Foi desenvolvido um processo tecnológico para concentrar apatita das camadas 6 e 7 do depósito sedimentar de Bayóvar (deserto de Sechura - Peru) por flotação. O minério é composto por apatita (84%), feldspatos (12%), quartzo (4%) e traços de mica, anfibólio e carbonatos. As partículas de apatita apresentaram grau de liberação maior que 90% na sua granulometria (-800 mm). Embora a flotação direta da apatita com ácido graxo ser tecnicamente viável, os melhores resultados metalúrgicos foram produzidos com a flotação catiônica reversa utilizando amidoamina (concentração na solução da flotação = 107 mg/L e dosagem = 250 g/t) como coletor em pH natural (7,4 - 8,2) e a água do mar da região de Bayóvar. Produziu-se um concentrado de fosfato com teor de 30% de P2O5 e recuperação metalúrgica de apatita maior que 90%. A amidoamina provou ser adequada para ser usada em condições desfavoráveis causadas pela utilização da flotação em água do mar no deserto de Sechura: variações na temperatura (25oC - 40oC), concentração de eletrólitos muito alta na água de processo (força iônica de 0,71 mol/L) e variação da concentração de eletrólitos na água do mar causada pela evaporação (22 - 37 g/L de cloretos). A tese também abordou estudos fundamentais com minerais puros (apatita e feldspato) e utilização de água salgada com concentrações de sais puros semelhantes à da água do mar Bayóvar, com objetivo de contribuir para um melhor entendimento sobre como a seletividade da separação apatita/feldspato ocorre em pH 8. Por causa do potencial zeta da apatita (de 0 a +5 mV) e do feldspato (de 0 a -5 mV) imersos em água salgada ser muito baixo, a teoria clássica de Gaudin-Fuerstenau-Somasundaran não é forte o suficiente para explicar a boa seletividade desta separação. Considerou-se então a precipitação de um sal composto do agente coletor amidoamina e os ânions presentes na água salgada (cloreto e sulfato), embora a turbidez das soluções de amidoamina em água do mar só começasse a ser observada em concentração de 1.000 mg/L, maior que a concentração do coletor usada nos testes de flotação (107 mg/L). Em pH 8, os precipitados apresentaram diâmetros de (236±20) nm e exibiram potencial zeta de +15 mV. Os ângulos de contato da apatita, feldspato e precipitado foram medidos com água, glicerol e diiodometano a 22oC. Os resultados foram usados para calcular a energia de superfície dos sólidos (46,38 mJ.m-2 para o precipitado, 56,54 mJ.m-2 para a apatita e 60,59 mJ.m-2 para o feldspato), constante de Hamaker (+1,06x10-20 J para feldspato/precipitado e +0,77x10-20 J para apatita/precipitado) e energia livre de adesão apatita/precipitado (-32,39 mJ.m-2) e feldspato/precipitado (-38,55 mJ.m-2) em meio aquoso. Esses resultados negativos indicam que tanto apatita/precipitado quanto feldspato/precipitado apresentam energia livre de adesão atrativa. Entretanto, a maior magnitude da energia livre de adesão para o feldspato/precipitado indica a preferência da flotação para o feldspato. Utilizando o racional oferecido pelas teorias de DLVO/X-DLVO, construíram-se as curvas de energia de interação da apatita/precipitado e feldspato/precipitado em função da distância entre as partículas (1 nm a 20 nm). Estes resultados indicaram que a contribuição da energia de Lifshitz-van der Waals é mais significativa que a contribuição da energia ácido-base. Com relação à contribuição eletrostática, não se espera que ela tenha contribuição significativa na separação em pH 8 porque o potencial zeta de ambos minerais são muito baixos em magnitude (ainda que tenham sinais diferentes). A energia de interação para o precipitado/feldspato em função da distância é mais negativa que a energia da apatita/precipitado para ambas as teorias DLVO/X-DLVO. Esta diferença pode explicar a seletividade da