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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Photochemistry of Polymethyl and Hydroxy-Polymethyl Cyclohexadienyl Cations.

Parrington, Barry 11 1900 (has links)
<p> Fluorosulphonic acid has been employed to generate cyclohexadienyl cations by protonation of weak bases in order to study the affect of uv light on such systems which are variably substituted. Differing substitution has been obtained by selecting polymethylbenzenes, cyclohexadienones and polymethylphenols as cation precursors. </p> <p> The photoisomerization of the 1,2,4,5-te-tramethylcyclohexadienyl cation to the 1,2,4,5-tetramethylbicyclo-[3 .1.O.] hexenyl cation has been studied by nmr methods and is discussed mechanistically in terms of competitive electrocyclic and [ δ2a + π2a] mechanisms of ring closure. Investigations of a similar 1,2,3,5-tetrarnethylcyclohexadienyl cation failed to uncover an analogous photoisomerization. This result is briefly discussed in relation to the demonstrated instability of the supposed photo-product which has been produced by a non photo chemical route. </p> <p> Both the 1-hydroxy-6,6-dimethyl- and 1-hydroxy-4 1 4 dimethylcyclohexadienyl cations have been generated from the corresponding cyclohexadienones by low temperature protonation in FS03H. Photoisornerization of these systems produced the same 2-hydroxy-6,6-dimethylbicyclo[3.l.0.] hexenyl cation which underwent further photorearrangement to various protonated phenols, the nature of which depended upon the frequency of irradiation. </p> <p> A number of protonated polymethylphenols have been investigated with respect to their site(s) of protonation in fluorosulphonic acid and their tendency to undergo photochemical reaction. Several members of this series have been shown to rearrange photochemically to isomeric phenols through a bicyclo[3.l.O.] hexenyl cation intermediate. A necessary criterion for this reaction has been established as protonation of a methyl bearing ring carbon. </p> <p> An exceptional example of the phenol photo- isomerization was the photo-conversion of protonated 2,4,6-trimethy·lphenol·to protonated 1,3,5-trimethyl. bicyclo[3.1.o] hex-3-en-2-one. This, as well as additional evidence led to the conclusion that a significant amount of meta protonation occurred with this phenol. </p> / Thesis / Master of Science (MSc)
2

A Classification System for the Spread of Polymethyl Methacrylate in Vertebral Bodies Treated with Vertebral Augmentation

Frankl, Joseph, Sakata, Michael P., Choudhary, Gagandeep, Hur, Seung, Peterson, Andrew, Hennemeyer, Charles T. 09 1900 (has links)
In this study, we develop a classification system for describing polymethyl methacrylate (PMMA) spread in vertebral bodies after kyphoplasty or vertebroplasty for vertebral compression fractures (VCFs) and for assessing whether PMMA spread varies between operators, VCF etiology, or vertebral level. Intraoperative fluoroscopic images of 198 vertebral levels were reviewed in 137 patients (women, 84; men, 53; mean age, 75.8 +/- 12.5; and those with a diagnosis of osteoporosis, 63%) treated with kyphoplasty between January 01, 2015 and May 31, 2015 at a single center to create a 5-class descriptive system. PMMA spread patterns in the same images were then classified by 2 board-certified radiologists, and a third board-certified radiologist resolved conflicts. A total of 2 primary PMMA spread patterns were identified, namely, acinar and globular, with subtypes of localized acinar, diffuse globular, and mixed, to describe an equal combination of patterns. Interrater reliability using the system was moderate (kappa = 0.47). After resolving conflicts, the most common spread class was globular (n = 63), followed by mixed (n = 58), diffuse globular (n = 30), acinar (n = 27), and localized acinar (n = 20). The spread class after treatment by the 2 most frequent operators differed significantly (n(1) = 63, n(2) = 70; P <.0001). There was no difference in the spread class between VCF etiologies or vertebral levels. PMMA spread may, therefore, be a modifiable parameter that affects kyphoplasty and vertebroplasty efficacy and adverse events.
3

Avaliação in vitro da citotoxicidade de resinas acrílicas para reembasamento baseadas em uma nova formulação

Costa, Cristiane Campos [UNESP] 19 March 2009 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:28:55Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-03-19Bitstream added on 2014-06-13T20:58:45Z : No. of bitstreams: 1 costa_cc_me_arafo.pdf: 3083928 bytes, checksum: 2605dd91339dbf0d4e3c26e02afc6696 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O objetivo deste estudo foi determinar a citotoxicidade in vitro de duas resinas reembasadoras experimentais autopolimerizáveis contendo alta concentração de agentes de ligação cruzada, etilenoglicol dimetacrilato (EGDMA) e 1,4-butanodiol dimetacrilato (BDMA) comparadas com uma resina reembasadora comercial (Tokuyama Rebase Fast II). Foram confeccionados corpos-de-prova em forma de discos das três resinas acrílicas reembasadoras rígidas sob condições assépticas. Os fibroblastos (L929) foram cultivados em placas com 96 compartimentos e incubadas por 24 h em meio de cultura Eagle. Os extratos foram preparados, colocando-se três amostras de cada resina em frascos de vidro estéreis com 9 mL de meio de Eagle e incubadas a 37º C por 24 h. O efeito citotóxico dos extratos foram avaliados utilizando os testes de incorporação do 3H-timidina e MTT, que refletem os níveis de síntese de DNA e metabolismo celular, respectivamente. Os dados foram analisados estatisticamente, utilizando análise de variância (P<0.05). Para o teste de incorporação do 3H-timidina, não foram observadas diferenças significativas (P>0.05) entre os materiais. A média da quantidade do isótopo incorporado no DNA celular para todas as resinas acrílicas foi estatisticamente menor do que para o controle. Todas as resinas acrílicas foram classificadas pelo teste de incorporação do 3Htimidina como moderadamente citotóxicas. Da mesma forma, para o teste do MTT, não foi encontrada diferença significativa para a citotoxicidade entre os materiais (P>0.05). Quando a citotoxidade foi comparado com o grupo controle, todas as resinas foram classificadas entre não citotóxicas e discretamente citotóxicas pelo teste do MTT. Assim, conclui-se que a incorporação dos agentes de ligação cruzada, EGDMA e BDMA não influenciaram significativamente sobre a citotoxicidade observada. Não houve diferença... / The aim of this study was to determine the cytotoxicity in vitro of two trials autopolymerizing reline systems made with higher concentration of cross-linking agents, EGDMA and BDMA compared to a commercial reline resin. Sample disks of the three hard reline acrylic resins were fabricated under aseptic conditions. The Fibroblast L929 cells were cultured in 96-well plates and incubated for 24 h in Eagle's medium. Eluates were prepared by placing three samples into a sterile glass vial with 9 mL of Eagle's medium and incubating at 37ºC for 24 h. The cytotoxic effect from the eluates was evaluated using the 3H-thymidine incorporation and MTT assays, which reflect DNA synthesis levels and cell metabolism, respectively. The data were statistically analyzed by using the one-way analysis of variance (P<.05). With the 3H-thymidine incorporation assay, no significant differences (P > .05) were found between the materials. The mean quantity of isotope incorporated into cellular DNA for all acrylic resins was statistically smaller than for the control. All acrylic resins were graded by the 3Hthymidine incorporation assay as moderate cytotoxic. Similarly, with the MTT assay, no significant difference in cytotoxicity was found between the materials (P > .05). When the cytotoxicity was compared with control group, all resins assay were between non cytotoxic and slight cytotoxic by the MTT. The incorporation of cross-linking agents, EGDMA and BDMA had no significant influence on the cytotoxicity observed. There was no cell viability difference between all materials in both assays.
4

