O objetivo deste estudo foi avaliar a resistência de união à dentina de primeiros e segundos molares decíduos de sistemas adesivos baseados no condicionamento ácido total e autocondicionantes e analisar a interface de união adesiva sob microscopia eletrônica de varredura. Amostras de dentina de 35 a 65% de distância pulpar (dentina intermediária) foram obtidas do terço médio das faces vestibular e lingual/palatina de 108 molares decíduos, mediante corte com disco diamantado de dupla-face, sob refrigeração. Posteriormente, as superfícies dentinárias foram polidas com lixas de carboneto de silício de granulação 400 e 600. Cinco sistemas adesivos foram empregados nas amostras dos primeiros e segundos molares (n=15/grupo): Adper Single Bond; Prime & Bond NT; AdheSE; Clearfil SE Bond; Adper Prompt L-Pop. Os corpos de prova foram confeccionados com a resina composta Filtek Z250, com uma área de adesão de 2 mm de diâmetro. Após 24 hs de armazenagem em água destilada a 37ºC, fez-se o ensaio de tração a 0,5 mm/min. Na análise da interface de união adesiva entre sistema adesivo e dentina, 50 amostras foram preparadas com os mesmos materiais descritos acima (n=5/grupo). Não foram observadas diferenças estatisticamente significantes entre primeiros (16,02±5,23 MPa) e segundos (16,03±5,05 MPa) molares (ANOVA:p=0,2721). Os valores médios em MPa obtidos para os sistemas adesivos testados foram de 14,32±3,57 (Adper Single Bond), 15,65±3,70 (Prime & Bond NT), 19,47±7,09 (AdheSE), 17,14±5,35 (Clearfil SE Bond) e 14,22±3,20 (Adper Prompt L-Pop). O sistema adesivo AdheSE apresentou o maior valor e diferença estatisticamente significante com os demais grupos (Tukey=3,47), com exceção do Clearfil SE Bond, com o qual não diferiu estatisticamente. Nas demais comparações não foram encontradas diferenças estatísticas significativas. A análise ao microscópio eletrônico de varredura demonstrou a formação de camada híbrida e “tags” em todos os sistemas adesivos e nos dois tipos dentários / The aim of this study was to evaluate bond strength of self-etching and total-etching adhesive systems to dentin of first and second primary molars and to analyze the adhesive interface under scanning electron microscopy. Dentin samples pulp distant 35% to 65% (intermediate dentin) were obtained from buccal and lingual surfaces at the middle third of the crown of 108 primary molars by sectioning with a diamond-impregnated disc under water cooling. Dentin surfaces were polished with 400 and 600-grit silicon carbide paper under running water. Five adhesive systems were tested on the first and second primary molar surfaces (n=15/group): Adper Single Bond; Prime & Bond NT; AdheSE; Clearfil SE Bond; Adper Prompt L-Pop. Inverted, truncated cones of resin composite (Filtek Z250) were built with a 2.0 mm bonding diameter. After 24-hour storage in distilled water at 37°C, the specimens were submited to the tensile test at a crosshead speed of 0.5 mm/min. To analyze adhesive interface 50 samples were prepared with the same protocol described above (n=5/group). No differences between first (16.02±5.23 MPa) and second (16.03±5.05 MPa) primary molars bond strength values could be observed (ANOVA:P=0.2721). Bond strength mean values registered in MPa obtained were 14.32±3.57 (Adper Single Bond), 15.65±3.70 (Prime & Bond NT), 19.47±7.09 (AdheSE), 17.14 ±5.35 (Clearfil SE Bond) and 14.22±3.20 (Adper Prompt L-Pop). AdheSE adhesive system presented the greatest bond strength values statistically different to the other groups (Tukey=3.47), while no statistically significant difference was observed for Clearfil SE Bond. In the other comparisons no differences were found. Scanning electron microscopy analysis showed the presence of hybrid layer and tags in all adhesive systems on both dentin types