separação entre a apatita e o feldspato com amidoamina (107 mg/L) em pH 8. / A technological process was developed to concentrate apatite from the layers 6 and 7 of the sedimentary phosphate of Bayóvar (desert of Sechura - Peru) by froth flotation. The ore is composed of apatite (84%), feldspars (12%), quartz (4%) and traces of mica, amphibole and carbonates. Particles of apatite achieve a liberation degree higher than 90% as particle size is lower than 800 mm. Although direct anionic flotation of apatite with fatty acids works well, the best metallurgical results were yielded by cationic reverse flotation by using amidoamine (concentration in flotation solution = 107 mg/L and dosage= 250 g/t) as collector at natural pH (7.4 - 8.2) and seawater from Bayóvar region. A phosphate concentrate assaying 30% of P2O5 was yielded accompanied by apatite recovery higher than 90%. Amidoamine proved to be suitable to work under harsh conditions posed by seawater in the desert of Sechura for flotation purposes: prominent gap in temperature (25oC - 40oC), very high concentration of electrolytes (ionic strength of 0.71 mol/L) and variation electrolyte concentration of seawater caused by water evaporation (22 - 37 g/L of chlorides). The thesis also approached fundamental studies with pure minerals (apatite and feldspar) and salty water produced by pure salts with concentration similar to Bayóvar seawater, in order to contribute towards a better understanding on how the selectivity of the separation apatite/feldspar takes place at pH 8. Because zeta potential of apatite (from 0 to +5 mV) and feldspar (from 0 to -5 mV) immersed in salty water at pH 8 are very low, the classic theory of Gaudin-Fuerstenau- Somasundaran is not strong enough to explain the good selectivity of the achieved separation. Precipitation of a salt composed by amidoamine and anions from salty water (chloride and sulfate) was considered to happen, although turbidity of solutions solely start to happen in concentration 1,000 mg/L higher than collector concentration used in flotation experiments (107 mg/L). At pH 8, precipitates show diameter of (236 ± 20) nm and exhibit zeta potential of +15 mV. Contact angle of apatite, feldspar and precipitate was measured with water, glycerol and diiodomethane at 22oC. The results were used to calculate surface energy of solids (46.38 mJ.m-2 for precipitate, 56.54 mJ.m-2 for apatite and 60.59 mJ.m-2 for feldspar), Hamaker constant (+1.06x10-20 J for feldspar/precipitate and +0.77x10-20 J for apatite/precipitate) and free energy of adhesion apatite/precipitate (-32.39 mJ.m-2) and feldspar/precipitate (- 38.55 mJ.m-2) in aqueous media. These negative results indicate that both apatite/precipitate and feldspar/precipitate present total energy of adhesion are attractive. However, the higher magnitude of free energy of adhesion for feldspar/precipitate may indicate the preferential flotation of feldspar. The rationale maintained by DLVO and X-DLVO theories was used to build curves of interaction energy of apatite/precipitate and feldspar/precipitate versus the distance between particles (1 nm to 20 nm). These results indicate that contribution from Lifshitz-van der Waals energy play a more prominent role than acid-base contribution. Regarding electrostatic contribution, it is not expected to play a major role in the selectivity of the separation at pH 8 because the zeta potential of both minerals is very low in magnitude (although different in signal). The interaction energy for feldspar/precipitate versus distance is more negative than the energy of apatite/precipitate versus distance from both DLVO and X-DLVO theories. Such a difference could explain the selectivity of separation between apatite and feldspar with amidoamine (107 mg/L) at pH 8.

