[l]phenanthrene (1). The following Hinsberg thiophene synthesis probably worked but due to solvation problems the product could not be isolated. The final product after hydrolysis and decarboxylation of the remaining ester groups after the Hinsberg thiophene synthesis was tested but the results were difficult to confirm.  In the synthesis of 1-thia-7,8-diaza-cyclopenta[l]phenanthrene (2) several attempts to make 3,4-diamino-N,N-diethyl-benzamide were made. The attack from the primary amines on the carbonyl carbon made it necessary to protect them. The attempt to synthesize 3,4-bis-acetylamino-N,N-diethyl-benzamide also failed, both the attempt directly from the carboxylic acid and through the acylchloride, even though the amines were protected.

Hiphop och Rap är en kultur med stark genomslagskraft över hela världen och även bland ungdomar i Sverige.  Syftet med detta examensarbete är att, genom kvalitativa forskningsintervjuer med fem stycken respondenter, undersöka hur ungdomarna som ägnar sig åt Rap i sitt musikskapande kan skildra sin omvärld samt att undersöka hur de beskriver att deras skildringar behandlas i skolan. För att operationalisera syftet valde jag att ha en grupp högstadie- och gymnasieelever som ägnar sig åt Rap som undersökningspersoner. Resultatet visar på att ungdomarna via sitt musikskapande skildrar en ambivalent inställning till det egna bostadsområdet, där interaktioner med polisen, droger och våldsamheter kan vara en del av vardagen. Samtidigt skildras även förorten som en kärleksfull plats där barndomsminnen och de närmaste vännerna även beskrivs. Återkommande teman i respondenternas musikskapande är genomgående livet i förorten.  Vidare visar resultatet att uppfattningen om hur skolan behandlar den värld som skildras genom musiken skiljer sig mellan respondenterna beroende på vilket stadie de studerar vid.  Slutsatserna visar på att olika socialisations processer spelar en stor roll i valen av teman hos respondenterna. Samt att högstadieskolorna på ett mer användbart sätt behandlar den omvärld som respondenterna skildrar i sin musik. / Hip Hop and Rap is a culture with a strong appeal worldwide and also among young people in Sweden. The purpose of this thesis is that, through qualitative research interviews with five respondents, to examine how young people that are engaged in the RAP in its music creation can depict the world around them and to examine how they describe their depictions are treated in school. To meet the purpose of this essay, I chose to have a group of junior high school students and high school students that are engaged in RAP as study subjects. The results show that the respondent through their music creation depicts an ambivalent attitude towards their own neighborhood, where interactions with police, drugs and violence can be a part of everyday life. At the same time also depicted suburbia as a loving place where childhood memories and closest friends are also described. Recurring themes in respondents' music-making is consistently the life in the suburbs. Furthermore, the results show that the perception of how the school treats the world as depicted through the music is different between respondents depending on which stage they are studying at. The findings suggest that different socialization processes play a major role in the choice of themes among respondents. And that secondary schools in a more useful way deals with the outside world as respondents depict in their music.