Adição de nanopartículas de prata ao Poli (metil metacrilato): análise microbiológica

Takamiya, Aline Satie [UNESP] 08 February 2010 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:28:57Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-08Bitstream added on 2014-06-13T19:37:36Z : No. of bitstreams: 1 takamiya_as_me_araca.pdf: 2744019 bytes, checksum: 436939ec1fb2e59f419b688a517c064c (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O objetivo do presente estudo foi verificar a atividade antimicrobiana de uma resina acrílica à base de poli (metil metacrilato) (PMMA) contendo nanopartículas de prata frente ao microorganismo Candida albicans. Utilizou-se a resina acrílica termopolimerizável Lucitone 550 e as nanopartículas de prata foram sintetizadas por meio da redução dos íons prata do nitrato de prata pelo citrato de sódio. A forma e o tamanho das partículas foram confirmados por microscopia eletrônica de varredura (MEV) e de transmissão (MET), tendo-se obtido partículas na forma esférica e com tamanhos médios de 5 e 10 nm. A resina acrílica foi proporcionada de acordo com as instruções do fabricante e a solução coloidal de nanopartículas de prata foi adicionada ao componente líquido da resina acrílica nas concentrações de 0,05%, 0,5% e 5% baseadas na massa do polímero. Após o processamento, os espécimes foram esterilizados por radiação de Co-60. Foram analisados a adesão de microorganismos à superfície do poli (metil metacrilato)/prata (PMMA/Ag) e a formação de biofilme por Candida albicans sobre a superfície polimérica através de microscopia de luz e de MEV. Os resultados mostraram redução estatisticamente significante (P < 0,05) da adesão de microorganismos à superfície do nanocompósito para os grupos com 0,05 e 0,5% de nanopartículas de prata com tamanho de 5nm quando comparados ao grupo controle. A microscopia de luz nãomostrou diferença na formação de biofilme entre os grupos dos nanocompósitos e o grupo controle. A MEV sugeriu uma redução na quantidade de células na superfície dos grupos contendo nanopartículas de prata, especialmente até 12 horas de crescimento fúngico. Os resultados sugerem ação inibitória sobre a adesão e formação de biofilme por Candida albicans quando da adição de nanopartículas de prata de tamanho 5 nm à resina acrílica nas concentrações de 0,05% e 0,5% / The aim of this study was to verify the antimicrobial activity of a poly (methyl methacrylate) acrylic resin containing silver nanoparticles against Candida albicans microorganism. The heat-polymerized acrylic resin Lucitone 550 was used and the silver nanoparticles were synthesized through the reduction of silver ions of silver nitrate by sodium citrate. The shape and size of the particles were confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and showed spherical particles with medium size of 5 and 10 nm. The acrylic resin was proportioned according to the manufacturer’s instructions and the silver nanoparticles colloid solution was added to the liquid of the acrylic resin in 0.05%, 0.5% and 5% of concentration based on the polymer mass. After being processing, the specimens were sterilized by Co-60 radiation. The adhesion of cells of Candida albicans and the biofilm formation on the surface of the polymer were evaluated by light microscopy and SEM. The results demonstrated significantly reduction (P < .05) of the microorganisms adhesion on the surface of the nanocomposites for the groups containing 0.05 and 0.5% of silver nanoparticles with size of 5nm when compared to the control group. The light microscopy did not show difference in the biofilm formation among the groups evaluated. The SEM images suggested reduction of growth of Candida albicans cells for the nanocomposite groups, mainly up to the period of 12 hours. It was concluded that the addition of silver nanoparticles with size of 5 nm to the PMMA in 0.05% and 0.5% concentrations showed antimicrobial effect against Candida albicans
5

Efeito do tipo de revestimento estetico e da eletroerosão sobre a desadaptação de infra-estruturas metalicas implantossuportadas / Influence of vennering material and spark erosion on marginal misfit of implant-suported frameworks