Les architectures moléculaires qui se forment exclusivement sur une surface sont encore rares. L’électrodéposition est un procédé exploitant des « signaux » électriques afin de déclencher et contrôler l’assemblage de films. Récemment, une nouvelle méthode : l’autoconstruction de films en « une étape » par l’utilisation d’un morphogène (un gradient de catalyseur généré depuis une électrode), a attiré l’attention de la communauté scientifique. En effet, elle permet l’auto-assemblage rapide de films polymériques robustes. Cependant, cette technique était limitée à des systèmes basés sur la chimie click du Cu (I). Le but de ce travail était d’étendre cette stratégie à d’autres systèmes en utilisant une approche bio-inspirée. Le concept du morphogène a été appliqué pour développer deux nouveaux systèmes d’autoconstruction déclenchées par électrochimie. Le premier système est basé sur l’autoconstruction covalente de films polymériques induite par l’oxydation d’une molécule organique, inspirée de la moule. Le deuxième est basé sur l’auto-assemblage de films de polyphénols par électro-assemblage par liaisons de coordinations. Enfin, nous avons appliqué ces deux concepts pour immobiliser électrochimiquement une enzyme sur une électrode afin de créer un biosenseur. / Molecular architectures that spontaneously grow exclusively near a surface are rare. Electrodeposition is a process in which imposed electrical « signals » are employed to direct the assembly of thin films. Recently, a new method based on the one-pot self-construction of films by means of a morphogen (a catalyst gradient generated from a surface) has attracted attention since it allows the quick self-assembly of robust films. Nevertheless, this technique was quite limited to systems based on click chemistry.The purpose of this work was to extend this strategy to other systems using a bio-inspired approach. The one-pot morphogen concept was applied to design two new electro-triggered self-construction concepts. The first one is based on the self-construction of covalent polymer films triggered by mussel-inspired molecule oxidation. The second one is based on the electro-self-assembly of polyphenols films based on ionic bonds coordination. Finally, we tried to apply these concepts in order to electrochemically immobilize an enzyme on an electrode to create a biosensor.

Organic crystals are found in everyday goods such as foods, drugs, dyes, and agricultural products. To better understand the solid-state behaviour of organic crystals, the study of their surfaces is crucial, as several reactions occur at the interface between the crystal surface and its immediate environment. While atomic force microscopy (AFM) is a useful tool for studying surfaces, it is not a common technique for studying organic crystals. The rst part of this report aims to address problems of imaging organic crystals by AFM which arise from the nature of the imaging technique and the material property of organic crystals. Methods of detecting and predicting the likelihood of the problems encountered in imaging organic crystals are suggested in order for a more accurate interpretation of the information obtained by this technique. The e ect of humidity on aspirin crystal surfaces is then investigated by AFM. The growth of new features on the surface is believed to be a result of the hydrolysis of aspirin molecules. Mechanisms are suggested based on the observed surface response of aspirin, where surface defects and the mobility of surface molecules are believed to be important factors a ecting reactivity. The last section investigates the solid-state photochemical reaction of anthracene, which is a reaction that should not occur according to the topochemical postulate. The surface response of anthracene crystals to UV light was studied, and the results indicate strong reactivity at sites of surface defects, which is likely due to photodimerisation. A similar mechanism that described the behaviour of aspirin surfaces was suggested for this reaction. In summary, both reactions that were studied provided a better insight towards understanding the solid-state reactivity of organic crystals. The proposed surface mechanisms imply that surface defects and the presence of humidity or solvent vapour are very likely to play a role in determining reactivity. Further studies on the origin of defects are suggested in order to better control the behaviour of organic crystals in the solid-state.

