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Made available in DSpace on 2014-06-11T19:23:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-03-22Bitstream added on 2014-06-13T18:50:46Z : No. of bitstreams: 1 oliveira_pl_me_arafcf.pdf: 2094182 bytes, checksum: 926895d5e73c0de69bc13d5a0444ffcd (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Universidade Estadual Paulista (UNESP) / As hipóteses mais modernas baseiam o processo de envelhecimento cutâneo em duas teorias: o intrínseco (ou cronológico) e o extrínseco (ou fotoenvelhecimento). Tanto no envelhecimento intrínseco como no extrínseco, as principais alterações da pele são caracterizadas por formação de rugas, flacidez e perda da elasticidade. O palmitato de retinol (PR) é um análogo sintético da vitamina A indicado topicamente para prevenir ou retardar algumas mudanças estruturais e funcionais da pele associadas ao processo de envelhecimento cutâneo, porém é um princípio ativo que apresenta estabilidade química limitada frente à umidade, oxigênio, ácidos, metais e exposição à luz. Assim, o objetivo deste trabalho foi desenvolver um sistema líquido-cristalino à base de silicone para a liberação prolongada e maximização da estabilidade do palmitato de retinol. Utilizando-se o método de titulação da fase aquosa, foram construídos dois diagramas ternários de fases, ambos constituídos por Procetyl AWS® (tensoativo) e água e por silicone DC 5330® (fase oleosa no diagrama 1) ou silicone DC 5329® (fase oleosa no diagrama 2). Nos estudos de estabilidade preliminar, as formulações do diagrama 1 (A, B, C e D) e do diagrama 2 (E, F, G e H) foram avaliadas nos seguintes estudos: microscopia de luz polarizada, centrifugação, pH, condutividade eletrolítica, índice de refração e reologia. Dentre estas formulações estudas preliminarmente, a formulação GPR foi selecionada para ser conduzida aos estudos posteriores após a incorporação de 1% do princípio ativo, pois demonstrou a formação de fases líquido-cristalinas evidenciadas sob luz polarizada no microscópio óptico, apresentou-se compatível com o pH fisiológico da pele, apresentou pequeno coeficiente de variação das medidas realizadas referentes aos parâmetros físico- químicos e menor capacidade de desestruturar... / Current hypotheses based on the process of skin aging in two theories: the intrinsic (or chronological) and extrinsic (or photoaging). Both in the extrinsic as intrinsic aging, the main skin disorders are characterized by wrinkles, flaccidity and loss of elasticity. Retinyl palmitate (RP) is a synthetic analogue of vitamin A given topically to prevent or delay some structural and functional changes of the skin associated with aging, but is an active principle that has limited chemical stability against moisture, oxygen, acids , metals and exposure to light. Thus, the aim of this study was to develop liquid crystalline system silicon-based for extended release and maximizing the stability of retinyl palmitate in order to optimize the use of topically active principle in the prevention and / or mitigation of aging skin. Using the method of titration of the aqueous phase, was built two ternary phase diagrams, both consist of Procetyl AWS ® (surfactant) and water and silicone DC 5330 ® (oil phase diagram 1) or silicone DC 5329 ® (phase oil in diagram 2). In preliminary studies of stability, the formulations of the diagram 1 (A, B, C and D) and the formulations of the diagram 2 (E, F, G and H) were evaluated in the following studies: polarized light microscopy, centrifugation, pH, electrolitic conductivity, refraction index and rheology. Among these formulations studied preliminarily, the formulation G RP-loaded was selected to be conducted to further studies, since it showed the formation of liquid crystalline phases evidenced by polarized light in an optical microscope, presented consistent with the physiological pH of skin, had a small coefficient of variation of measurements related to the physicochemical and less ability to disrupt the lipid bilayer of the skin due to have a lower concentration of surfactant. The validated analytical methodology for chemical quantification of retinyl... (Complete abstract click electronic access below)

