O diagnóstico das lesões incipientes de erosão em esmalte é difícil de ser realizado e, em situações clínicas, poderá ocorrer a colagem de braquetes em superfícies erodidas. Este trabalho in vitro avaliou a adesão de braquetes ortodônticos ao esmalte dentário bovino hígido e previamente erodido, utilizando dois materiais para colagem. Os fatores em estudo foram condição prévia do esmalte em 2 níveis (com e sem erosão) e tipo de material de colagem em 2 níveis (Transbond XT e Fuji Ortho LC). A amostra foi composta por 160 coroas de incisivos bovinos, sendo metade dela submetida a desafio erosivo para formação de lesões artificiais de erosão e a outra metade permaneceu hígida. Na ciclagem erosiva as coroas foram imersas 8X/dia em Coca-cola® (10 min), seguido da imersão em saliva artificial (2 h), durante 5 dias. A outra metade da amostra ficou em saliva artificial por 5 dias. Braquetes de incisivo central superior foram colados às coroas hígidas (H) e erodidas (E), seguindo orientações dos fabricantes de cada material. As variáveis de resposta foram resistência ao cisalhamento e índice de remanescente adesivo (IRA). Os dados de resistência ao cisalhamento foram analisados por ANOVA 2 critérios e Teste de Tukey (p<0,05). Os resultados, expressos em megapascal, não mostraram diferenças na resistência ao cisalhamento entre esmalte erodido e hígido, tanto no grupo colado com resina (RH = 15,25 +3,72; RE = 15,79 +4,41) quanto colado com ionômero (IH = 10,70 +3,73; IE = 11,26 +3,70). A resina apresentou resistência à colagem superior ao ionômero. Na comparação do índice de remanescente adesivo, por meio do teste de Mann Whitney, o esmalte erodido apresentou valores mais altos para o IRA, evidenciando uma maior quantidade de material remanescente no esmalte, tanto no grupo colado com resina (p=0,044) quanto com ionômero (p<0,001). Conclui-se que a presença da lesão de erosão não interfere na resistência ao cisalhamento de braquetes colados ao esmalte tanto com resina quanto com cimento de ionômero de vidro. No entanto, independentemente do material de colagem, o índice de remanescente adesivo evidenciou uma maior adesão ao esmalte com erosão. / The diagnosis of initial erosion lesions on enamel is difficult and in some clinical situations, the professional bonds brackets to eroded surfaces without noting.This in vitro study evaluated the bond strength of orthodontic brackets bonded to eroded and sound bovine enamel with two different materials. The factors under study were enamel condition in two levels (with and without erosion) and type of bonding material in two levels (Transbond® XT and Fuji Ortho LC). The sample consisted of 160 bovine lower incisor teeth, half of the specimens was subjected to erosive challenge to form artificial erosive lesions and the other half remained sound. In the erosive cycling tooth crowns were immerged 8x/day in Coca-cola® (10 min), followed by immersion in artificial saliva for (2 h), for 5 days. The other half of the sample was maintained in artificial saliva for 5 days. At sequence, brackets were bonded to eroded (E) and sound (S) enamel, according to manufacturing recommendations of each material. The response variables were shear bond strength and adhesive remnant index (ARI). Shear bond strength data were analyzed by Two-way ANOVA and Tukeys test (p<0,05). The results, expressed in megapascal, did not show any difference between eroded and sound enamel, in both composite resin (RS = 15,25 +3,72; RE = 15,79 +4,41) and glass ionomer (IS = 10,70 +3,73; IE = 11,26 +3,70) groups. Composite resin showed higher shear bond strength compared to glass ionomer cement. In the comparison of adhesive remnant index using Mann Whitney test, eroded enamel presented higher scores for ARI, showing greater amount of material remaining on enamel, in both resin (p=0,04) and ionomer (p<0,001) groups. It was concluded that the presence of erosion lesions did not interfere on shear bond strength of brackets bonded to enamel with composite resin or glass ionomer cement. However, independently of the bonding material, adhesive remnant index showed higher bond strength to eroded enamel.