Lipossomos de cloreto de dioctadecildimetilamonio (DODAC) com 0,51µ de diâmetro externo médio e transição de fase ocorrendo em uma faixa estreita de temperaturas (0,5-1,0°C) foram obtidos por vaporização de clorofórmio e comparados com vesículas sonicadas de DODAC (cerca de 250 Å de diâmetro externo). Sacarose foi impermeante através de lipossomos grandes de DODAC ou de vesículas sonicadas de DODAC podendo ser utilizada para determinações de volume interno em ambas as preparações. Volume interno aparente para lipossomos grandes de DODAC foi 9,7 ± 1,3 1/mol e para vesículas sonicadas de DODAC, 0,33 ± 0,20 1/mol (adsorção de sacarose à bicamada de, respectivamente, 0,64 ± 0,30 e 0,20 ± 0,08 1/mol). Lipossomos grandes de DODAC comportaram-se como osmômetros em relação à sacarose e ao KCl (0-50mM KCl). Já as vesículas sonicadas de DODAC foram osmoticamente não-responsivas em relação à sacarose, floculando em presença de KCl. Essa não-responsividade osmótica foi interpretada como decorrente da presença única e exclusiva de água de hidrataçao no compartimento aquoso interno das vesículas sonicadas. Outras propriedades de lipossomos grandes de DODAC foram análogas às apresentadas por lipossomos de fosfolípides. Permeabilidades relativas (KCl como referência incorporado ao compartimento aquoso interno) do NaCl, HCl e sacarose foram similares às descritas para lipossomos de fosfatidilcolina; NaCl e sacarose sendo tão impermeantes quanto o KCl e HCl, sendo ligeiramente mais permeante que o KCl. Nas vizinhanças da temperatura de transição de fase, ocorreu um acentuado aumento da velocidade inicial de encolhimento e a extensão total de encolhimento chegou a um mínimo. A comparaçao de algumas propriedades físicas e funcionais de vesículas sonicadas e de lipossomos grandes de DODAC permitiu concluir que lipossomos grandes de DODAC constituem um modelo mais adequado para estudos de transporte. Adicionalmente, o método de vaporização de clorofórmio foi testado para o dihexadecilfosfato de Na+ (DCP) sendo obtidas dispersões homogêneas desse anfifílico capazes de incorporar um volume de 13 ± 4 1/mol e de responderem como osmômetros a gradientes osmóticos de sacarose, um soluto que praticamente nao é adsorvido à bicamada de DCP e que resultou impermeante através da mesma. / Dioctadecyldimethylammonium chloride (DODAC) liposomes with 0.51µ mean external diameter and sharp phase transitions were obtained by chloroform vaporization and compared with (small) sonicated DODAC vesicles. Sucrose was impermeant through large DODAC liposomes and sonicated vesicles and was used for internal volume determinations. The apparent internal volumes for large DODAC liposomes and sonicated DODAC vesicles were, respectively, 9.7 ± 1.3 and 0.33 ± 0.20 1/mol. (External sucrose adsorption were, respectively, 0.64 ± 0.30 and 0.20 ± 0.08 l/mol). Ideal osmometer behaviour towards KCl over the 0-50mM concentrations range and towards sucrose were observed only for large DODAC liposomes. Sonicated DODAC vesicles were osmotically non responsive towards sucrose and floculate with KCl. Other properties of large DODAC liposomes closely resembled those of phospholipid liposomes. At temperatures near the phase transition temperature, a steep increase in the initial shrinkage rate and a minimum for the total extent of shrinkage occured. Relative permeabilities (KCl as reference entrapped inside) to NaCl, HCl and sucrose were similar to those of phosphatidyl choline liposomes. NaCl and sucrose were as impermeant as KCl, and HCl slighthly more permeant than KCl. Large DODAC liposomes are proposed as an adequate synthetic membrane model, in contrast to sonicated DODAC vesicles. In addition, the chlroform vaporization method was tested for sodium dihexadecylphosphate (DCP). Large DCP liposomes were demonstrated to be impermeant towards sucrose entrapping 13 ± 4 l/mol and behaving as an osmometer towards this solute.

Die Arbeit befasst sich mit dem chemischen Verhalten von Oberflächen an Siliciumnanopartikeln. Diese stehen in ihrer Reaktivität, aufgrund des großen Verhältnisses Oberfläche zu Volumen, zwischen einzelnen Atomen und ausgedehnten Kristallen. Durch Umsetzung mit unterschiedlich funktionalisierten Molekülen gelingt es, die Oberfläche der Partikel zu modifizieren. Dabei wurde eine neue Möglichkeit gefunden, Si-C-Bindungen auf Si-Oberflächen zu erzeugen. Die Modifizierung mit Wasserstoff (durch Behandlung mit HF) oder mit Chlor (durch Umsetzung mit Chlorierungsmitteln) schafft neue, synthetisch wertvolle Ausgangssituationen. Darauf aufbauend konnten Alkyl, Alkoxy- und Amingruppen kovalent angeknüpft werden. Die chemische Modifizierung der Nanopartikel führt zu verändertem Photoleitfähigkeits- sowie Photolumineszenzverhalten. Es wurde ein Vorschlag zur Deutung dieser Effekte entwickelt.