Oliveira, Luciana Valadares 26 June 2007 (has links)
Orientador: Marcelo Ferraz Mesquita / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-09T19:25:40Z (GMT). No. of bitstreams: 1 Oliveira_LucianaValadares_D.pdf: 36824583 bytes, checksum: 7a4d2a0d063c3cd9180327ea1a830f60 (MD5) Previous issue date: 2007 / Resumo: As distorções oriundas das técnicas de aplicação dos revestimentos estéticos sobre infraestruturas metálicas de próteses fixas podem resultar em margens cervicais desadaptadas. Este trabalho avaliou o efeito do tipo de revestimento estético, da simulação dos ciclos de cocção da porcelana e da eletroerosão sobre o desajuste de infra-estruturas implantossuportadas. Foi utilizada uma matriz metálica simulando um arco mandibular, contendo 5 pilares intermediários do tipo Microunit (Conexão Sistema de Próteses, Brasil). Sobre essa matriz, foram enceradas 40 infra-estruturas, fundidas em liga de CoCr (Remanium 2000, Alemanha). Para cada infra-estrutura, foi confeccionado um index, parafusando-se 5 réplicas em cada uma das infra-estruturas. Esse conjunto foi posicionado em gesso pedra especial com auxílio de delineador, antes da aplicação dos revestimentos estéticos, para avaliar o desajuste provocado apenas pela fase de aplicação dos revestimentos estéticos e ciclo de cocção da porcelana. As infra-estruturas foram separadas aleatoriamente: G1: resina acrílica termopolimerizável (Clássico, Clássico, Brasil); G2: resina fotopolimerizável (Versyo.com, Heraeus Kulzer, Brasil); G3: porcelana (Carmen, Dentaurum, Alemanha); G4: simulação dos ciclos de cocção da porcelana. Antes da aplicação dos revestimentos estéticos, foi realizada a avaliação do desajuste marginal sobre o index, após aperto de 10 Ncm em um único parafuso, correspondente ao implante A. Através desse procedimento, verificou-se a adaptação dos componentes C e E. O procedimento foi repetido no outro implante mais distal (E), para mensuração nos implantes A e C. As leituras foram realizadas utilizando microscópio mensurador (STN ¿ Olympus Optical, Japão). Procedeu-se o processo de eletroerosão (Tel Med Technologies, EUA), e novamente avaliação do desajuste marginal. Os resultados obtidos foram submetidos à Análise de Variância e teste de Tukey (p<0,05). Os valores de desajuste marginal das infra-estruturas antes da aplicação dos revestimentos estéticos não apresentaram diferença estatística significante entre si: G1: 56,97 µm (± 16,86); G2: 43,27 µm (± 16,49); G3: 49,26 µm (± 17,11); G4: 40,66 µm (+ 10,85). A aplicação dos revestimentos estéticos e simulação dos ciclos de cocção da porcelana aumentaram significantemente os valores médios de desajuste marginal para todos os grupos: G1: 170,01 µm (±53,98); G2: 72,32 µm (±27,49); G3: 164,84 µm (±27,67); e G4: 86,28 µm (±20,01). Os grupos G1 e G3 não apresentaram diferença estatisticamente significante entre si, mas apresentaram diferença quando comparados aos G2 e G4. Após eletroerosão, as médias de desajuste marginal apresentaram valores significamente menores para os grupos: Gl: 108, 54 µm (±40,75); G3: 109,61 µm (±24,42); e G4: 59,63 µm (±22,13). A média de desajuste marginal para o grupo de resina fotopolimerizável não apresentou diferença estatística significante: G2: 49,70 µm (±16,65). Como observado anteriormente, os grupos G1 e G3 não apresentaram diferença estatística significante, mas ambos apresentaram diferença dos grupos G2 e G4. Conclui-se que os revestimentos estéticos em resina acrílica e porcelana produzem os maiores valores de desajuste marginal para próteses implantossuportadas, enquanto a resina fotopolimerizável, os menores. A aplicação de porcelana resultou em maiores valores de desajuste marginal que apenas a simulação dos ciclos de cocção. A eletroerosão foi eficaz na redução dos desajustes marginais até os limites considerados clinicamente aceitáveis / Abstract: The demand for a passive fit of frameworks for osseointegrated endousseous implants abutments is well known, because the tightening of an inaccurate framework to the abutments can transmit stress to the bone-metal interface. The purpose of the present study was to evaluate the influence of the veneering application and porcelain firing cycle on the misfit level of implant-supported frameworks. Forty Co-Cr (Remanium 2000, Dentaurum, Germany) alloy frameworks were fabricated from a metallic index containing 5 Branemark type multi unit abutments. Analogs of the abutments were positioned to the framework, to construct an index for each framework. This index allowed the observation of the marginal gaps caused by the application of the veneering material. The frameworks were grouped (n=10): 1) heat acrylic resin (Clássico, Clássico, São Paulo, Brazil); 2) light polymerized resin (Versyo.com, Heraeus Kulzer, Brazil); 3) porcelain application (Carmen, Dentaurum, Germany); 4) simulation of porcelain firing cycle. Marginal refinement with spark erosion was conducted on specific equipment (Tel Med Technologies, U.S.A.). The marginal gap was obtained before and after the veneering materials and the spark erosion procedure, following the single screw test protocol (using a tightening force of 10 Ncm). A traveling microscope (STN ¿ Olympus Optical Co. Ltd Japan (120X) was used, tightening 10N in the titanium screw of the extremity distal implant, measuring the gaps at the central and distal implants. Data were subject Analysis of Variance followed by Tukey test (5%). Marginal gap mean values of the frameworks before the veneering application were not significantly different: G1: 56.97(± 16.86); G2: 43.27(± 16.49); G3: 49.26(± 17.11); G4: 40.66(± 10.85). The application veneering materials and the simulation of porcelain firing cycle increased significantly the misfit mean values of all groups: G1: 170.01 µm (±53.98); G2: 72.32 µm (+±27.49); G3: 164.84 µm (±27.67); e G4: 86.28 µm (±20.01). There were no significant differences between G1 and G3, but they were significantly different from both G2 and G3. After the spark erosion process, marginal gap mean values decreased significantly for the following groups: G1: 108. 54 µm (±40.75); G3: 109.61 µm (±24.42); and G4: 59.63 µm (±22.13). The light curing group decreased the marginal gap mean values, but not significantly after the spark erosion procedure: G2: 49.70 µm (±16.65). As occurred after the application of veneering materials, G1 and G3 groups did not show significant difference, but they both were significantly different from G2 and G4 groups. It can be concluded that heat cured acrylic resin and porcelain produced the highest mean values of marginal gaps, while light cured acrylic resin, the lowest. The application of porcelain produced higher misfit values than the simulation of porcelain firing cycles only. The spark erosion procedure was efficacious in reducing the frameworks marginal gaps to the levels clinically accepted for all groups evaluated. / Doutorado / Protese Dental / Doutor em Clínica Odontológica
6

Influencia da adição de politetrafluoretileno (PTFE) nas propriedades fisicas, mecanicas e aderencia microbiana em resinas acrilicas / Influence of polytetrafluorethylene (PTFE) added to acrylic resin on its physical and mechanical properties and microorganism adherence on acrylic resin

Straioto, Fabiana Gouveia 15 August 2018 (has links)
Orientadores: Altair Antoninha Del Bel Cury, Alfredo Julio Fernandes Neto / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-15T07:28:18Z (GMT). No. of bitstreams: 1 Straioto_FabianaGouveia_D.pdf: 1136819 bytes, checksum: 94255ae316940aec09bc64b1ad3b35c2 (MD5) Previous issue date: 2010 / Resumo: Resinas acrílicas são materiais amplamente empregados na Odontologia, especialmente os polímeros a base de polimetilmetacrilato (PMMA) para confecção de próteses. Dentre as vantagens deste material estão à estabilidade de cor, propriedades ópticas, estética satisfatória, estabilidade dimensional, fácil manipulação e propriedades físicas adequadas para aplicações odontológicas. Entretanto, como desvantagem deste material, está à susceptibilidade à aderência e desenvolvimento de biofilme por microrganismos presentes na cavidade bucal, como fungos e bactérias. A aderência de microrganismo é o primeiro evento para o desenvolvimento do biofilme o qual está relacionado ao estabelecimento de quadros clínicos patológicos como estomatite protética. Recentemente, a adição de modificadores na composição da resina acrílica tem sido proposta com o objetivo de melhorar as características de superfície, e conseqüentemente controlar a aderência de microrganismos. Entretanto, a mudança na composição da resina acrílica não deverá comprometer as propriedades físicas. Politetrafluoretileno (PTFE) tem sido usado como modificador para confecção de stents e cateteres devido a biocompatibilidade, alta resistência a agentes químicos e baixa energia de superfície. Assim, o objetivo neste estudo foi avaliar as propriedades físicas, características de superfície, aderência de microrganismos e formação de biofilme de suas resinas acrílicas, uma polimerizada em água quente com ciclo longo e a outra polimerizada pelo ciclo curto, contendo 2% de PTFE em sua composição e comparar com as mesmas resinas sem adição de PTFE. Para isto, três estudos foram realizados: 1- Propriedades físicas da resina acrílica - espécimes das resinas foram confeccionados de acordo com a norma ISO 1567:1999 (n=10) para cada teste mecânico: dureza de superfície, resistência ao impacto, resistência a flexão e o módulo de elasticidade e carga máxima foram calculados; 2 - Características de superfície da resina acrílica e aderência de Candida albicans: espécimes retangulares (n=10) para cada resina foram confeccionados e avaliados quanto à rugosidade, ângulo de contato, energia livre de superfície e aderência de Candida albicans. As células aderidas foram expressas por unidade formadora de colônia por área da superfície; 3- Biofilme formado na resina acrílica e sua composição: discos de resina acrílica (n=6) foram usados para formação de biofilme de Streptococcus mutans UA159, Streptococcus sanguinis ATCC 10556 e Actinomyces naeslundii ATCC 12104. A composição de polissacarídeos e unidades formadoras de colônia foram comparadas. Em todos os estudos, os resultados foram submetidos à análise variância a dois fatores e comparados pelo teste de Tukey (p=0,05). Os resultados não mostraram diferença estatisticamente significante para os valores de dureza de superfície (p>0,05). Entretanto, para os valores de resistência ao impacto e flexão para os grupos experimentais, contendo PTFE, apresentaram resultados significantemente menores (p<0,05) quando comparados aos grupos não adicionados de PTFE. Os valores de módulo de elasticidade da resina acrílica adicionada com 2% de PTFE polimerizada com o ciclo longo apresentaram os maiores valores comparados aos demais grupos (p<0,05). Não houve diferenças significativas para rugosidade, ângulo de contato e energia livre de superfície (p>0,05); houve uma tendência de redução de células de C. albicans no grupo com PTFE, mas não foi estatisticamente significante. Em relação, a formação e composição de polissacarídeo os resultados não apresentaram diferenças entre os grupos de resina acrílica (p>0,05). Os resultados sugerem que 2% de PTFE adicionada à resina acrílica não foi suficiente para promover mudanças nas propriedades mecânicas, aderência e composição do biofilme. / Abstract: Acrylic resins have been widely used in Dentistry, especially polymers of poly (methyl methacrylate) for fabricating dentures. This material has as advantages stable color and optical properties, satisfactory esthetic and dimensional stability, it is easy to be processed, and its physical properties have been proven adequate for dental applications. However, as disadvantage acrylic resins surface is susceptible to adherence and biofilm development of oral microorganism, such as fungi and bacteria. Microorganism's adherence is the first step to biofilm development, and it is related to pathogenic condition, leading to denture stomatitis. Recently, it had been proposed addition of modifiers to acrylic resin composition that could be able to improve its surface properties, and consequently controlling microorganisms' adherence. However, this change in composition of acrylic resin should not compromise its physical properties. Polytetrafluorethylene has been used as modifiers to fabricate medical devices such as stents and catheters because it is a biocompatible material, high resistance to chemical reagents and low surface energy. Thus, the aim of this study was to evaluate the physical properties, surface characteristics, adherence of microorganisms and biofilm formation of two acrylic resins, one polymerized by long and other polymerized by short cycle, with 2% (w/w) of PTFE added and to compare with the same resins with no PTFE added. For this, three studies were conducted: 1 - Physical properties of acrylic resins - specimens were prepared for each acrylic resin according to the ISO standard 1567:1999 (n=10) for each mechanical test: surface hardness, impact strength, flexural strength and flexural modulus and peak load were calculated; 2 - Characteristics of acrylic resin surface and adherence of Candida albicans: rectangular specimens (n=10) of each resin were prepared and evaluated for surface roughness, contact angle, surface free energy and C.albicans adherence. Adhered cells were expressed in colony forming units per surface area; 3- Biofilm formed on acrylic resins and its composition: acrylic resin discs (n=6) were used to Streptococcus mutans UA 159, Streptococcus sanguinis ATCC 10556 and Actinomyces naeslundii ATCC 12104 biofilm formation. Polysaccharide composition and colony forming units were compared. For both three studies the results of were analyzed by Two-Way ANOVA and Tukey test (P<.05). The results showed no statistical significant differences for surface hardness (P>0.05). However, impact and flexural strengths values for experimental groups, with PTFE added were significantly lower (P<.05) when compared to the groups with no PTFE added. The flexural modulus values of acrylic resin containing 2% PTFE polymerized by long cycle was higher than other resins (P<0.05). No statistical differences were found for roughness, contact angle, surface free energy (P>.05); there was a reduction trend in C. albicans adherence in acrylic resin with PTFE added, but it was not statistically significant. Regarding, the formation and composition of polysaccharide matrix the results showed no differences among the acrylic resin groups (P>0.05). The results showed that the 2% of PTFEE incorporated to acrylic resins was not enough to affect the mechanical properties, adherence and composition of biofilm. / Doutorado / Protese Dental / Doutor em Clínica Odontológica
7

Development of Candida albicans biofilms in the presence of fluconazole = effects on extracellular matrix = Desenvolvimento de biofilmes de Candida albicans na presença de fluconazol : efeitos na matriz extracelular / Desenvolvimento de biofilmes de Candida albicans na presença de fluconazol : efeitos na matriz extracelular

