Synthesis and characterization of phosphorylcholine-substituted chitosans soluble in physiological pH conditions

A polymer analogous synthesis involving the reductive amination of phosphorylcholine (PC)-glyceraldehyde with primary amines of deacetylated chitosan (M-w approximate to 57000 g mol(-1)) was used to prepare phosphorylcholine-substituted chitosans (PC-CH) with a degree of substitution (DS) ranging from similar to 11 to similar to 53 mol% PC-substituted glucosamine residues. The PC-CH derivatives were characterized by H-1 NMR spectroscopy, FTIR spectroscopy, and multiangle laser light scattering gel permeation chromatography (MALLS-GPC). The pKa of the PC-substituted amine groups (pKa approximate to 7.20) was determined by H-1 NMR titration. The PC-CH samples (1.0 g L-1) were shown to be nontoxic using an MTT assay performed with human KB cells. Aqueous solutions of PC-CH samples (4.0 g L-(1)) of DS g 22 mol% PC-substituted glucosamine residues remained clear, independently of pH (4.0 < pH < 11.0). The remarkable water solubility and nontoxicity displayed by the new PC-CH samples open up new opportunities in the design of chitosan-based biomaterials and nanoparticles.

O cinema sem rua

The project consists of a book-report on the street movie theaters in Brazil, which are increasingly scarce. Multiplexes are taking the market by several factors, including scheduling and directed to the blockbusters that malls provide security, which does not occur in street theaters, which have a more independent programming. The report will portray the film as a physical space and playful all the influence that the place provides, yet is losing its audience

Cidade média de limiar superior: um estudo a partir de Ribeirão Preto (SP)

This papper aims to discuss Ribeirão Preto as a switched-over intermediate city classification, contrastating with the concept of Metropolitan Region of Ribeirão Preto. The agribusiness sector will be analysed as the main responsible for the representation of Ribeirão Preto city as an Agribusiness Center. Due to this fact, Sertãozinho city example will be presented as Agribusiness City, where acctually concentrates the agro-industrial complex of sugarcane production, while Ribeirão Preto is in fact centralizes management activities. According to the balance of trade analysis, other elements showed up and fortifies the role of this cities. These elements unfolded the analysis of higher education guideline and shopping malls. We also analyzed the urban network of Ribeirão Preto under the concept of the Região de Influência das Cidades (REGIC) and the creation of the project Metropolitan Region of Ribeirão Preto in order to strengthen the central hypothesis as a switched-over medium sized city. In order to reach this point, besides the analysis of the data we had t literature review of the Medium Sized Cities and Urban Network concepts and Spatial Interactions and Switched- over terms

Deslocamentos pendulares, consumo e shopping centers em cidades médias paulistas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Centralidades segmentadas: os shopping centers da cidade de São José do Rio Preto/SP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Repensando a metodologia do Índice de Potencial de Consumo (IPC) para estudos sobre consumo nas cidades medias

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

Shopping popular Feiraguai: estudos sobre a produção de um espaço de comércio em Feira de Santana - BA

Pós-graduação em Geografia - IGCE

Review of Prairie Time: A Blackland Portrait by Matt White

Nowadays, the Blackland Prairies of north Texas are the kind of landscape most people think of as great for subdivisions and strip malls: generally flat, easily bulldozed, and not too far from Dallas-Fort Worth. Prairie Time: A Blackland Portrait traces a similar utilitarian vision of the prairie in 19th-century pioneer descriptions as well: good for plowing, grazing, and-once the buffalo and Native Americans are exterminated-not too far from outposts of commerce. The book serves as an environmental jeremiad for a place too easily seen as useful and thus too often ignored for preservation. Matt White gives readers a context in which to begin to value the Blackland Prairie by combining a heartfelt story with a thorough sense of its ecological wonder, our post-settlement history and its environmental impact on the land, and some remarkable stories of current preservationists working to find and save remnant gems of unplowed prairie.

Repensando a metodologia do Índice de Potencial de Consumo (IPC) para estudos sobre consumo nas cidades medias

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

Shopping popular Feiraguai: estudos sobre a produção de um espaço de comércio em Feira de Santana - BA

Pós-graduação em Geografia - IGCE

Consumer attitudes, knowledge, and behavior related to salt consumption in sentinel countries of the Americas

Objective. To describe individual attitudes, knowledge, and behavior regarding salt intake, its dietary sources, and current food-labeling practices related to salt and sodium in five sentinel countries of the Americas. Methods. A convenience sample of 1 992 adults (>= 18 years old) from Argentina, Canada, Chile, Costa Rica, and Ecuador (approximately 400 from each country) was obtained between September 2010 and February 2011. Data collection was conducted in shopping malls or major commercial areas using a questionnaire containing 33 questions. Descriptive estimates are presented for the total sample and stratified by country and sociodemographic characteristics of the studied population. Results. Almost 90% of participants associated excess intake of salt with the occurrence of adverse health conditions, more than 60% indicated they were trying to reduce their current intake of salt, and more than 30% believed reducing dietary salt to be of high importance. Only 26% of participants claimed to know the existence of a recommended maximum value of salt or sodium intake and 47% of them stated they knew the content of salt in food items. More than 80% of participants said that they would like food labeling to indicate high, medium, and low levels of salt or sodium and would like to see a clear warning label on packages of foods high in salt. Conclusions. Additional effort is required to increase consumers' knowledge about the existence of a maximum limit for intake and to improve their capacity to accurately monitor and reduce their personal salt consumption.