In the field of electronic organic materials, conjugated polymers (CPs) have attracted much attention in recent years. It has been well-established that performances of thin-film devices based on π-conjugated polymers, such as light-emitting diodes, field-effect transistors and photovoltaic cells, are strongly dependent on the organisation of the polymer molecules and their interactions with other constituents in multicomponent devices. The use of CPs in integrated circuits, solar cells, light-emitting diodes or sensors often requires their covalent fixation and patterning on various surfaces. CPs can be grafted to functionalized surfaces by (electro)chemical cross-linking; however, it is difficult to control a structural order within the cross-linked films. The attachment of CP chains to substrates by their end-points to form polymer brushes would be an interesting alternative, and could possibly be crucial for many devices requiring charge injection and charge transport processes. The main aim of this work, which was the synthesis of covalently grafted conjugated polymer brushes on solid substrates using a "grafting from" approach, was successfully performed. During the course of this work, the process of surface-initiated polycondensation was investigated. The newly developed method to selectively graft conjugated polymers from different substrates such as Si-wafers, quartz slides or modificated nanoparticles allowed us to produce different architectures which were earlier possible to prepare only non-conductive polymers. Exposure of the substrate with an activated surface layer into the monomer solution produced polymer brushes in a very economical way. Since only monomer was consumed for grafting from the surface. The grafting process was extensively investigated by different methods, and the thickness of the obtained poly(fluorene) films was elucidated by Null-ellipsometry and confirmed by the AFM scratch-test. Preliminary characteristics of the device, based on PS(Br)-core poly(octylfluorene)-shell nanoparticles, showed satisfactory results (such as turn-on voltage and electroluminescence in a blue region). They could be improved by replacement of the insulating PS(Br)-core of nanoparticles with other substances (semiconductive, etc.). There is still plenty of room for further development and improvement of the synthesis of poly(fluorene)-based polymer brushes. The polymer structures developed in this work can be utilized as an active layer in lab-on-chip devices. Alkyl groups in the 9th position of the poly(fluorene) monomer unit can be replaced by tailored receptors to detect specific species including small molecules, metal ions and biomolecules due to enhanced sensitivity through sensory signal amplification. Post-polymerization modifications may lead to highly water-swellable conjugated polyelectrolyte brushes. Also, polymerization of initially optically active fluorene-monomers may be the crucial step to the generation of a light source devices with a large degree of circularly polarized electroluminescence. This is of great interest for utilization as backlight for liquid crystalline displays. We believe that the utilization of covalently surface-immobilized conjugated polymers may have a great impact on the development of present-day technological processes.

This licentiate thesis is focused on two methods for protein immobilization to biosensor surfaces for future applications in protein microarray formats. The common denominator is a surface chemistry based on a gold substrate with a self-assembled monolayer (SAM) of functionalized alkanethiolates. Both methods involve photochemistry, in the first case for direct immobilization of proteins to the surface, in the other for grafting a hydrogel, which is then used for protein immobilization. Paper I describes the development and characterization of Chelation Assisted Photoimmobilization (CAP), a three-component surface chemistry that allows for covalent attachment and controlled orientation of the immobilized recognition molecule (ligand) and thereby provides a robust sensor surface for detection of analyte in solution. The concept was demonstrated using His-tagged IgG-Fc as the ligand and protein A as the analyte. Surprisingly, as concluded from IR spectroscopy and surface plasmon resonance (SPR) analysis, the binding ability of this bivalent ligand was found to be more than two times higher with random orientation obtained by amine coupling than with homogeneous orientation obtained by CAP. It is suggested that a multivalent ligand is less sensitive to orientation effects than a monovalent ligand and that island formation of the alkanethiolates used for CAP results in a locally high ligand density and steric hindrance. Paper II describes the development of nanoscale hydrogel structures. These were photografted on a SAM pattern obtained by dip-pen nanolithography (DPN) and subsequent backfilling. The hydrogel grew fast on the hydrophilic patterns and slower on the hydrophobic background, which contained a buried oligo(ethylene glycol) (OEG) chain. Using IR spectroscopy, it was found that the OEG part was degraded during UV light irradiation and acted as a sacrificial layer. In this process other OEG residues were exposed and acted as new starting points for the self-initiated photografting and photopolymerization (SIPGP). A biotin derivative was immobilized to the hydrogel density pattern and interaction with streptavidin was demonstrated by epifluorescence microscopy.