Gonçalves, Letícia Machado, 1987- 27 September 2013 (has links)
Orientador: Wander José da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-23T13:26:50Z (GMT). No. of bitstreams: 1 Goncalves_LeticiaMachado_D.pdf: 3139804 bytes, checksum: 4f3ad00e23ae5ec0336267a151dbe2e0 (MD5) Previous issue date: 2012 / Resumo: O fluconazol (FLZ) é um antifúngico amplamente utilizado no tratamento da candidose associada ao uso de prótese dental. No entanto, o sucesso desta terapia pode ser dificultado pela presença da matriz extracelular dos biofilmes de Candida albicans. Estudos já foram conduzidos avaliando o efeito do FLZ em biofilmes de C. albicans, no entanto, estudos que simulem uma condição na qual os biofilmes são desenvolvidos na presença do FLZ são escassos. Ainda, na tentativa de avaliar a organização tridimensional destes biofilmes, várias técnicas de microscopia já foram descritas, apesar de pouca atenção ser dada na análise da matriz extracelular. Frente ao exposto, o objetivo deste trabalho foi avaliar a matriz extracelular de biofilmes de C. albicans na presença de concentração salivar de FLZ. Dois estudos foram conduzidos e, em ambos, discos (10 mm x 2 mm) de resina acrílica à base de poli (metil metacrilato) foram confeccionados e cobertos com uma película de saliva sobre a qual biofilmes de C. albicans foram desenvolvidos. O primeiro estudo foi conduzido com o objetivo de definir uma metodologia para análise da matriz extracelular. Biofilmes de C. albicans ATCC 90028 foram desenvolvidos em meio de cultura sem suplementação (controle) ou suplementado com glicose ou sacarose, por 72 horas. Durante o desenvolvimento dos biofilmes foi adicionado o corante Concanavalina A (ConA) para a marcação da matriz extracelular. Após o desenvolvimento, os biofilmes foram corados com SYTO 9 para a marcação das células. As imagens obtidas por microscopia confocal foram analisadas pelo software COMSTAT. Para confirmação dos resultados, os biofilmes foram coletados e analisados bioquimicamente para determinação da composição da matriz de polissacarídeos pelo método fenol-sulfúrico. Os dados foram analisados por ANOVA seguido do teste de Tukey com nível de significância de 5%. Para o segundo estudo, biofilmes de C. albicans (ATCC 90028) e de dois isolados clínicos (P01 e P34) foram desenvolvidos em meio de cultura contendo FLZ na concentração biodisponível na saliva (2,56 ?g/mL), durante 48h. O grupo controle foi desenvolvido sem a presença de fluconazol. O número de células viáveis foi quantificado por diluição seriada, e a matriz extracelular analisada bioquimicamente, além da avaliação por microscopia confocal. Os dados foram analisados pelo teste t de Student com nível de significância de 5%. No primeiro estudo, observou-se que o uso de ConA permitiu uma marcação eficaz da matriz extracelular, confirmada pela análise bioquímica (p < 0,05). No segundo estudo, houve uma redução de 80% no número de células viáveis dos biofilmes desenvolvidos na presença de FLZ (p < 0,001). Considerando-se a proporção de polissacarídeos produzidos pelo número de células viáveis, observou-se que nos grupos experimentais, C. albicans foi capaz de produzir mais matriz extracelular do que os grupos controle (p < 0,05). Este resultado foi confirmado pelas imagens obtidas por microscopia confocal. Conclui-se que a microscopia confocal é uma ferramenta efetiva na análise da matriz extracelular de biofilmes de C. albicans, e que os biofilmes de C. albicans desenvolvidos na presença de FLZ apresentaram maior produção de matriz extracelular / Abstract: Fluconazole (FLZ) is a commonly used antifungal agent to treat patients with Candida-associated denture stomatitis. However, the success of this therapy may be compromised by the presence of extracellular matrix of C. albicans biofilms. Although studies have been conducting evaluating the effect of FLZ on C. albicans biofilms, studies that simulate the condition in which biofilms were allowed to grow in the presence of FLZ are limited. Additionally, in order to evaluate the three-dimensional organization of these biofilms, several microscopic techniques have been described, although little attempt has been paid to assess the extracellular matrix. The objective of this study was to investigate the extracellular matrix of C. albicans biofilms in the presence of salivary concentration of FLZ. For this, two studies were conducted. For both studies, discs (10 mm x 2 mm) were fabricated using poly (methyl methacrylate). Salivary pellicle was formed on disc surface and C. albicans biofilms were developed. In the first study a methodology for analyzing the extracellular matrix was defined. C. albicans ATCC 90028 biofilms were developed in culture media without (control) or with supplementation by glucose or sucrose for 72 hours. During development, biofilms were stained with Concanavalin A (ConA) in order to label the extracellular matrix. After, cells were also labeled with SYTO-9. Images obtained by confocal microscopy were analyzed by COMSTAT software. In order to confirm the results, biofilms were subjected by the biochemical phenol-sulfuric method. Data were analyzed by ANOVA followed by Tukey's test at a significance level set at 5%. For the second study, biofilms of an ATCC 90028 and two clinical isolates (, P01 and P34) were developed for 48 hours. FLZ at 2.56 ?g/mL, concentration bioavailable in saliva, was added to culture media of experimental groups. Biofilms were investigated for the number of viable cells by serial dilution and extracellular matrix production was analyzed by phenol-sulfuric method and confocal microscopy. Data were analyzed by Student's t-test, with significance level set at 5%. In the first study, the use of ConA provided an effective labeling of extracellular matrix, which was confirmed by phenol-sulfuric method (p < 0.05). In the second study, a reduction of 80% was observed in the number of viable cells for C. albicans biofilms developed in the presence of FLZ (p < 0.001). Considering the proportion of polysaccharides produced by the number of viable cells, it was observed that in the experimental groups, C. albicans was able to produce more extracellular matrix than the control groups (p < 0.05). This result was confirmed by confocal images. It was concluded that confocal microscopy is an effective tool to investigate the extracellular matrix of C. albicans biofilms; and C. albicans biofilms developed in the presence of FLZ present increased extracellular matrix production / Doutorado / Protese Dental / Doutora em Clínica Odontológica
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Evaluation of multispecies biofilms formed on different substrata and exposed to salivary concentrations of antimicrobial agents = Avaliação de biofilmes multiespécies formados em diferentes substratos e expostos a concentrações salivares de agentes antimicrobianos / Avaliação de biofilmes multiespécies formados em diferentes substratos e expostos a concentrações salivares de agentes antimicrobianos