Synthese und Charakterisierung von Poly(tert-butylacrylat)- und Polyacrylsäure-Sternpolymeren

Sternpolymere aus Poly(tert.-butylacrylat)-Armen und einem Mikrogel-Core aus Ethylenglykoldimethacrylat wurden nach der arm-first Strategie hergestellt. Diese weisen eine enge Armzahlverteilung auf. Mit sinkender Precursorlänge, mit steigendem Verhältnis [bifunktionelles Monomer]/[Initiator], sowie mit zunehmender Reaktionszeit und Gesamtkonzentration nimmt die mittlere Armzahl fn zu. Die Sternbildung verläuft ähnlich einer Polykondensation. Die Molekulargewichte wurden mittels GPC gekoppelt mit einem online-Viskosimeter und einem online-Vielwinkellichtstreudetektor (MALLS) bestimmt.Die intrinsischen Viskositäten der Sternpolymere sind sehr niedrig. Für Armzahlen f ca. 8 erhält man ein Maximum in der doppellogarithmischen Auftragung der intrinsischen Viskosität und des Molekulargewichts. Die Trägheitsradien nehmen nur wenig mit dem Molekulargewicht zu. Die erhaltenen Koeffizienten liegen im von Daoud und Cotton vorhergesagten Bereich. Die Schrumpfungsfaktoren sinken auf g ca. 0,2 bzw. g' ca. 0,25. Aus den Poly(tert.-butylacrylat)-Sternpolymeren wurden durch Verseifung mit HBr in Methanol Polyacrylsäure-Sternpolymere hergestellt, welche ebenfalls mittels GPC-Viskosimetrie und GPC-MALLS charakterisiert wurden. Für die ionischen Sternpolymere findet man deutlich höhere Schrumpfungsfaktoren, kein Maximum in der intrinsischen Viskosität und höhere Exponenten als von Daoud und Cotton vorhergesagt. Erklärt wurde dies mit der hohen Segmentdichte in Sternpolymeren, die bei den ionischen Sternpolymeren zu einer hohen Ladungsdichte führt. Dadurch müssen sich die Arme stärker strecken als bei nicht-ionischen Sternen und es resultieren größere Moleküldimensionen.

Synthesis and characterization of polyelectrolyte brushes

On the pathway to synthesizing synthetic model systems for human cartilage, macroinitiators for the ATRP of styrene sulfonate esters with different chain lengths and initiation site densities from 10 % to 100 % were synthesized. Polymer brushes from styrene sulfonate ethyl ester and styrene sulfonate dodecyl ester with varying grafting density, backbone length and side chain length were synthesized and characterized by 1H-NMR, AUC, AFM, TEM, and in the case of the ethyl esters, GPC-MALLS. Polyelectrolyte brushes from styrene sulfonate were synthesized from the corresponding esters. These brushes were characterized in solution (GPC-MALLS, static and dynamic light scattering, SANS, 1H-NMR) and on solid interfaces (AFM and TEM). It was shown that these brushes may form extended aggregates in solution. The aggregation behavior and the size and shape of the aggregates depend on the side chain length and the degree of saponification. For samples with identical backbone and side chain length, but varying degrees of ester hydrolysis, marked differences in the aggregation behavior were observed. A functionalized ATRP macroinitiator with a positively charged head group was synthesized and employed for the synthesis of a functionalized polyelectrolyte brush. These brushes were found to form complexes with negatively charged latex particles and are thus suitable as proteoglycan models in the proteoglycan-hyaluronic acid complex.

From amphiphilic block copolymers to ferrocenyl-functionalized polymers for biosensoric applications

The present thesis can be divided in three main parts. In all parts new polymer architecturesrnwere synthesized and characterized concerning their special features.rnThe first part will emphasize the advantage of a polystyrene-block-(hyperbranchedrnpolyglycerol) copolymer in comparison to an analogue polystyrene-block-(linear polyglycerol)rncopolymer. Therefore a synthethic route to prepare linear block copolymersrnhas been developed. Two strategies were examined. One strategy was based on thernclassic, sequential anionic polymerization; the second strategy was based on arn“Click-Chemistry” coupling reaction. In a following step glycidol was hypergraftedrnfrom these block copolymers by applying a hypergrafting reaction with glycidol. Thernbehavior of the amphiphilic block copolymers synthesized was studied in differentrnsolvents. Furthermore the polarity of the solvent was changed to form the correspondingrninverse micelles. DLS, SLS, SEC-MALLS-VISCO, AFM and Cyro TEMrnmeasurements were performed to obtain a visual image from the appearance of thernaggregates. It was found that a linear-hyperbranched architecture is necessary, ifrnwell defined, monodisperse aggregates are required, e.g. for the preparation of orderedrnnanoarrays. Linear-linear block copolymers formed only polydisperse aggregates.rnAdditionally it was found that size distribution could be improved dramaticallyrnby passing the aggregates through a SEC column with large pores. The SEC columnsrnacted like a template in which the aggregates adopt a more stable conformation.rnIn the second part anionic polymerization was employed to synthesize silaneendfunctionalizedrnmacromonomers with different molecular weights based on polybutadienernand polyisoprene. These were polymerized by a hydrosilylation reaction inrnbulk to obtain branched polymers, using Karstedt’s catalyst. Surprisingly the additionrnof monofunctional silanes during the polymerization had only a minimal effect concerningrnthe degree of polymerization. It was possible to introduce silanes without increasingrnthe overall number of reaction steps by a very convenient “pseudo-copolymerization”rnmethod. All branched polymers were analyzed by SEC, SEC-MALLS,rnSEC-viscometry, 1H-NMR-spectroscopy and DSC concerning their branching ratio.rnThe branching parameters for the branched polymers exhibited similar characteristicsrnas hyperbranched polymers based on AB2 monomers. Detailed kinetic study showedrnthat the polymerization occurred very rapidly in comparison to the hydrosilylation polymerizationrnof classical AB2 type carbosilanes monomers.rnThe last part will deal with ferrocenyl-functionalized polymers. On the one hand,rnferrocenyl-functionalized polyglycerols (PG) were studied. Esterification of PGs withrndifferent molecular weight using ferrocenemonocarboxylic acid gave the ferrocenylrnfuntionalized polymers in high yields. On the other hand three different block copolymersrnwere prepared with different ratios of styrene to butadiene units (10:1, 4:1, 2:1).rnThe double bonds of the 1,2-PB block were hydrosilylated using silanes bearing onern(HSiMe2Fc) or two (HSiMeFc2) ferrocene units. High degrees of functionalizationrnwere obtained (up to 83 %). In this manner, six different ferrocenyl-rich block copolymersrnwith different fractions of ferrocene were prepared and analyzed, employingrnNMR-spectroscopy, SEC, SEC/MALLS/viscometry, DLS and cyclic voltammetry. Thernredox properties of the studied polymers varied primarily with the nature of the silanernunit attached. Additionally, the redox properties in solution of the studied polymersrnwere influenced by the block length ratio of the block copolymers. Unexpectedly, withrnincreasing block length of the ferrocenyl block the fraction of active ferrocenes decreased.rnNevertheless, in case of thin monolayer films this behaviour was not observed.rnAll polymers (PG and PS-b-PB based) exhibited good electrochemical propertiesrnin a wide range of solvents, which rendered them very interesting for biosensoricrnapplications.

Dramaturgien der Wirklichkeit: Dokumentarfilme im Theater

Die Wirklichkeit ist durchdrungen von dramaturgischen Erzählmustern. Parallel dazu verschwinden Mythen und Utopien aus dem Theater und wandern in die Medien ab. Zeitgenössische Theateraufführungen verwenden dokumentarische Filmstoffe und Dokumentarfilme nutzen theatrale Formen: Dramaturgien sind austauschbar. Das Buch liefert eine Methodik, die das Beziehungsgefüge zwischen theatralen Phänomenen im Alltag, ihrer medialen Verwertung im Dokumentarfilm und der Transformation dieser Dokumentarfilme auf dem Theater klärt. Ausgangspunkt des dramaturgischen Vergleichs bilden zwei Dokumentarfilme, die als Vorlage von Theaterinszenierungen dienten: Die Dekonstruktion des nationalen Mythos eines gefallenen Skihelden; die verkaufte Utopie der idealen Stadt als Shopping-Mall. Am 8. Dezember 2002 stürzt der Skirennfahrer Silvano Beltrametti bei der Abfahrt in Val-d’Isère und ist seither querschnittgelähmt. Ein Jahr nach seinem Unfall strahlt das Schweizer Fernsehen den Dokumentarfilm «Silvano Beltrametti – Mit kleinen Siegen zurück ins Leben» aus. Der Film zeichnet das Bild eines Optimisten, der trotz Behinderung im Herzen ein Sportler bleibt. 2004 bringt das Theaterkollektiv 400asa den Dokumentarfilm auf die Bühne und hinterfragt mit der Aufführung «B. Ein Stück über Sport und Behinderung» den nationalen Mythos des gefallenen Helden. Doch nicht nur in der Welt des Sports können dramaturgische Wirkungsstrategien nachgewiesen werden. Harun Farocki zeigt in seinem Dokumentarfilm «Die Schöpfer der Einkaufswelten» den inszenatorischen Gestaltungsprozess, der der Entstehung einer Shopping-Mall vorausgeht. In der gleichnamigen Theaterinszenierung versetzt Tom Kühnel die akribische Planung der Malls ins maoistische China und verkehrt die Utopie der idealen Einkaufsstadt in ein buntes Spektakel.