To investigate conditions of silver electroless deposition on silicon (100), optical microscope, atomic force microscope (AFM) and attenuated total reflection infrared spectroscopy (ATR-FTIR) spectroscopy were used. Twenty second dipping in 0.8mM AgNO3/4.9% solution coats a silicon (100) wafer with a thin film of silver nanoparticles very well. According to AFM results, the diameter of silver particles is from 50 to 100nm. After deposition, arithmetic average of absolute values roughness (Ra) increased from ~0.7nm to ~1.2nm and the root mean square roughness (Rq) is from ~0.8nm to ~1.5nm. SCN- ions were applied to detect the existence of silver on silicon surface by ATR-FTIR spectroscopy and IR spectra demonstrate SCN- is a good adsorbent for silver metal. Patina is the general name of copper basic salts which forms green-blue film on the surface of ancient bronze architectures. Patina formation has been found on the surface of platinum or ruthenium after several scans of cyclic voltammetry in 2mM CuSO4/0.1M K2SO4, pH5 solution. Evidence implies that oxygen reduction reaction (ORR) triggers the patina formation. ORR is an important step of fuel cell process and only few sorts of noble metals like platinum can be worked as the catalyst of ORR. Mechanisms of patination involving ORR were investigated by cyclic voltammetry, optical microscope, AFM, rotating disk electrode and other experimental methods: the occurrence of ORR cause the increase of local pH on electrode, and Cu2+ ions prefer to form Cu2O by reduction. Patina forms while Cu2O is oxidizing back to Cu2+.

Indiana University-Purdue University Indianapolis (IUPUI) / The field of two-dimensional (2D) nanomaterials first began in earnest with the discovery of graphene in 2004 due to their unique shape-dependent optical, electronic, and mechanical properties. These properties arise due to their one-dimensional confinement and are further influenced by the elemental composition of the inorganic crystal lattice. There has been an intense focus on developing new compositions of 2D nanomaterials to take advantage of their intrinsic beneficial properties in a variety of applications including catalysis, energy storage and harvesting, sensing, and polymer nanocomposites. However, compared to the field of bulk materials, the influence of surface chemistry on 2D nanomaterials is still underdeveloped. 2D nanomaterials are considered an “all-surface” atomic structure with heights of a single to few layers of atoms. The synthetic methods used to produce 2D materials include bottom-up colloidal methods and top-down exfoliation related techniques. Both cases result in poorly controlled surface chemistry with many undercoordinated surface atoms and/or undesirable molecules bound to the surface. Considering the importance surfaces play in most applications (i.e., catalysis and polymer processing) it is imperative to better understand how to manipulate the surface of 2D nanomaterials to unlock their full technological potential. Through a focus of the ligand-surface atom bonding in addition to the overall ligand structure we highlight the ability to direct morphological outcomes in lead free halide perovskites, maximize optoelectronic responses in substoichiometric tungsten oxide, and alter physicochemical properties titanium carbide MXenes. The careful control of precursor materials including poly(ethylene glycol) (PEG) surface ligands during the synthesis of bismuth halide perovskites resulted in the formation of 2D quasi-Ruddlesden-Popper phase nanomaterials. Through small angle X-ray scattering (SAXS) and in conjunction with X-ray photoelectron spectroscopy (XPS) we were able to conclude that an in-situ formation of an amino functional group on our PEG-amine ligand was inserted into the perovskite crystal lattice enabling 2D morphology formation. Additionally, through UV-vis absorption and ultraviolet photoelectron spectroscopies we were able to develop a complete electronic band structure of materials containing varying halides (i.e., Cl, Br, and I). Furthermore, through the increased solubility profile of the PEG ligands we observed solvent controlled assemblies of varying mesostructures. We developed an ex-situ ligand treatment to manipulate the localized surface plasmon resonance (LSPR) response of anion vacancy doped tungsten oxide (WO3-x) nanoplatelets (NPLs). Upon ligand treatment to alter the surface passivating ligand from carboxylic acid containing myristic acid (MA) to tetradecylphosphonic acid (TDPA) we observed a >100 nm blue shift in the LSPR response. Using Fourier transform infrared (FTIR) and