Orientador: Regina Maria Puppin Rontani / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-10-05T18:49:21Z (GMT). No. of bitstreams: 1 Correr_AnaRosaCosta_D.pdf: 3218831 bytes, checksum: f30505368b581fed81781723b234fbd9 (MD5) Previous issue date: 2013 / Resumo: O propósito deste estudo foi avaliar a influencia de diferentes tipos de substrato (Capitulo 1) e tratamento com etanol 100% (Capitulo 2) ou digluconato de clorexidina a 2% (CHX) (Capitulo 3) na resistência e longevidade da união compósito/dentina, apos diferentes períodos de armazenagem. Os dentes humanos hígidos foram divididos em 3 grupos, de acordo com o substrato dentinario: (Sd) dentina hígida, (Ci) dentina infectada (manutenção da carie) e (Ca) dentina afetada (remoção parcial de carie). As superfícies oclusais de terceiros molares hígidos foram removidas com disco diamantado dupla face sob refrigeração, a fim de expor a superfície plana dentinaria hígida, a qual foi submetida ao desenvolvimento da lesão de carie artificial com S. mutans. Brocas esféricas foram usadas para remover parcialmente o tecido cariado pigmentado, ate que permanecesse apenas a dentina levemente corada (Ca). Em seguida, os dentes foram novamente subdivididos, de acordo com o tratamento da superfície: Grupo Controle (Ct) - nenhum tratamento (Capitulo 1); Ct e (Et) - aplicação de etanol 100% (Capitulo 2); e, Ct e (CHX) - aplicação de digluconato de clorexidina a 2% (Capitulo 3). O substrato foi condicionado com acido fosfórico a 35% por 15 s, lavado por 30 s e seco com leve jato de ar. CHX ou Et foram aplicados apos o condicionamento acido. O sistema adesivo Adper Single Bond 2 (3M ESPE) foi aplicado de acordo com as recomendações do fabricante e fotoativado por 20 s com a fonte de aparelho de luz XL 2500. Sobre a superfície de união foram inseridos incrementos de 2 mm do compósito Z350 (3M ESPE), polimerizados usando a fonte de luz XL 2500 por 40 s, ate confeccionar um bloco com 6 mm de altura. As amostras foram armazenadas em água destilada a 37o C por 24 horas. Apos, os dentes foram seccionados perpendicularmente a área de união, de modo a obter palitos com área de secção transversal de 1mm2. Os palitos foram armazenadas em três períodos: 24 horas, 6 meses e 1 ano. Em seguida, as amostras foram submetidas ao ensaio de resistência de união a microtração usando a maquina de ensaio EZ test (EZS, Shimadzu) a velocidade de 0,5 mm/minuto. Os dados foram submetidos a Analise de Variância e ao teste de Tukey HSD (?=0,05). A união em Sd mostrou valores de resistência de união significativamente maior quando comparado a Ca e Ci. As amostras armazenadas nos períodos de 6 meses e 1 ano resultou na diminuição da resistência de união, independente do tipo de substrato e/ou tratamento. O etanol não foi efetivo em melhorar a resistência de união para os três substratos de dentina avaliados. A clorexidina não influenciou na resistência de união nos períodos de armazenagem avaliados, independente dos substratos / Abstract: The aim of this study was to evaluate the effect of 2% chlorhexidine digluconate (CHX) and 100% ethanol wet-bonding (Et) on the degradation of the adhesive system bond strength in sound or artificial caries-affected/infected dentin after different storage times under microtensile test (_TBS). The sound teeth were divided into 3 groups, according to dentin substrates: sound dentin, caries-infected dentin (maintained of caries) and caries-affected dentin (partial removal of caries). Non-carious human third molars had their occlusal enamel removed with a slow speed diamond saw, under copious water-cooling to expose a flat-surfaced sound dentin, which was submitted to the microbiological challenge (S. mutans) for the development of artificial caries. Spherical drill was used to remove soft pigmented carious tissue till hard and slightly pigmented dentin remains (Ca). After, the teeth will be assigned into 3 subgroups according to surface treatment: water wet- bonding (Ct) (Chapter 1); Ct and 100% ethanol application (Et) (Chapter 2); and, Ct and chlorhexidine digluconate 2% application (CHX) (Chapter 3). The substrate will was etched with 35% phosphoric acid gel for 15 s, rinsed for 30 s with tap water and dried with oil/water-free air. The CHX or Et was applied for 60 s, just after etching with 35% phosphoric acid gel. The adhesive system Adper Single Bond 2 (3M ESPE) was applied according to the manufacturer's instruction and polymerized for 10 s by a light-curing unit XL 2500. The bonded surfaces were coupled with a composite resin Filtek Z350 (3M ESPE) applied in 2 mm increments and polymerized using a curing unit XL 2500 (3M ESPE) for 40 s for each increment and to build 6 mm thick block. The restored teeth were stored in distilled water at 37o C for 24 h. After this period, the restored teeth were longitudinally sectioned across the bonded interface to produce a series of 1.0mm2 beams. The specimens were then submitted to three storage periods: 24 hours, 6 months, or 1 year. Afterwards, the storage periods, the specimens were submitted to a microtensile bond strength (_TBS) using EZ test machine (EZS, Shimadzu) at a crosshead speed of 0.5 mm/min until failure. Data were submitted to ANOVA and Tukey's HSD test (?=0.05). The bonding with sound dentin showed _TBS values significant higher when compared to caries-affected and caries-infected dentin. The 6 months and 1 year storage periods resulted in decreased bond strengths for all dentin conditions and/or treatment. The ethanol was not effective to improve the _TBS for the three dentin substrates evaluated. The CHX did not affect the 24- hour, 6 and 12 months _TBS, independent of the tested dentin substrates / Doutorado / Materiais Dentarios / Doutora em Materiais Dentários

Orientador: Regina Maria Puppin-Rontani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-10-05T18:32:34Z (GMT). No. of bitstreams: 1 Costa_AnaRosa_M.pdf: 3213917 bytes, checksum: 992b632a45094f40763749a7a2048776 (MD5) Previous issue date: 2009 / Resumo: O propósito neste estudo foi avaliar o efeito da ciclagem dinâmica de pH (solução DES/RE) e o tempo de armazenagem na degradação da união resina/dentina, por meio do ensaio de resistência da união à microtração e quantificar os íons flúor liberados do sistema adesivo. A superfície da face oclusal de terceiros molares humanos extraídos foi desgastada com lixa de carbeto de silício de granulação 600. Em seguida, os dentes foram separados em 2 grupos de acordo com o sistema adesivo utilizado (n=4): Clearfil Protect Bond (PB) (Kuraray) e Clearfil SE Bond (SE) (Kuraray). Um bloco de resina composta TPH (Dentsply) de aproximadamente 6 mm de espessura foi unido ao dente com os sistemas adesivos, preparados de acordo com as recomendações do fabricante e cada camada de 2 mm de espessura foi irradiada por 40 segundos. Após 24 horas em umidade relativa à 37º C, as amostras foram seccionadas perpendicularmente à área de união, para obter palitos com área de secção transversal de 1mm2 e separados em 6 grupos de acordo com o período de armazenagem: G1 - PBI (imediato - controle); G2 - PBC (ciclagem dinâmica de pH); G3 - PBA (armazenagem em água deionizada por 140 dias); G4 - SEI (imediato - controle); G5 - SEC (ciclagem dinâmica de pH); e, G6 - SEA (armazenagem em água deionizada por 140 dias). Em seguida, os palitos foram submetidos ao ensaio de resistência de união à microtração em máquina de ensaio universal (Instron) a velocidade de 0,5 mm/minuto. Para análise da liberação de flúor, os palitos foram armazenados individualmente em 1 mL de solução DES (n=8), RE (n=8) ou água deionizada (n=23) para o sistema adesivo Clearfil Protect Bond com um eletrodo íon específico conectado a um potenciômetro, usando 0,05 mL do sistema tampão concentrado TISAB III adicionado a 0,5 mL da solução da amostra, por 1 a 4 (DES, RE e água deionizada) e 30 dias (água deionizada). Os dados foram submetidos à Análise de Variância, ao teste de Tukey (5%) e ao teste de Friedman's. Os valores de resistência de união à microtração (MPa) foram: 30,4±11,6 (PBI), 29,5±9,1 (PBC), 27,1±11,6 (PBA), 28,9±11,1 (SEI), 27,1±7,6 (SEC) e 21,3±10,9 (SEA). Nenhuma diferença estatística foi observada entre os dois sistemas adesivos em todas as condições de tratamento (p>0,05). O PBI e o SEI apresentaram valores de resistência de união à microtração significativamente maiores em relação ao PBA e ao SEA (p<0,05). A ciclagem dinâmica de pH no PB e SE não mostrou diferença significativa nos valores de resistência de união à microtração, quando comparado com o imediato e a armazenagem em água deionizada por 140 dias (p>0,05). A concentração de flúor presente nas soluções DES/RE foi menor que 0,03125 ppm e nenhuma quantidade esteve presente na água, para o sistema adesivo testado (Clearfil Protect Bond). Conclui-se, portanto, que nenhuma diferença significativa foi observada entre os sistemas adesivos. A armazenagem em água deionizada por 140 dias diminuiu os valores de resistência da união à microtração, para os dois sistemas adesivos. / Abstract: The purpose of this study was to evaluate the effect of the dynamic chemical challenge pH (DES/RE solutions) and storage regimen on degradation of resin/dentin-bonding using the microtensile bond strength (µTBS) and quantify fluoride release from the adhesive system. Superficial occlusal dentin of extracted human molars was exposed and wet ground with 600-grit SiC paper. Then, teeth