Made available in DSpace on 2017-07-10T14:57:31Z (GMT). No. of bitstreams: 1 paulo_ guilherme.pdf: 1519251 bytes, checksum: 15d6c712ac248d997ddd8dbce7c01880 (MD5) Previous issue date: 2016-03-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The adhesion evolution in dentistry, currently, has suggested the nanoparticles addition to the composites in order to improve their mechanical properties. The aim of this study was to compare direct and indirect bracket bonding and to evaluate possible changes due to carbon nanotubes (CN) addition to two adhesives used in indirect bonding by examining the following variables: shear bond strength (SBS), bond failure location and microleakage in the enamel/composite interface. One hundred and eighty bovine incisors underwent 37% phosphoric acid etching and were randomly divided into 9 groups (n=20): (1) direct bonding with Transbond XT adhesive; (2) indirect bonding with Sondhi adhesive; (3), (4) and (5) indirect bonding with Sondhi to which CN at 0.5%, 0.25% and 0.05% concentrations were included; (6) indirect bonding with Concise adhesive; (7), (8) and (9) indirect bonding with Concise to which CN at 0.5%, 0.25% and 0.05% concentrations were included. Transbond XT resin was used in all groups. Maximum SBS was measured with a mechanical testing machine, the location of bond failure was evaluated using the Adhesive Remnant Index (ARI) and the microleakage was measured utilizing scores. One-way analysis of variance followed by the Tukey test (P<.05) was used to compare the SBS among groups, and the differences in ARI and microleakage scores were evaluated using the Kruskal-Wallis test (P<.05). The SBS in group 1 was statistically higher than groups 2 to 6 (P<.05). ARI analysis did not reveal statistically significant differences among the groups (P>.05). In CN groups, there was no statistical difference (P>.05) in SBS or ARI. About the microleakage in the enamel/composite interface, there was a statistically significant difference in group 1 compared to groups 2 and 6, and in group 4 compared to groups 3 and 5 (P<.05). The direct technique was superior to the indirect technique in SBS and microleakage. CN addition to Concise and Sondhi, at the concentrations used, did not significantly increase SBS, ARI or microleakage. / A evolução na área da adesão em Odontologia tem, atualmente, sugerido o acréscimo de nanopartículas ao material adesivo com o propósito de melhorar as suas propriedades mecânicas. Diversos tipos de partículas de carga podem ser adicionados, e entre eles, estão os nanotubos de carbono. A técnica de colagem indireta de bráquetes ortodônticos, na qual os acessórios são posicionados no modelo de gesso da arcada dentária do paciente e, através de uma moldeira, são transferidos aos dentes, parece ser bastante vantajosa, porém, a adesão ainda gera dúvidas com relação à resistência e ao índice de falhas. O objetivo deste trabalho foi comparar as técnicas direta e indireta de colagem de bráquetes, além de avaliar possíveis alterações causadas pela adição de nanotubos de carbono a dois tipos de sistemas adesivos na colagem indireta de bráquetes com relação às seguintes variáveis: resistência de união por microcisalhamento, quantidade de compósito remanescente sobre o esmalte dentário, através do Índice de Remanescente Adesivo (IRA), e microinfiltração ocorrida sob os bráquetes. Para tanto, foram utilizados 180 incisivos bovinos divididos aleatoriamente nos seguintes grupos: G1 (Transbond Controle): colagem direta com adesivo Transbond XT (3M Unitek - Monrovia - EUA); G2 (Sondhi Controle): colagem indireta com adesivo Sondhi Rapid Set (3M Unitek, Monrovia, USA); G3, G4, G5: colagem indireta utilizando o adesivo Sondhi Rapid Set (3M Unitek, Monrovia, USA), com sua porção base acrescida de nanotubos de carbono nas concentrações, respectivamente de 1%, 0,5% e 0,1%; G6: (Concise Controle): colagem indireta com adesivo Concise (3M Unitek - Monrovia - EUA); G7, G8 e G9: colagem indireta utilizando o adesivo Concise (3M Unitek - Monrovia - EUA), com sua porção base acrescida de nanotubos de carbono nas concentrações, respectivamente de 1%, 0,5% e 0,1%. Para a colagem, em todos os grupos foi utilizada a resina composta 10 Transbond (3M Unitek - Monrovia - EUA). Os dados obtidos foram submetidos à análise estatística específica para cada uma das variáveis. Com relação à resistência ao microcisalhamento, observou-se diferença estatisticamente significante do grupo 1 em relação aos grupos 2 e 6 (p<0,05). No que diz respeito ao IRA, não houve diferença estatisticamente significante entre os grupos (p>0,05). Já com relação à microinfiltração ocorrida sob os bráquetes, houve diferença estatisticamente significante do grupo 1 em relação aos grupos 2 e 6, e do grupo 4 em relação aos grupos 3 e 5 (p<0.05). Com base nos resultados obtidos, concluiu-se que a técnica direta mostrou-se superior em relação à técnica indireta nos quesitos de resistência ao microcisalhamento e microinfiltração. Além disto, a adição de nanotubos de carbono aos sistemas adesivos Concise (3M Unitek - Monrovia - EUA) e Sondhi Rapid Set (3M Unitek, