COINCIDENCES OF FIBREWISE MAPS BETWEEN SPHERE BUNDLES OVER THE CIRCLE

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

High-Pressure Micellar Solutions of Polystyrene-block-polybutadiene and Polystyrene-block-polyisoprene in Propane Exhibit Cloud-Pressure Reduction and Distinct Micellization End Points

Micellar solutions of polystyrene-block-polybutadiene and polystyrene-block-polyisoprene in propane are found to exhibit significantly lower cloud pressures than the corresponding hypothetical nonmicellar solutions. Such a cloud-pressure reduction indicates the extent to which micelle formation enhances the apparent diblock solubility in near-critical and hence compressible propane. Concentration-dependent pressure-temperature points beyond which no micelles can be formed, referred to as the micellization end points, are found to depend on the block type, size, and ratio. The cloud-pressure reduction and the micellization end point measured for styrene-diene diblocks in propane should be characteristic of all amphiphilic diblock copolymer solutions that form micelles in compressible solvents.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.

Contesting Sphere Boundaries Online: Private/Technical/Public Discourses in Polycystic Ovarian Syndrome Discussion Groups

The internet is fast becoming a means for people to obtain information, creating a unique forum for the intersection of the public, technical, and private spheres. To ground my research theoretically, I used Jürgen Habermas’s sphere theory. Habermas (1987) explains that the technical sphere colonizes the private sphere, which decreases democratic potential. In particular, the internet is a place for altering technical colonization of the private and public spheres. My research focuses on women’s health because it is a particularly useful case study for examining sphere tensions. Historically, the biomedical health establishment has been a powerful agent of colonization, resulting in detrimental effects for women and their health. The purpose of this study is to examine how the internet encourages expert and female patient deliberation, which empowers women to challenge the experts and, thus, make conversations between the private/technical spheres more democratic. I used PCOS (Polycystic Ovarian Syndrome) as a case to observe the changing sphere boundaries by studying the discourse that took place on multiple patient and doctor websites over a four-year period. Through my research, I found that the PCOS women challenge the biomedical model by appropriating medical language. By understanding the medical talk, the women are able to feel confident when discussing their health conditions with the doctor and with each other. The PCOS women also become lay-experts who have personal and medical experience with PCOS, reducing private sphere colonization. This case study exemplifies how female empowerment can influence expert culture, challenging our conventional understanding of democracy.

Influence of Growth Media and Temperature on Bacterial Adhesion to Polystyrene Surfaces

Bacterial adhesion to inert surfaces is a complex process influenced by environmental conditions. In this work, the influence of growth medium and temperature on the adhesion of Pseudomonas aeruginosa, Serratia marcescens, Staphylococcus aureus, Micrococcus luteus and Listeria monocytogenes to polystyrene surfaces was studied. Most bacteria demonstrated the highest adhesion when cultured in TSYEA, except S. marcescens, which showed to be positively influenced by the pigment production, favored in poor nutrient media (lactose and peptone agar). P. aeruginosa adhesion to polystyrene increased at low temperatures whatever the medium used. The culture medium influenced the surface properties of the bacteria as assessed by the MATS test.

Morphology and topography analysis of mesoporous titania templated by micrometric latex sphere arrays

In this work, mesoporous titania is prepared by templating latex sphere arrays with four different sphere diameters at the micrometric scale (phi > 1 mu m). The mesoporous titania homogeneously covers the latex spheres and substrate, forming a thin coating characterized by N-2 adsorption isotherm, small angle X-rays scattering, atomic force, field emission and transmission electronic microscopies. Mesoporous titania has been templated into different shapes such as hollow particles and monoliths according to the amount of sol used to fill the voids of the close packed latex spheres. Titania topography strongly depends on the adsorption of polymeric segments over latex spheres surface, which could be decreased by changing the dimensions of latex spheres (phi = 9.5 mu m) generating a lamellar architecture. Thus, micrometric latex sphere arrays can be used to achieve new surface patterns for mesoporous materials via a fast and inexpensive chemical route for construction of functional devices in different technological fields such as energy conversion, inclusion chemistry and biomaterials. (C) 2011 Elsevier Inc. All rights reserved.

Influence of growth media and temperature on bacterial adhesion to polystyrene surfaces

Bacterial adhesion to inert surfaces is a complex process influenced by environmental conditions. In this work, the influence of growth medium and temperature on the adhesion of Pseudomonas aeruginosa, Serratia marcescens, Staphylococcus aureus, Micrococcus luteus and Listeria monocytogenes to polystyrene surfaces was studied. Most bacteria demonstrated the highest adhesion when cultured in TSYEA, except S. marcescens, which showed to be positively influenced by the pigment production, favored in poor nutrient media (lactose and peptone agar). P. aeruginosa adhesion to polystyrene increased at low temperatures whatever the medium used. The culture medium influenced the surface properties of the bacteria as assessed by the MATS test.

Weighted Fourier–Laplace transforms in reproducing kernel Hilbert spaces on the sphere

We study the action of a weighted Fourier–Laplace transform on the functions in the reproducing kernel Hilbert space (RKHS) associated with a positive definite kernel on the sphere. After defining a notion of smoothness implied by the transform, we show that smoothness of the kernel implies the same smoothness for the generating elements (spherical harmonics) in the Mercer expansion of the kernel. We prove a reproducing property for the weighted Fourier–Laplace transform of the functions in the RKHS and embed the RKHS into spaces of smooth functions. Some relevant properties of the embedding are considered, including compactness and boundedness. The approach taken in the paper includes two important notions of differentiability characterized by weighted Fourier–Laplace transforms: fractional derivatives and Laplace–Beltrami derivatives.

Sharp estimates for eigenvalues of integral operators generated by dot product kernels on the sphere

We obtain explicit formulas for the eigenvalues of integral operators generated by continuous dot product kernels defined on the sphere via the usual gamma function. Using them, we present both, a procedure to describe sharp bounds for the eigenvalues and their asymptotic behavior near 0. We illustrate our results with examples, among them the integral operator generated by a Gaussian kernel. Finally, we sketch complex versions of our results to cover the cases when the sphere sits in a Hermitian space.

Sphärische Bürsten in polymeren Schmelzen

Colloidal nanoparticles are additives to improve or modify several properties of thermoplastic or elastic polymers. Usually colloid-polymer mixtures show phase separation due to the depletion effect. The strategy to overcome this depletion demixing was to prepare surface-modified colloidal particles, which can be blended with linear polymer chains homogeneous. A successful synthesis strategy for the preparation of hairy nanospheres was developed by grafting polystyrene macromonomer chains onto polyorganosiloxane microgels. The number of hairs per particle with a core radius of approximately 10nm exceeded 150 hairs in all cases. The molecular weight of the hairs variied between 4000-18000g/mol.The compatibility of these hairy spheres mixed with linear polymer chains was investigated by AFM, TEM and SAXS. Homogeneous mixtures were found if the molecular weight of the polymer hairs on the particle surface is at least as large as the molecular weight of the matrix chains. If the chains are much shorter than the hairs, the colloidal hair corona is strongly swollen by the matrix polymer, leading to a long-range soft interparticle repulsion ('wet brush'). If hairs and chains are comparable in length, the corona shows much less volume swelling, leading to a short-range repulsive potential similar to hard sphere systems ('dry brush'). Polymerketten und Kolloidpartikel entmischen aufgrund von Depletion-Wechselwirkungen. Diese entropisch bedingte Entmischung konnte durch das Ankoppeln von Polymerhaaren verschiedenen Molekulargewichts auf die Kugeloberflächen der Kolloide bis zu hohen Konzentrationen vermieden werden. Zur Darstellung sphärischer Bürsten und haariger Tracerpartikel wurde eine neue Synthesestrategie ausgearbeitet und erfolgreich umgesetzt.Das Kompatibilitätsverhalten dieser sphärischen Bürsten in der Schmelze von Polymerketten als Matrix wurde mittels Elektronenmikroskopie und Kleinwinkelröntgenstreuung untersucht. Die Mischungen setzten sich aus sphärischen Bürsten und Matrixketten mit unterschiedlichen Molekulargewichten zusammen.Es zeigte sich, daß die Mischbarkeit entschieden durch das Verhältnis von Haarlänge zu Länge der Matrixketten beeinflußt wird.Aus den Untersuchungen des Relaxationsverhaltens mittels Rheologie und SAXS ergibt sich, daß das Konzept der 'dry brush'- und 'wet brush'-Systeme auf diese Mischungen übertragbar ist. Die Volumenquellung der Haarcorona durch die Matrixketten ist, wie die Experimente gezeigt haben, bereits im Fall von Polymeren mit relativ niedrigen Molekulargewichten zu beobachten. Sie ist umso stärker ausgeprägt, je größer das Längenverhältnis zwischen Polymerhaaren und Matrixketten ist. Die Quellung bedeutet eine Vergrößerung des effektiven Radius der Partikel und entspricht somit einer Erhöhung des effektiven Volumenbruchs. Dies führt zur Ausbildung einer höheren Ordnung und zu einem Einfrieren der Relaxation dieser strukturellen Ordnung führt.

Polymer properties measured by micromechanical cantilever technique

Surface stress changes induced by specific adsorption of molecules were investigated using a micromechanical cantilever sensor (MCS) device. 16 MCS are grouped within four separate wells. Each well can be addressed independently by different liquid enabling functionalization of MCS separately by flowing different solutions through each well and performing sensing and reference experiments simultaneously. In addition, each well contains a fixed reference mirror, which allows measuring the absolute bending of MCS. The effect of the flow rate on the MCS bending change was found to be dependent on the absolute bending value of MCS. In addition, the signal from the reference mirror can be used to follow refractive index changes upon mixing different solutions. Finite element simulation of solution exchange in wells was compared with experiment results. Both revealed that one solution can be exchanged by another one after a total volume of 200 µl has flown through. Using MCS, the adsorption of thiolated deoxyribonucleic acid (DNA) molecules and 6-mercapto-1-hexanol (MCH) on gold surfaces, and the DNA hybridization were performed. The nanomechanical response is in agreement with data reported by Fritz et al.1 Thus, the multiwell device is readily applicable for sensing of multiple chemical and biological recognition events in a single step. In this context controlled release and uptake of drugs are currently widely discussed. As a model system, we have used polystyrene (PS) spheres with diameters in the order of µm. The swelling behavior of individual PS spheres in toluene vapor was studied via mass loading by means of micromechanical cantilever sensors. For 4–8% cross-linked PS a mass increase of 180% in saturated toluene vapor was measured. In addition, the diameter change in saturated toluene vapor was measured and the corresponding volume increase of 200% was calculated. The mass of the swollen PS sphere decreases with increasing exposure time to ultraviolet (UV) light. The swelling response is significantly different between the first and the second exposure to toluene vapor. This is attributed to the formation of a cross-linked shell at the surface of the PS spheres. Shape persistent parts were observed for locally UV irradiated PS spheres. These PS spheres were found to be fluorescent and cracks occur after exposure in toluene liquid. The diffusion time of dye molecules in PS spheres increases with increasing chemical cross-linking density. This concept of locally dissolving non cross-linked PS from the sphere was applied to fabricate donut structures on surfaces. Arrays of PS spheres were fabricated using spin coating. The donut structure was produced simply after liquid solvent rinsing. The complete cross-linking of PS spheres was found after long exposure time to UV. We found that stabilizers play a major role in the formation of the donut nanostructures.

Optical resonances of sphere-on-plane geometries

The optical resonances of metallic nanoparticles placed at nanometer distances from a metal plane were investigated. At certain wavelengths, these “sphere-on-plane” systems become resonant with the incident electromagnetic field and huge enhancements of the field are predicted localized in the small gaps created between the nanoparticle and the plane. An experimental architecture to fabricate sphere-on-plane systems was successfully achieved in which in addition to the commonly used alkanethiols, polyphenylene dendrimers were used as molecular spacers to separate the metallic nanoparticles from the metal planes. They allow for a defined nanoparticle-plane separation and some often are functionalized with a chromophore core which is therefore positioned exactly in the gap. The metal planes used in the system architecture consisted of evaporated thin films of gold or silver. Evaporated gold or silver films have a smooth interface with their substrate and a rougher top surface. To investigate the influence of surface roughness on the optical response of such a film, two gold films were prepared with a smooth and a rough side which were as similar as possible. Surface plasmons were excited in Kretschmann configuration both on the rough and on the smooth side. Their reflectivity could be well modeled by a single gold film for each individual measurement. The film has to be modeled as two layers with significantly different optical constants. The smooth side, although polycrystalline, had an optical response that was very similar to a monocrystalline surface while for the rough side the standard response of evaporated gold is retrieved. For investigations on thin non-absorbing dielectric films though, this heterogeneity introduces only a negligible error. To determine the resonant wavelength of the sphere-on-plane systems a strategy was developed which is based on multi-wavelength surface plasmon spectroscopy experiments in Kretschmann-configuration. The resonant behavior of the system lead to characteristic changes in the surface plasmon dispersion. A quantitative analysis was performed by calculating the polarisability per unit area /A treating the sphere-on-plane systems as an effective layer. This approach completely avoids the ambiguity in the determination of thickness and optical response of thin films in surface plasmon spectroscopy. Equal area densities of polarisable units yielded identical response irrespective of the thickness of the layer they are distributed in. The parameter range where the evaluation of surface plasmon data in terms of /A is applicable was determined for a typical experimental situation. It was shown that this analysis yields reasonable quantitative agreement with a simple theoretical model of the sphere-on-plane resonators and reproduces the results from standard extinction experiments having a higher information content and significantly increased signal-to-noise ratio. With the objective to acquire a better quantitative understanding of the dependence of the resonance wavelength on the geometry of the sphere-on-plane systems, different systems were fabricated in which the gold nanoparticle size, type of spacer and ambient medium were varied and the resonance wavelength of the system was determined. The gold nanoparticle radius was varied in the range from 10 nm to 80 nm. It could be shown that the polyphenylene dendrimers can be used as molecular spacers to fabricate systems which support gap resonances. The resonance wavelength of the systems could be tuned in the optical region between 550 nm and 800 nm. Based on a simple analytical model, a quantitative analysis was developed to relate the systems’ geometry with the resonant wavelength and surprisingly good agreement of this simple model with the experiment without any adjustable parameters was found. The key feature ascribed to sphere-on-plane systems is a very large electromagnetic field localized in volumes in the nanometer range. Experiments towards a quantitative understanding of the field enhancements taking place in the gap of the sphere-on-plane systems were done by monitoring the increase in fluorescence of a metal-supported monolayer of a dye-loaded dendrimer upon decoration of the surface with nanoparticles. The metal used (gold and silver), the colloid mean size and the surface roughness were varied. Large silver crystallites on evaporated silver surfaces lead to the most pronounced fluorescence enhancements in the order of 104. They constitute a very promising sample architecture for the study of field enhancements.

La PCA per la riduzione dei dati di SPHERE IFS

Nel primo capitolo di questa tesi viene presentata una panoramica dei principali metodi di rivelazione degli esopianeti: il metodo della Velocità Radiale, il metodo Astrometrico, il metodo del Pulsar Timing, il metodo del Transito, il metodo del Microlensing ed infine il metodo del Direct Imaging che verrà approfondito nei capitoli successivi. Nel secondo capitolo vengono presentati i principi della diffrazione, viene mostrato come attenuare la luce stellare con l'uso del coronografo; vengono descritti i fenomeni di aberrazione della luce provocati dalla strumentazione e dagli effetti distorsivi dell'atmosfera che originano le cosiddette speckle; vengono poi presentate le moderne soluzioni tecniche come l'ottica attiva e adattiva, che hanno permesso un considerevole miglioramento della qualità delle osservazioni. Nel terzo capitolo sono illustrate le tecniche di Differential Imaging che permettono di rimuovere efficacemente le speckle e di migliorare il contrasto delle immagini. Nel quarto viene presentata una descrizione matematica della Principal Component Analysis (Analisi delle Componenti Principali), il metodo statistico utilizzato per la riduzione dei dati astronomici. Il quinto capitolo è dedicato a SPHERE, lo strumento progettato per il Very Large Telescope (VLT), in particolare viene descritto il suo spettrografo IFS con il quale sono stati ottenuti, nella fase di test, i dati analizzati nel lavoro di tesi. Nel sesto capitolo vengono mostrate le procedure di riduzione dati e l'applicazione dell'algoritmo di IDL LA_SVD che applica la Principal Component Analysis e ha permesso, analogamente ai metodi di Differenzial Imaging visti in precedenza, di rimuovere le speckle e migliorare il contrasto delle immagini. Nella parte conclusiva, vengono discussi i risultati.