were randomly distributed into 2 groups according to adhesive systems (n=4): Clearfil Protect Bond (PB) (Kuraray) and Clearfil SE Bond (SE) (Kuraray). A block of composite resin TPH (Dentsply) with 6 mm thickness was bonded to the tooth with the adhesive systems according to manufacturer's instructions and each thickness with 2 mm was light cured for 40 seconds. After 24 hours in moist environment at 37oC, the specimens were sectioned perpendicular to the bonding area to obtain 1mm2 sectional area sticks, which were randomly divided into 6 groups according to storage regimen: G1 - PBI (immediate-control); G2 - PBC (pH cycling model); G3 - PBW (140 days water storage); G4 - SEI (immediate - control); G5 - SEC (pH cycling model); and, G6 - SEW (140 days water storage). After that, the sticks were submitted to microtensile bond strength (µTBS) test in a Universal machine (Instron) at a crosshead speed of 0.5mm/min. Fluoride concentration in demineralization (n=8) / remineralization (n=8) solutions and deionized water (n=23) was obtained by collecting 0,5 mL of these solutions and 0,05 mL of TISAB III, from 1 to 4 days ( De, Re and deionized water) and 30 days (deionized water). Fluoride release was detected using a fluoride-specific electrode connected to a microprocessor ion analyzer.The data were submitted to ANOVA and Tukey's tests (p<0.05) and Friedman's tests. Microtensile bond strength- µTBS (MPa) mean values were 30.4±11.6 (PBI), 29.5±9.1 (PBC), 27.1±11.6 (PBW), 28.9±11.1 (SEI), 27.1±7.6 (SEC) and 21.3±10.9 (SEW). There was no significantly statistical difference between PB and SE in all conditions of treatment (p>0.05). The PBI and SEI showed significantly higher µTBS values compared to PBW and SEW (p<0.05). The pH cycling model in the PB and SE didn't show significantly difference on µTBS values when compared immediate and the deionized water storage for 140 days (p>0.05). Fluoride concentrations present in the DES/RE were less than 0.03125 ppm and no in deionized water, regardless of the adhesive system tested. No significantly difference was found between adhesive systems in all conditions. The 140-day water storage decreased the µTBS values from two adhesives systems. / Mestrado / Materiais Dentarios / Mestre em Materiais Dentários

Non-covalent interactions are fundamental to molecular recognition processes that underpin the structure and function of chemical and biological systems. Their study is often difficult due to the interplay of multiple interactions and solvent effects common in complex systems. Herein, chapter one provides some general background on the area before presenting a literature review of key, contemporary developments on the use of folding molecules for the quantification of non-covalent interactions. Chapter two investigates the magnitude and extent of energetic cooperativity in H-bond chains. Utilising supramolecular complexes and synthetic molecular torsion balances, direct measurements of energetic cooperativity are presented in an experimental system in which the geometry and number of H-bonds in a chain were systematically controlled. Strikingly, it was found that adding a second H-bond donor to form a chain can almost double the strength of the terminal H-bond, while further extension had very little effect. Computations provide insights into this strong, short-range cooperative effect in a range of H-bonding contexts. Chapters three and four build on the concepts and molecular models discussed in chapter two. Chapter three discusses the effects of interplay and competition between strong H-bond acceptors such as formyl groups and the weaker organofluorine H-bond acceptor. There has been some debate in recent literature about the latter’s ability to accept H-bonds, the work presented shows that although organofluorine is a weak H-bond acceptor, it can have a significant modulating effect on stronger interactions when in direct competition. Chapter four investigates deuterium isotope effects on conformational equilibria governed by non-covalent interactions. The results show that any deuterium isotope effect which exists is less than the margins of experimental error. Finally, chapter five discusses a molecular torsion balance designed to investigate halogen∙∙∙arene interactions. The interaction energies were investigated in a range of solvents and mixtures in order to dissect out the dispersive and solvophobic components of folding. Overall, these interactions were found to be weak. Nonetheless, a model was used to dissect trends in solvophobic and electronic contributions to the binding using multiple linear regression based upon the cohesive energy density and polarisabilities of the solvents.

O tratamento ortodôntico em adultos, nos últimos tempos, tem ganhado popularidade na tentativa de melhorar a estética e a função. No entanto, é uma característica comum nestes pacientes, ter os dentes restaurados com facetas de resina, coroas metalo-cerâmicas e/ou porcelana pura. Neste contexto, o ortodontista se defronta com o desafio de colar braquetes em diferentes sistemas cerâmicos, de capacidade desconhecida de resistir às forças de cisalhamento. Portanto, os objetivos deste trabalho foram: 1) Verificar se a força de cisalhamento em braquetes colados em superfícies de porcelana feldspática e AllCeram é afetada por diferentes tempos de ataque com ácido hidrofluorídrico e 2) Observar se existe uma relação direta entre os valores obtidos da força de cisalhamento e o índice remanescente de adesivo (IRA). Sessenta espécimes de porcelana em formato cilíndrico foram aleatoriamente divididos em 3 grupos de 20 espécimes de acordo com o tempo de ataque do ácido hidrofluorídrico de 1 minuto, 30 segundos e 15 segundos (grupos 1, 2 e 3 respectivamente). Outros sessenta espécimes de porcelana AllCeram, com o mesmo formato e divididos da mesma maneira de acordo com o tempo de ataque ácido (grupos 4, 5 e 6 respectivamente). A colagem dos braquetes na superfície cerâmica incluiu aplicação de silano, colocação de resina fotoativada sobre a base do braquete e cimentação com força padronizada de 500g. Vinte e quatro horas após a cimentação, os espécimes foram submersos em água destilada a 37OC e submetidos ao teste de resistência ao cisalhamento em uma máquina de ensaio universal, com velocidade de 0,5 mm/min, cujos valores registrados em Kgf e convertidos em MPa. O tipo de falha também foi egistrado usando o IRA através de um estereoscópio com magnificação de 4x. A força de cisalhamento mais alta foi registrada no grupo 1 (21.21 MPa), que foi significativamente diferente dos grupos 2, 3, 4, 5 e 6 (11.01, 10.64, 14.31, 10.59, 10.39 MPa, respectivamente). Os valores mais baixos encontrados nos grupos remanescentes não diferiram entre si. A mediana dos escores do IRA para os grupos 1, 2, 3, 4, 5 e 6 foi 2, 3, 3, 0, 3, e 3, respectivamente. O grupo 1 (porcelana feldspática 1 minuto) foi afetado pelos diferentes tempos de ataque com ácido hidrofluorídrico, quando comparado aos grupos 2 e 3, ao passo em que os grupos 4, 5 e 6 de porcelana AllCeram não foram. Não houve relação direta entre o escore do IRA e os valores da força de cisalhamento. / Orthodontic treatment in the adult population has lately gained popularity in an attempt to improve esthetic and function. It is, however, a common feature in these patients, that their dentition is restored by resin veneers, porcelain fused to metal and all ceramic crowns. In this context, the orthodontist faces the challenge of bonding brackets to different porcelain based materials, of unknown ability to resist shear forces. Thus, the aim of this investigation was: 1) to test the null hypothesis that shear strength of brackets bonded to feldspathic and AllCeram porcelain surfaces is not affected by different hydrofluoridric etching times and 2) to test the null hypothesis that there is no direct relation between shear strength values and the adhesive remanescent index (ARI). Sixty feldspathic porcelain disc shaped specimens were randomly divided into 3 groups of 20 each, according to hydrofluoridric acid etching time of either 15, 30 seconds and 1 minute (groups 1, 2 and 3, respectively). Another 60 AllCeram specimens of the same shape were subjected to the same division, according to etching time (groups 4, 5, and 6 respectively). Bonding the brackets to the porcelain surfaces included silane coating, an overlying photoactivated resin and a standardized 500g cementation force. Twenty-four hours after cementation, at 37oC in destilled water, specimens were subjected to a shear force in a universal testing machine at a cross-head speed of 0,5mm/min and shear values registered in Kgf and then converted to MPa. Type of failure was lso recorded using ARI by means of a stereoscope at 4x augmentation. The highest shear strength was found for group 1 (21.21 MPa), which was significantly different than groups 2, 3, 4, 5, and 6 (11.01, 10.64, 14.31, 10.59, 10.39 MPa). The lower values found in the remaining groups were not different among each other. Median ARI scores for groups 1, 2, 3, 4, 5, and 6 were 2, 3, 3, 0, 3, and 3, respectively. The first hypothesis must be partially rejected since only feldspathic porcelain group 1 was affected by different hydrofluoric etching times, when compared to groups 2 and 3, while AllCeram groups 4, 5, and 6 were not. On the other hand, the second null hypothesis must be accepted since no direct relation between ARI score and shear strength values could be determined.

Elastômeros termoplásticos têm sido largamente empregados como adesivos hot melt em diferentes setores da indústria. Neste trabalho foram estudados dois copolímeros em bloco de poliuretano na forma particulada, base poliéster (TPU1) e policaprolactona (TPU2), com o objetivo de avaliar o desempenho dos mesmos como adesivos particulados. Foram preparadas diferentes composições dos TPUs com aditivos de policarbodiimida (A), resina hidrocarbônica (B) e poliisocianato (C). Os TPUs aditivados em diferentes composições foram avaliados por termogravimetria (TGA) e calorimetria diferencial de varredura (DSC) e quanto à resistência da colagem. A cinética de cristalização dos TPUs particulados puros e aditivados em diferentes isotermas foi acompanhada por DSC. Os adesivos TPU1 apresentaram velocidade de cristalização mais lenta, com exceção do TPU1 contendo os aditivos A e B (TPU1AB). Os adesivos TPU2 apresentaram taxa de cristalização maior somente quando aditivado com mistura de aditivos (TPU2AB; TPU2BC; TPU2ABC; TPU2AC). O expoente de Avrami (n) foi inferior para os TPUs aditivados, o que sugere a ocorrência de alteração no tipo de nucleação e geometria de crescimento dos cristalitos. Os TPU1 (poliéster) e TPU2 (policaprolactona) apresentaram perfil de degradação térmica diferenciados devido a diferenças na estrutura química dos mesmos. Os adesivos TPU2 apresentaram valores de resistência mecânica mais elevados que os TPU1, em colagens de substratos de PVC. Os adesivos com maiores valores de resistência (TPU1A e TPU2A) foram extrusados e micronizados para uso como tal. O adesivo TPU1A micronizado apresentou aumento da resistência mecânica. As colagens com os adesivos TPU1 e TPU2 apresentaram falha coesiva e as composições TPU1B e TPU2AC demonstraram falha coesiva e adesiva em ensaio de tração. O processamento dos adesivos TPU1 por tratamento de plasma favoreceu um incremento dos valores de resistência de colagens em substratos de PVC. / Thermoplastic elastomers have widely been used as hot melt adhesives in different industry sectors. In this paper were studied two polyurethane block copolymers in particulate form, based polyester (TPU1) and polycaprolactone (TPU2), in order to evaluate their performance as adhesives. Different compositions of TPUs were prepared with polycarbodiimide (A), hydrocarbon resin (B) and polyisocyanate (C) additives. The TPUs with additives in different compositions were evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and by the bond strength. The kinetics crystallization of pure and additivated TPUs at different isotherms were followed by DSC. The TPU1 adhesives showed lower crystallization rate, except the TPU1 with both A and B additives (TPU1AB). The TPU2 adhesives showed higher crystallization rate only when formulated with mixture of additives (TPU2AB; TPU2BC; TPU2ABC; TPU2AC). The Avrami exponent (n) was lower for the TPUs containing additives, which suggests changes in the nucleation type and crystallites growth geometry. The thermal degradation profile of both TPU1 (polyester) and TPU2 (polycaprolactone) adhesives were quite different due to chemical differences. The TPU2 adhesives showed higher strength values than TPU1s on PVC substrates. The adhesives with higher bond strength (TPU1A and TPU2A) were extruded and micronized, and the TPU1A adhesive showed improved bonding property. The TPU1 and TPU2 adhesives on PVC collages showed cohesive failure and the TPU1B and TPU2AC compositions showed cohesive and adhesive failure under tension test. The adhesive plasma treatment promoted a bonding increasing of TPU1 on PVC substrates.

Yau, Chung Wah. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 55-57). / Abstracts in English and Chinese. / Acknowledgement --- p.i / Abstract --- p.ii / Table of Contents --- p.iv / Index of Compounds --- p.v / Chapter 1. --- Introduction / Chapter 1.1 --- Fundamentals of inclusion chemistry --- p.1 / Chapter 1.2 --- Hydrogen bonding in supramolecular chemistry and crystal engineering --- p.3 / Chapter 1.3 --- Hydrogen-bonded rosette system --- p.4 / Chapter 1.4 --- Research plan --- p.7 / Chapter 2. --- Descriptions of crystal structures / Chapter 2.1 --- Supramolecular rosette layer and rosette ribbon constructed from guanidinium cations and hydrogen carbonate dimers /carbonate anions / Chapter 2.1.1 --- (Et4N+)[C(NH2)3+]7(C032-)3[C3N2H2(C00-)2] (1) --- p.11 / Chapter 2.1.2 --- [(n-Bu)4N+]3[C(NH2)3+]4(HC03-)4[H+{C3N2H-(C00-)(C00H)}2] (2) --- p.14 / Chapter 2.1.3 --- [(n-Bu)4N+]2[C(NH2)3+]2(HC03-)2[NCC6H4(C00-)]2 ´Ø 2H20 (3)…… --- p.16 / Chapter 2.1.4 --- "[(n-Bu)4+]8[C(NH2)3+]8(HCO3-)8[4,4'-C12H8(C00-)2]4 ´Ø 8H20 ´″…" --- p.17 / Chapter 2.2 --- Channel- and layer-type anionic host structures constructed from benzene hexacarboxylic acid and guanidinium cation / Chapter 2.2.1 --- [C6(COO-)6][C(NH2)3]6 ´Ø H20 (5) --- p.20 / Chapter 2.2.2 --- [C6(COOH)3(COO´ؤ)3][C(NH2)3+]3 ´Ø 2H20 (6) --- p.23 / Chapter 2.2.3 --- [(n-Pr)4N+][C6(COOH)5(COO-)] ´Ø 3H20 (7) --- p.27 / Chapter 2.2.4 --- [(n-Bu)4N+]4[C6(COOH)5(COO-)]2[C6(COOH)4(COO-)2]2 [C(NH2)3+]2.8H2O(8) --- p.30 / Chapter 2.2.5 --- (Et4N+)2[C6(COOH)4(COO-)2]2[C(NH2)3+]2 ´Ø 2H20 (9) --- p.35 / Chapter 2.2.6 --- (Me4N+)[C6(COOH)3(COO-)3][C(NH2)3+]2 ´Ø H20 (10) --- p.37 / Chapter 3. --- Summary and discussion / Chapter 3.1 --- Robustness of hydrogen-bonded supramolecular rosette networks --- p.40 / Chapter 3.2 --- Versatile hydrogen bonding modes of guanidinium with mellitate anions --- p.43 / Chapter 4. --- Experimental / Chapter 4.1 --- Preparation methods --- p.48 / Chapter 4.2 --- X-ray crystallography --- p.52 / Chapter 5. --- References --- p.55 / "Appendix A: Tables of atomic coordinates, thermal parameters, bond lengths and angles and hydrogen bonds" --- p.58

The vibrational frequencies of atom to atom bonds within a molecule are a function of the bond energies. Each bond has its characteristic frequency, and most of these frequencies can be detected with the infrared spectrophotometer. When one compound reacts with another or is adsorbed on the surface of a solid, detectable frequency changes or shifts may occur. These changes or shifts yield valuable information about the bonds which are formed or broken.

Organizations have traditionally accomplished connectivity among their workers by co-locating them in shared organizational workplaces. However, information and communication technologies (ICTs) are offering alternative ways to accomplish this kind of connection. This change raises important questions about what it is possible to accomplish through such mediated communicative connections, and if there are work activities that are best accomplished face-to-face. Practitioners and researchers have historically identified informal communication as a process essential to organizational success that is difficult or impossible to accomplish outside of shared physical environments. This study documents the ways full-time teleworkers are accomplishing informal communication without being in shared work environments. In doing this, this work also identifies for what purposes these participants find shared organizational workplaces important and/or essential for successful informal communication. To complete this study required that two additional questions needed to be addressed: 1) defining full-time telework in the context of modern ICT-mediated corporate work environments, and 2) a re-examination of the parameters of telework to define them for modern workplace environments, so as be able to use effectively to examine past and present telework research efforts. In order to document the context of each of the participants as fully as possible, a narrative case study based research protocol was used. Participants were engaged through two active interviews and a journaling exercise so as to identify and document instances of informal communication and their purposes or roles in their workdays. This study’s key finding is that among this group of full-time teleworkers, all were engaging in informal communication to accomplish bonding and learning, both in ways that paralleled those communicative practices commonly accomplished in shared environments, but also in new ways that were made possible because of emergent sociomaterial practices supported by new information and communication technology affordances. While all the study’s participants indicated that their work processes, including informal communication, could be entirely accomplished virtually, nearly all noted the importance of face-to-face communication for key aspects of bonding and learning. Additionally, the successful work practices of these teleworkers were strongly dependent on the ubiquitous adoption of ICT tools and platforms throughout these participants’ organizations, and by the distribution and mobility of increasing numbers of workers, in these organizations and others, that are using these technologies as a routine part of their daily work practices.

Objective: Carious and eroded dentin represent common modified dental substrates, which mostly require restorative procedures. MDP-based dentin bonding system (DBS) and digluconate chlorhexidine (CHX) are presented as promising agents to minimize intrinsic degradation of the resin-dentin interface by interaction with calcium (Ca). Therefore, the purpose of this study was to explore the possible interaction between MDP in a universal adhesive system with 10-MDP in self-etching mode and CHX on substrates artificially modified by caries and erosion, through microtensile bond strength (TBS). Additional characterization of the adhesive interface was performed by SEM/EDS analyses. Material and methods: Flat dentin surfaces were obtained from 120 specimens (n=20/group) prepared from extracted sound human third molars and randomly divided into three groups according to the dentin substrate: sound-control (S), artificial carious (C) and artificial eroded (E). Half of these specimens were pretreated with distilled water (W) and other half with 2% CHX, constituting 6 groups: SW, S-CHX, C-W, C-CHX, E-W, E-CHX. After, all the specimens were restored with a universal adhesive system (Apder Single Bond Universal) using self-etching mode and two increments of composite resin (Filtek Z-350), following manufacturers instructions. Slices (0.8mm) were obtained to SEM analysis and beams (0.64mm²) were obtained and evaluated by EDS analysis and TBS in universal testing machine (500N/ 0.5mm/min) after 24 hours and 6 months. Data was statistically analyzed by two-way ANOVA and Tukey tests (p<0.05). Results: Substrate type was a statistically significant factor (p<0.0001), whereas the pretreatment (p=0.189), time (p=0.337) and the interaction between three factors (p=0.452) were not significant. Conclusion: Carious and eroded dentin substrates negatively interfered on the bond strength of an MDP- based universal adhesive systems, regardless its use with CHX. Likely, the reduction of available calcium from these substrates impaired the effectiveness of this system. / Objetivo: Substratos dentinários cariados e erodidos representam os substratos modificados mais comuns na prática clínica. Sistemas adesivos baseados em MDP e CHX são apresentados como promissores agentes para minimizar a degradação intrínseca da interface resina-dentina devido a suas interações com cálcio. O objetivo deste estudo foi explorar a possível interação entre MDP em um sistema adesivo universal com 10-MDP em modo autocondicionante e CHX em substratos artificialmente modificados por cárie e erosão através da resistência de união (TBS). Caracterizações adicionais das interfaces adesivas foram realizadas por análise em MEV/EDS. Material e métodos: Cento e vinte terceiros molares hígidos foram preparados e randomizados em três grupos de avaliação de acordo com a condição dentinária (n=20/grupo): hígida (controle), cariada e erodida. Metade dos espécimes foram tratados com água (controle) e a outra metade com solução aquosa de CHX a 2%. Todos os espécimes foram restaurados com sistema adesivo Adper Single Bond Universal no modo autocondicionante e resina composta Filtek Z250, seguindo as instruções do fabricante. Fatias (0,8mm) foram obtidas paras as análises em MEV e, na sequência, palitos (0,64mm²) para as avaliações de EDS e TBS em máquina de ensaios universal (500N/0,5mm/min) depois de 24 horas e 6 meses. Os dados foram submetidos à análise estatística (ANOVA e teste Tukey (p<0,05). Resultados: O tipo de substrato foi o único fator estatisticamente significante (p<0,0001), enquanto o pré-tratamento (p=0,189), tempo (p=0,337) e a interação entre os três fatores (p=0,452) não foram significantes. Conclusão: Substratos dentinários cariados e erodidos interferem negativamente na resistência de união de sistemas adesivos universais baseados em MDP, independente do uso de CHX. Provavelmente a redução da disponibilidade de cálcio nesses substratos prejudica a efetividade deste sistema.