The pulsed field gradient fourier transform nuclear magnetic resonance (PFG-FTNMR) method to measure translational diffusion coefficients in multicomponent systems has been applied to amphiphilic molecules forming liquid crystalline phases. By analyzing the concentration dependence of the diffusion coefficients of water and amphiphile in a micellar system of N,N-dimethyldodecy lamine oxide (DDAO) in water it was possible to conclude that the micelles formed were polydisperse in size and shape. It was also shown that solubilization of small amounts of hydrophobic molecules into the micelles induces spherical micelles of a narrow size distribution. From the magnitude of the lateral diffusion coefficient in the cubic phase of DDAO/water it was concluded that this phase is built up of bicontinous aggregates. The lipid lateral diffusion in the cubic phase of monooleoylglycerol (MO)/water has been measured. The decrease in the lateral diffusion of MO in this phase, when the water was replaced by glycerol, was ascribed to changes in viscosity in the polar region. Measurements by electron spin resonance and time-resolved fluorescence spectroscopy showed that changes in viscosity of the solvent also affected the motions in the hydrocarbon region. The diffusion coefficients of all three components in the cubic phase located in the lowwater region of the ternary system of diacylglycerol (DAG)/soybean phosphatidylcholine (SPC)/water have been determined. Conclusive evidence was provided for that this cubic phase is built up of reversed micelles containing mainly SPC in a continous matrix of mainly DAG. The effect on the phase properties of DDAO upon incorporation of the peptide gramicidin D has been investigated. It was shown that gramicidin D induces a lamellar phase at all water contents. The change in the order parameter profile of the C-2H bonds in perdeuterated DDAO upon incorporation of gramicidin D is compatible with theoretical calculations for proteins exhibiting a positive hydrophobic mismatch. A method for using the PFG FTNMR technique in measurements of the transmembrane exchange rate of small molecules in vesicular suspensions is discussed and some preliminary data is shown. / <p>Diss. (sammanfattning) Umeå : Umeå universitet, 1994, härtill 4 uppsatser</p> / digitalisering@umu

Resumo: As hipóteses mais modernas baseiam o processo de envelhecimento cutâneo em duas teorias: o intrínseco (ou cronológico) e o extrínseco (ou fotoenvelhecimento). Tanto no envelhecimento intrínseco como no extrínseco, as principais alterações da pele são caracterizadas por formação de rugas, flacidez e perda da elasticidade. O palmitato de retinol (PR) é um análogo sintético da vitamina A indicado topicamente para prevenir ou retardar algumas mudanças estruturais e funcionais da pele associadas ao processo de envelhecimento cutâneo, porém é um princípio ativo que apresenta estabilidade química limitada frente à umidade, oxigênio, ácidos, metais e exposição à luz. Assim, o objetivo deste trabalho foi desenvolver um sistema líquido-cristalino à base de silicone para a liberação prolongada e maximização da estabilidade do palmitato de retinol. Utilizando-se o método de titulação da fase aquosa, foram construídos dois diagramas ternários de fases, ambos constituídos por Procetyl AWS® (tensoativo) e água e por silicone DC 5330® (fase oleosa no diagrama 1) ou silicone DC 5329® (fase oleosa no diagrama 2). Nos estudos de estabilidade preliminar, as formulações do diagrama 1 (A, B, C e D) e do diagrama 2 (E, F, G e H) foram avaliadas nos seguintes estudos: microscopia de luz polarizada, centrifugação, pH, condutividade eletrolítica, índice de refração e reologia. Dentre estas formulações estudas preliminarmente, a formulação GPR foi selecionada para ser conduzida aos estudos posteriores após a incorporação de 1% do princípio ativo, pois demonstrou a formação de fases líquido-cristalinas evidenciadas sob luz polarizada no microscópio óptico, apresentou-se compatível com o pH fisiológico da pele, apresentou pequeno coeficiente de variação das medidas realizadas referentes aos parâmetros físico- químicos e menor capacidade de desestruturar... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Current hypotheses based on the process of skin aging in two theories: the intrinsic (or chronological) and extrinsic (or photoaging). Both in the extrinsic as intrinsic aging, the main skin disorders are characterized by wrinkles, flaccidity and loss of elasticity. Retinyl palmitate (RP) is a synthetic analogue of vitamin A given topically to prevent or delay some structural and functional changes of the skin associated with aging, but is an active principle that has limited chemical stability against moisture, oxygen, acids , metals and exposure to light. Thus, the aim of this study was to develop liquid crystalline system silicon-based for extended release and maximizing the stability of retinyl palmitate in order to optimize the use of topically active principle in the prevention and / or mitigation of aging skin. Using the method of titration of the aqueous phase, was built two ternary phase diagrams, both consist of Procetyl AWS ® (surfactant) and water and silicone DC 5330 ® (oil phase diagram 1) or silicone DC 5329 ® (phase oil in diagram 2). In preliminary studies of stability, the formulations of the diagram 1 (A, B, C and D) and the formulations of the diagram 2 (E, F, G and H) were evaluated in the following studies: polarized light microscopy, centrifugation, pH, electrolitic conductivity, refraction index and rheology. Among these formulations studied preliminarily, the formulation G RP-loaded was selected to be conducted to further studies, since it showed the formation of liquid crystalline phases evidenced by polarized light in an optical microscope, presented consistent with the physiological pH of skin, had a small coefficient of variation of measurements related to the physicochemical and less ability to disrupt the lipid bilayer of the skin due to have a lower concentration of surfactant. The validated analytical methodology for chemical quantification of retinyl... (Complete abstract click electronic access below) / Orientador: Maria Virgínia Costa Scarpa / Coorientador: Marlus Chorilli / Banca: Eneida de Paula / Banca: Sandra Helena Pulcinelli / Mestre

Orientador: Marlus Chorilli / Resumo: A candidíase vulvovaginal (CVV) é o tipo mais comum de vaginite aguda entre as mulheres, causada por fungos do gênero Candida spp. A Candida albicans é a espécie responsável por 80-90% dos casos, contudo nos últimos anos, houve um aumento no número de casos envolvendo outras espécies, sendo a Candida glabrata, a segunda mais reportada e mais resistente aos tratamentos convencionais. As terapias existentes para CVV apresentam desvantagens devido aos efeitos colaterais dos agentes antifúngicos utilizados e resistência fúngica prevalente. Como alternativa, compostos naturais como o ácido p-cumárico (p-AC) vêm sendo estudados devido à sua potencial atividade antifúngica. Todavia, seu caráter lipofílico dificulta sua solubilidade em água, diminuindo sua eficácia. A incorporação do p-AC em um sistema de liberação de fármacos (SLF), como os cristais líquidos (CLs), pode auxiliar na sua administração tópica, e assim aumentar sua solubilidade, eficácia, reduzir efeitos colaterais sistêmicos e potencializar sua ação na mucosa vaginal. Dessa forma, este trabalho teve como objetivo desenvolver sistemas liquido-cristalinos com propriedades mucoadesivas para liberação controlada do ácido p-cumárico no tratamento de candidíase vulvovaginal, via administração tópica. A atividade antifúngica do p-AC foi avaliada a partir dos ensaios de concentração inibitória mínima (CIM), concentração fungicida mínima (CFM) , formação de biofilme e ensaio in vivo contra cepas de C. albicans (SC5314), C. glab... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Vulvovaginal candidiasis (VVC) is the most common type of acute vaginitis among women, caused by fungi of the genus Candida spp. Candida albicans is the species responsible for 80-90% of cases, however in recent years, there has been an increase in the number of cases involving other species, with Candida glabrata being the second most reported and most resistant to conventional treatments. Existing therapies for VVC have disadvantages due to the side effects of the antifungal agents used and the prevailing fungal resistance. As an alternative, natural compounds such as p-cumaric acid (p- CA) have been studied due to their potential antifungal activity. However, its lipophilic character hinders its solubility in water, reducing its effectiveness. The incorporation of p-CA in a drug delivery system (DDS), such as liquid crystals (LCs), can assist in its topical administration, and thus increase its solubility, effectiveness, reduce systemic side effects and enhance its activity on the vaginal mucosa. Thus, this work aimed to develop liquid-crystalline systems with mucoadhesive properties for controlled release of p-cumáric acid in the treatment of vulvovaginal candidiasis, via topical administration. The antifungal activity of p-CA was analysed by assays of minimum inhibitory concentration (MIC), minimum fungicidal concentration (MFC), biofilm formation and in vivo assay against strains of C. albicans (SC5314), C. glabrata (ATCC 2001) and C. krusei (ATCC 6528). For the develop... (Complete abstract click electronic access below) / Mestre

Η διασπορά κβαντικών τελειών ως πυρήνων αταξίας σε οργανωμένα συστήματα, έχει προσελκύσει επιστημονικό ενδιαφέρον και ερευνητικές δραστηριότητες, τόσο στο πεδίο της φυσικής στερεάς κατάστασης, όσο και σε αυτό της επιστήμης των υλικών. Δεν είναι σπάνια η διαπίστωση ότι υβριδικά συστήματα που προκύπτουν από συνδυασμούς όπως αυτός των υγρών κρυστάλλων και των νανοσωματιδίων, παρουσιάζουν αξιοσημείωτες και συχνά αναπάντεχες νέες ιδιότητες. Το θέμα της παρούσας διδακτορικής διατριβή κινείται σε δύο άξονες: το σχεδιασμό και την χημική σύνθεση κβαντικών τελειών επιφανειακά κατεργασμένων, για ελεγχόμενη αλληλεπίδραση με υγρούς κρυστάλλους, και τη μελέτη των φυσικών ιδιοτήτων των σύνθετων νανοδομημένων υγροκρυσταλλικών συστημάτων, που σχηματίζονται με διασπορά των νανοσωματιδίων αυτών σε χειρόμορφους θερμοτροπικούς υγρούς κρυστάλλους. Στο πρώτο μέρος της διατριβής παρουσιάζεται η χημική σύνθεση και επιφανειακή τροποποίηση κβαντικών τελειών CdSe, με υδρόφοβες επιφανειοδραστικές ομάδες τρι– οκτυλοφωσφίνης (TOP)/ελαϊκής αμίνης (ΟΑ), TOP/οκταδεκυλαμίνης, ΤOP/δωδεκυλα-μίνης, TOP/οκτυλαμίνης και τριφαινυλφωσφίνης/τριφαινυλαμίνης. Ο χαρακτηρισμός της δομής και των οπτικών ιδιοτήτων των νανοσωματιδίων έγινε με περίθλαση σκόνης ακτίνων Χ, φασματοσκοπία υπεριώδους–ορατού και φασματοσκοπία υπερύθρου, ενώ για τη διερεύνηση της μορφολογίας τους και τον προσδιορισμό των διαστάσεών τους, χρησιμοποιήθηκε ηλεκτρονική μικροσκοπία διέλευσης. Οι χημικές συνθέσεις, βασισμένες στην θερμολυτική διάσπαση οργανομεταλλικών ενώσεων, οδήγησαν σε επιτυχημένη παραγωγή σφαιρικών νανοσωματιδίων, μέσης διαμέτρου 3–4 nm, με στενή κατανομή μεγεθών και καλή διαλυτότητα σε οργανικούς διαλύτες. Στη συνέχεια μελετήθηκαν οι επιπτώσεις από τη διασπορά των νανοσωματιδίων CdSe με TOP και OA, με μέση διάμετρο 3.2 nm στη θερμοδυναμική και μοριακή οργάνωση χειρόμορφων υγρών κρυστάλλων, με τις τεχνικές της θερμιδομετρίας εναλλασσόμενης θερμικής εισόδου και με περίθλαση σκόνης ακτίνων Χ. Το ενδιαφέρον επικεντρώθηκε στη θερμοκρασιακή περιοχή των Μπλε φάσεων και στη μετάπτωση φάσης SmA–SmC*. Οι Μπλε φάσεις παρόλο που παρουσιάζουν εξέχουσες ιδιότητες για καινοτόμες εφαρμογές στη βιομηχανία οθονών και αισθητήρων, ωστόσο, είναι σταθερές σε πολύ στενά θερμοκρασιακά εύρη, μεταξύ Ισοτροπικής και Χειρόμορφης Νηματικής φάσης, γεγονός που δεν ευνοεί τη χρήση τους. Οι πειραματικές μετρήσεις αποκάλυψαν νέα φαινόμενα, όπως τη σταθεροποίηση της θερμοκρασιακής περιοχής της Μπλε φάσης ΙΙΙ (BPIII) σε μεγάλο θερμοκρασιακό εύρος, σε σχέση με τον αμιγή υγρό κρύσταλλο, και τη μετατόπιση των θερμοκρασιών μετάπτωσης σε μικρότερες τιμές. Η θεωρητική μελέτη που πραγματοποιήθηκε καταδεικνύει ισχυρή αλληλεπίδραση των νανοσωματιδίων με τις σειρές πλεγματικών ατελειών του υγρού κρυστάλλου. Παράλληλα τα αποτελέσματα φανερώνουν ότι ο χαρακτήρας Μέσου Πεδίου–Landau της μετάπτωσης SmA–SmC*, για το ίδιο σύστημα, δεν αλλοιώνεται. Η αλληλεπίδραση των κβαντικών τελειών CdSe με επιφανειακή δραστικοποίηση ΟΑ και TOP με χειρόμορφους υγρούς κρυστάλλους, παρέχει δυνατότητες και δημιουργεί σημαντικές προϋποθέσεις για νέες τεχνολογικές εφαρμογές και επιστημονικές εξελίξεις. / One dimensional semiconductor structures are intriguing materials for both fundamental research and industrial applications. On the other hand the long-range nature of the orientational order of liquid crystals is responsible for many fascinating optical, electromechanical and critical properties of these materials. Hybridization of these two fields may lead to novel materials with unusual optical and physical properties that are of considerable importance for technological applications as well as for basic physics studies on phase transitions and critical phenomena. In this context, complex soft materials were formulated that result from the dispersion of surface functionalized quantum dots in thermotropic chiral LCs. Special attention was paid to the synthesis and properties of the nanocrystals and to the dispersion state, as well as to the thermal and structural study of the composite materials. In the first part of this Thesis a chemical approach for the synthesis of semiconducting quantum dots is presented. The method, based on the thermolytic decomposition of organometallic compounds, leads to the production of spherical nanocrystalline particles highly soluble in organic media, with an average diameter of 3.2 nm, capped with a variety of amine and phosphine molecules. The as-synthesized nanoparticles were characterized by means of powder X-ray diffraction, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy and transition electron microscopy. The second part of the Thesis is concentrated on the effects upon the Blue phases and smectic-A to chiral smectic-C* phase transition of the liquid crystal CE8, arising from the dispersion of CdSe quantum dots, surface-treated with oleylamine and trioctylphosphine. For this purpose, ac calorimetry and X-ray scattering studies have been carried out. Liquid– crystalline blue phases exhibit exceptional properties for applications in the display and sensor industry. However, in single component systems, they are stable only for a very narrow temperature range between the isotropic and the chiral nematic phase, a feature that severely hinders their applicability. The systematic high-resolution calorimetric studies revealed that Blue phase III is effectively stabilized in a wide temperature range by mixing surface-functionalized nanoparticles with chiral liquid crystals. The calorimetric measurements also revealed substantial downshifts of the transition temperature. Theoretical arguments show that the aggregation of nanoparticles at disclination lines is responsible for the observed effects. Furthermore, it was found that at the SmA–SmC* phase transition, as a function of increasing nanoparticle concentration, the heat capacity anomalies display an extended-mean-field to mean-field–like crossover behavior, while the temperature dependence of the tilt angle remains bulk-like with no occurrence of pretransitional effects. The interaction of CdSe quantum dots with the cores of disclination lines gains further support, as bound disclination lines are expected to affect smectic–smectic phase transitions in a very limited manner.