Raman spectroscopies in conjunction with DFT calculated Raman spectra we were able to conclude this shift was due to the formation of tridentate phosphonate bonds on the NPLs surface. Phosphonate bonding allows for an increase in surface passivation per ligand decreasing surface trapped electrons. These previously trapped electrons were then able to participate as free electrons in the LSPR response. Electron paramagnetic spectroscopy (EPR) further supported this decrease in surface traps through a decrease and shift of the EPR signal related to metal oxide surface trapped electrons. Lastly, using our knowledge of PEG ligands we were able to modify esterification chemistry to covalently attach PEG ligands to a MXene surface. The successful formation of an ester bond between a carboxylic acid containing PEG ligand and hydroxyl terminating group on the MXene surface was supported by FTIR spectroscopy and thermogravimetric analysis. The attachment of PEG resulted in a drastic change in the hydrophilicity of the MXene surface. Where MXenes were previously only processed in extremely polar solvents the PEG attachment allowed for high dispersibility in a wide range of polar and non-polar organic solvents, effectively increasing their processability. Further, this chemistry was modified to include an additional functional group on the PEG ligand to increase the valency of the post-modification MXene nanoflakes. Overall, work presented in this dissertation represents the development and application of surface chemistry to relatively new 2D nanomaterials. We believe our work significantly increases the knowledge of 2D halide perovskite formation, manipulation of LSPR active metal oxide materials, and the future processing of MXene materials.

The Swedish industrial research institutes are research organisations that exist somewhat in between academy and industry, fulfilling an intermediary role as well as providing a space for research relevant to industrial companies, and they have a history of being funded by both state and industry as a way to support technical research in Sweden. The present study examines the history one of these institutes – the Institute for Surface Chemistry – with respect to three dimensions of its knowledge production: the role that basic and applied research has played for the institute, its external connections and the heterogeneity of its knowledge production, and how it has evaluated the quality of its research. The time period considered is 1975-2005, a challenging time for the Swedish institute sector, and the analysis is based on an interpretation of annual reports, research programs and newsletters from the period, as well as on interviews with institute managers and researchers.This work contributes to a wider research field in two respects. First, it provides input to the ongoing debate about how a changing research system is linked to changes in knowledge production. Second, it increases our knowledge of the Swedish industrial research institute sector, something interesting in its own right but that also can provide input to the ongoing policy reorientation vis-à-vis these institutes. The main novelty of the work is that it engagessystematically and historically with changes in knowledge production within an industrial research institute, something not done in previous studies of the sector. To briefly summarise the results, applied research gradually becomes more important than basic research at the institute, but basic research still keeps playing a rather large role for some time, even as this roleis downplayed in the official publications. At the same time, the institute becomes more heterogeneous in its knowledge production, associates closer with its industrial partners, and loses some of its independent knowledge production in favour of a more classic intermediary role. During the study period, the institute mainly ascertains the quality of its work through the use of traditional academic standards, and it retains a strong publication culture throughout.Three main conclusions are drawn: that the institute generally has oriented itself more towards its industrial partners; that this is the result of adapting to a situation in which the traditional state funding and political support appear ever more insecure; and that in spite of this general dynamic of adaption, the institute, thanks to a unique knowledge base or strong and well-connected actors, has sometimes been able to defend its preferred modes of knowledge production instead of adapting,something which also has had a notable impact on its development.