Ricomini Filho, Antônio Pedro, 1983- 21 August 2018 (has links)
Orientador: Altair Antoninha Del Bel Cury / Tese (Doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-21T23:47:13Z (GMT). No. of bitstreams: 1 RicominiFilho_AntonioPedro_D.pdf: 2535934 bytes, checksum: eff4f940490cd7e063a65eb2cce8dcec (MD5) Previous issue date: 2013 / Resumo: A colonização de diferentes substratos presentes na cavidade oral por micro-organismos e o desenvolvimento de biofilme são fatores etiológicos da maioria das doenças orais. Além dos dentes, materiais como titânio e polimetilmetacrilato são comumente encontrados neste ambiente e o papel que estes substratos desempenham na prevalência de populações bacteriana e fúngica em biofilmes orais são pouco compreendidas. Além disso, o comportamento da população microbiana de biofilmes orais multiespécies na presença de antimicrobianos liberados na saliva permanece desconhecido. Assim, o objetivo deste estudo foi (i) avaliar o efeito de diferentes substratos na prevalência de micro-organismos em biofilmes orais multiespécies e (ii) o efeito de antimicrobianos liberados na saliva na população microbiana de biofilmes multiespécies. Para o primeiro estudo, discos de hidroxiapatita, titânio e polimetilmetacrilato (PMMA) foram utilizados como substrato para o desenvolvimento do biofilme mimetizando esmalte dental, implantes dentários e base de prótese, respectivamente. O modelo de biofilme multiespécies foi composto por cinco bactérias (Streptococcus oralis, Streptococcus mutans, Actinomyces naeslundii, Veillonella dispar e Fusobacterium nucleatum) e um fungo (Candida albicans). Biofilmes maduros (64,5 h de desenvolvimento) foram removidos por ondas ultrassônicas, plaqueados em meio ágar e as contagens de UFC de cada micro-organismo foram calculadas. A microscopia eletrônica de varredura foi utilizada para visualizar a superfície dos materiais. Os dados foram analisados por ANOVA um critério. Para o segundo estudo o mesmo modelo de biofilme multiespécies foi utilizado. Dois antibióticos, azitromicina e metronidazol, e um antifúngico, fluconazol, foram avaliados. Biofilmes maduros (64,5 h de desenvolvimento) foram expostos a azitromicina, metronidazol ou fluconazol em concentrações encontrada na saliva de 2,12 ug/mL, 15,15 ug/mL e 2,56 ug/mL, respectivamente, por 24h. Após este período, o biofilme foi removido por ondas ultrassônicas, plaqueados em meio ágar e as contagens de UFC de cada micro-organismo foram calculadas. Microscópio eletrônico de varredura e microscópio a laser de varredura confocal com células coradas por hibridização in situ por fluorescência (FISH) foram utilizados para avaliar a estrutura do biofilme. Os dados foram analisados por teste t para amostras independentes e testes não paramétricos de Mann-Whitney. O primeiro estudo não mostrou diferença na população para cada micro-organismo no biofilme entre os entre três materiais avaliados (p>0,05). No segundo estudo, todos os antimicrobianos avaliados foram capazes de alterar a população microbiana (p<0,05), no entanto nenhum dos agentes antimicrobianos foi capaz de eliminar completamente um micro-organismo específico do biofilme. Azitromicina reduziu as populações de A. naeslundii e V. dispar enquanto aumentou C. albicans (p<0,05). Metronidazol reduziu todos os micro-organismos avaliados, com uma grande redução para V. dispar e F. nucleatum (p<0,001). Fluconazol reduziu populações de C. albicans e F. nucleatum e aumentou as contagens de S. oralis e V. dispar (p<0,05). Pode concluir-se que os substratos não foram capazes de interferir na formação dos biofilmes multiespécies e que os antimicrobianos em concentrações semelhantes às liberadas na saliva alteraram a população microbiana / Abstract: The colonization of different substrata present in the oral cavity by microorganisms and the biofilm development are the etiological factors of the majority of oral diseases. Besides the teeth, materials such as titanium and polymethylmetacrylate are commonly found in this environment and the role these substrata play on the prevalence of bacterial and fungal population in oral biofilms are poorly understood. In addition, the behavior of microbial population of multispecies oral biofilms in the presence of antimicrobials released in saliva remains unknown. Thus, the aim of this study was (i) to evaluate the effect of different substrata on the prevalence of microorganisms in an oral multispecies biofilms and (ii) the effect of antimicrobials released in saliva on the microbial population of a multispecies biofilms. For the first study hydroxyapatite, titanium and polymethylmetacrylate (PMMA) discs were used as substrata for biofilm development mimicking tooth enamel, dental implant and denture base, respectively. The multispecies biofilm model was composed by five bacteria (Streptococcus oralis, Streptococcus mutans, Actinomyces naeslundii, Veillonella dispar and Fusobacterium nucleatum) and one yeast (Candida albicans). Mature biofilms (64.5 h of development) were removed by ultrasonic waves, plated on agar media and CFU counts of each microorganism were calculated. Scanning electron microscopy was used to visualize the materials' surface. Data were analyzed by one-way ANOVA. For the second study the same multispecies biofilm model was used. Two antibiotics, azithromycin and metronidazole, and one antifungal, fluconazole, were evaluated. Mature biofilms (64.5 h development) were exposed to azithromycin, metronidazole or fluconazole at concentrations found in saliva of 2.12 ug/mL, 15.15 ug/mL and 2.56 ug/ml, respectively, for 24h. After this period, the biofilm was removed by ultrasonic waves, plated on agar media and CFU counts of each microorganism were calculated. Scanning electron microscopy and confocal scanning laser microscopy with cells stained by fluorescent in situ hybridization (FISH) technique were used to assess the biofilm structure. Data were analyzed by independent-samples t-test and Mann-Whitney nonparametric test. The first study showed no difference in the biofilm population for each microorganism among the three materials evaluated (p>0.05). In the second study, all antimicrobials evaluated were able to change microbial population (p<0.05), however none of the antimicrobials was able to completely eliminate a specific microorganism from the biofilm. Azithromycin reduced A. naeslundii and V. dispar population while increased C. albicans (p<0.05). Metronidazole reduced all the microorganisms evaluated, with a great reduction for V. dispar and F. nucleatum (p<0.001). Fluconazole reduced C. albicans and F. nucleatum population and increased S. oralis and V. dispar counts (p<0.05). It can be concluded that the substrata were not able to interfere with the formation of multispecies biofilms and antimicrobials in concentrations similar to those released in the saliva changed microbial population, however they were not able to eliminate microorganisms / Doutorado / Protese Dental / Doutor em Clínica Odontológica
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The influence of mixing ratio on the fatigue behaviour of fibre reinforced polymers

Stuhlinger, Martin Ernst January 2013 (has links)
Magister Scientiae Dentium - MSc(Dent) / Statement of the problem: Fibre reinforcement of polymethyl methacrylate (PMMA) denture base material is known to improve the strength, as well as the fatigue behavior, of the material. The powder liquid (P/L) ratio of PMMA is often changed to modify the handling properties of the material. Little is known about the effect of this deviation from manufacturer’s guidelines on the fatigue behaviour of the fibre reinforced product. Purpose: This study compared the flexural strength (FS) of PMMA reinforced with glass fibre using different P/L ratios, before and after cyclic loading. Methods and materials: Three groups, with 50 glass fibre reinforced (everStick nonimpregnated fibers) heat-cured PMMA resin (Vertex Rapid Simplified) specimens each, were prepared using a custom-made template (dimensions 10x9x50mm). Each group had a different P/L ratio: the control group (100%) had the manufacturer’s recommended ratio; the 90% and 80% groups had reduced P/L ratios (by weight).Twenty five specimens from each group were subjected to a 3-point bending compression test using a universal testing machine. The remaining 25 specimens from each group were subjected to cyclic loading (104 cycles) before compression testing. The (FS) was calculated using the highest force (Fmax) before specimen failure. Flexural strength was calculated using the equation: FS=3WL/2bd2. Within each group, median FS values before and after cyclic loading were compared by means of a non-parametric analysis of variance. The Aligned Ranks Transform method was used for the analysis. Statistical significance was set at p=0.05. Results: The Fmax (N) of the control (100%), 90% and 80% groups fatigued and unfatigued were 100%: 1665 (fat), 1465 (unfat); 90%: 1679 (fat), 1548 (unfat) and 80%: 1585 (fat), 1467 (unfit) respectively. There was no significant interaction between Mix ratio and Fatigue state, and the 80% mix had a significantly higher mean than either the 90% or 100% mix (with differences of about 0.3 units for both). The Fatigued state had a higher mean than the Un- fatigued state by about 6.0 units. Using FS (MPa) it was found that the fatigued 80% mix specimens had the highest value. The FS MPa of the control (100%), 90% and 80% groups fatigued and un-fatigued were 64.3, 60.6; 66.9, 65.6 and 70.2, 69.3 respectively. The fact that fatiguing strengthened the specimens merits further research. When observing the broken specimens it was found that there was a complete debonding of the fibres and the PMMA. Conclusion and clinical relevance: a) Fibre: The benefit of using glass fibre bundles to reinforce prostheses fabricated using heat cured PMMA is questionable due to problems with bonding between the fibre bundles and the heat cured PMMA resin. b) Fatiguing: An average person chews 107 times during a 3 year period. A limited period of average masticatory forces should not have a detrimental effect on prostheses made from heat cured PMMA resin. c) Mix ratio: Within the normal parameters of laboratory techniques the mix ratio of PMMA resin had no significance on the fracture resistance of the prostheses. Due to the high cost of the fibres used for the reinforcement and the limited success and insignificant results achieved in this study, this researcher cannot recommend using Stickbond or Stick fibers for the reinforcement of dentures made with heat cured PMMA resin.
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Swift heavy ion irradiation of polyester and polyolefin polymeric film for gas separation application

Adeniyi, Olushola Rotimi January 2015 (has links)
Philosophiae Doctor - PhD / The combination of ion track technology and chemical etching as a tool to enhance polymer gas properties such as permeability and selectivity is regarded as an avenue to establish technology commercialization and enhance applicability. Traditionally, permeability and selectivity of polymers have been major challenges especially for gas applications. However, it is important to understand the intrinsic polymer properties in order to be able to predict or identify their possible ion-polymer interactions thus facilitate the reorientation of existing polymer structural configurations. This in turn can enhance the gas permeability and selectivity properties of the polymers. Therefore, the choice of polymer is an important prerequisite. Polyethylene terephthalate (PET) belongs to the polyester group of polymers and has been extensively studied within the context of post-synthesis modification techniques using swift heavy ion irradiation and chemical treatment which is generally referred to as ‘track-etching’. The use of track-etched polymers in the form of symmetrical membranes structures to investigate gas permeability and selectivity properties has proved successful. However, the previous studies on track-etched polymers films have been mainly focused on the preparation of symmetrical membrane structure, especially in the case of polyesters such as PET polymer films. Also, polyolefins such as polymethyl pentene (PMP) have not been investigated using swift heavy ions and chemical etching procedures. In addition, the use of ‘shielded’ material on PET and PMP polymer films prior to swift heavy ion irradiation and chemical etching to prepare asymmetrical membrane structure have not been investigated. The gas permeability and selectivity of the asymmetrical membrane prepared from swift heavy ion irradiated etched 'shielded' PET and PMP polymer films have not been determined. These highlighted limitations will be addressed in this study. The overall objective of this study was to prepare asymmetric polymeric membranes with porous surface on dense layer from two classes of polymers; (PET and PMP) in order to improve their gas permeability and selectivity properties. The research approach in this study was to use a simple and novel method to prepare an asymmetric PET and PMP polymer membrane with porous surface and dense layer by mechanical attachment of ‘shielded’ material on the polymer film before swift heavy ion irradiation. This irradiation approach allowed for the control of swift heavy ion penetration depth into the PET and PMP polymer film during irradiation. The procedure used in this study is briefly described. Commercial PET and PMP polymer films were mechanically ‘shielded’ with aluminium and PET foils respectively. The ‘shielded’ PET polymer films were then irradiated with swift heavy ions of Xe source while ‘shielded’ PMP polymer films were irradiated with swift heavy ions Kr. The ion energy and fluence of Xe ions was 1.3 MeV and 106 respectively while the Kr ion energy was 3.57 MeV and ion fluence of 109. After swift heavy ion irradiation of ‘shielded’ PET and PMP polymer films, the attached ‘shielded’ materials were removed from PET and PMP polymer film and the irradiated PET and PMP polymer films were chemically etched in sodium hydroxide (NaOH) and acidified chromium trioxide (H2SO4 + CrO3) respectively. The chemical etching conditions of swift heavy ion irradiated ‘shielded’ PET was performed with 1 M NaOH at 80 ˚C under various etching times of 3, 6, 9 and 12 minutes. As for the swift heavy ion irradiated ‘shielded’ PMP polymer film, the chemical etching was performed with 7 M H2SO4 + 3 M CrO3 solution, etching temperature was varied between 40 ˚C and 80 ˚C while the etching time was between 40 minutes to 150 minutes. The SEM (surface and cross-section micrograph) morphology results of the swift heavy ion irradiated ‘shielded’ etched PET and PMP films showed that asymmetric membranes with a single-sided porous surface and dense layer was prepared and remained unchanged even after 12 minutes of etching with 1 M NaOH solution as in the case of PET and 2 hours 30 minutes of etching with 7 M H2SO4 + 3 M CrO3 as observed for PMP polymer film. Also, the swift heavy ion irradiated ‘shielded’ etched PET polymer film showed the presence of pores on the polymer film surface within 3 minutes of etching. After 12 minutes chemical etching with 1 M NaOH solution, the dense layer of swift heavy ion irradiated ‘shielded’ etched PET polymer film experienced significant reduction in thickness of about 40 % of the original thickness of as-received PET polymer film. The surface morphology of swift heavy ion irradiated ‘shielded’ etched PET polymer film by SEM analysis revealed finely distributed pores with spherical shapes for the swift heavy ion irradiated ‘shielded’ etched PET polymer film within 6 minutes of etching with 1 M NaOH solution. Also, after 9 minutes and 12 minutes of etching with 1 M NaOH solution of the swift heavy ion irradiated ‘shielded’ etched PET polymer film, the pore walls experienced complete collapse with intense surface roughness. Interestingly, the 12 minutes etched swift heavy ion ‘shielded’ irradiated PET did not lose its asymmetrical membrane structure despite the collapse of the pore walls. In the case of swift heavy ion irradiated ‘shielded’ etched PMP polymer film, SEM morphology analysis showed that the pores retained their shape with the presence of defined pores without intense surface roughness even after extended etching with 7 M H2SO4 + 3 M CrO3 for 2 hours 30 minutes. Also, the pores of swift heavy ion irradiated ‘shielded’ etched PMP polymer films were observed to be mono dispersed and not agglomerated or overlapped. The SEM cross-section morphology of the swift heavy ion irradiated ‘shielded’ etched PMP polymer film showed radially oriented pores with increased pore diameters in the PMP polymer film which indicated that etching was radial instead of lateral, and no through pores were observed showing that the dense asymmetrical structure was retained. The SEM results revealed that the pore morphology i.e. size and shape could be accurately controlled during chemical etching of swift heavy ion ‘shielded’ irradiated PET and PMP polymer films. The XRD results of swift heavy ion irradiated ‘shielded’ etched PET revealed a single diffraction peak for various times of chemical etching in 1 M NaOH solution at 3, 6, 9 and 12 minutes. The diffraction peak of swift heavy ion irradiated ‘shielded’ etched PET was observed to reduce in intensity and marginally shifted to lower angles from 25.95˚ 2 theta to 25.89˚ 2 theta and also became broad in shape. It was considered that the continuous broadening of diffraction peaks due to an increase in etching times could be attributed to disorderliness of the ordered region within the polymer matrix and thus decreases in crystallinity of the swift heavy ion irradiated ‘shielded’ etched PET polymer film. The XRD analysis of swift heavy ion irradiated ‘shielded’ etched PMP polymer films indicated the presence of the diffraction peak at 9.75˚ 2 theta with decrease in intensity while the diffraction peaks located at 13.34˚, 16.42˚, 18.54˚ and 21.46˚ 2 theta disappeared after chemical etching in acidified chromium trioxide (H2SO4 + CrO3) after 2 hours 30 minutes. The TGA thermal profile analysis of swift heavy ion irradiated ‘shielded’ etched PET did not show the evolution of volatile species or moisture at lower temperatures even after 12 minutes of etching in 1 M NaOH solution in comparison with commercial PET polymer film. Also, it was observed that the swift heavy ion irradiated layered’ etched PET polymer film started to undergo degradation at a higher temperature than untreated PET which resulted in an approximate increase of 50 ˚C in comparison with the commercial PET polymer film. The TGA results of swift heavy ion irradiated ‘shielded’ etched PMP polymer film revealed an improvement of about 50 ˚C in thermal stability before thermal degradation even after etching in acidified chromium trioxide for 2 hours 30 minutes at 80 ˚C. Spectroscopy (IR) analysis of the swift heavy ion irradiated ‘shielded’ etched PET and PMP polymer films showed the presence of characteristic functional groups associated with either PET or PMP structures. The variations of irradiation and chemical etching conditions revealed that the swift heavy ion ‘shielded’ irradiated etched PET polymer film experienced continuous degradation of available functional groups as a function of etching time and also with complete disappearance of some functional groups such as 1105 cm-1 and 1129 cm-1 compared with the as-received PET polymer film which are both associated with the para-substituted position of benzene rings. In the case of swift heavy ion irradiated ‘shielded’ etched PMP polymer film, spectroscopic (IR) analysis showed significant variations in the susceptibility of associated functional groups within the PMP polymer film with selective attack and emergence of some specific functional groups such as at 1478 cm-1, 1810 cm-1 and 2115 cm-1 which were assigned to methylene, CH3 (asymmetry deformation), CH3 and CH2 respectively Also, the IR results for swift heavy ion irradiated ‘shielded’ etched PMP polymer showed that unsaturated olefinic groups were the dominant functional groups that were being attacked by during etching with acidified chromium trioxide (H2SO4+CrO3) which is an aggressive chemical etchant. The gas permeability analysis of swift heavy ion irradiated ‘shielded’ etched PET and PMP polymer films showed that the gas permeability was improved in comparison with the as-received PET and as-received PMP polymer films. The gas permeability of swift heavy ion irradiated ‘shielded’ etched PET increased as a function of etching time and was found to be highest after 12 minutes of chemical etching in 1 M NaOH at 80 ˚C. In the case of swift heavy ion irradiated ‘shielded’ etched PMP, the gas permeability was observed to show the highest gas permeability after 2 hours 30 minutes of etching in H2SO4 + CrO3 solution. The gas permeability analysis for swift heavy ion irradiated ‘shielded’ PET and PMP polymer films was tested for He, CO2 and CH4 and the permeability results showed that helium was most permeable compared with CO2 and CH4 gases. In comparison, the selectivity analysis was performed for He/CO2 and CH4/He and the results showed that the selectivity decreased with increasing in etching time as expected. This study identified some important findings. Firstly, it was observed that the use of ‘shielded’ material on PET and PMP polymer films prior to swift heavy ion irradiation proved successful in the creation of asymmetrical polymer membrane structure. Also, it was also observed that the chemical etching of the ‘shielded’ swift heavy ion irradiated PET and PMP polymer films resulted in the presence of pores on the swift heavy ion irradiated side while the unirradiated sides of the PET and PMP polymer films were unaffected during chemical etching hence the pore depth could be controlled. In addition, the etching experiment showed that the pores geometry can be controlled as well as the gas permeability and selectivity properties of swift heavy ion ‘shielded’ irradiated etched PET and PMP polymer films. The process of polymer bulk and surface properties modification using ion-track technology i.e. swift heavy ion irradiation and subsequent chemical treatment of the irradiated polymer serves to reveal characteristic pore profiles unique to the prevailing ion-polymer interaction and ultimately results in alteration of the polymer characteristics.

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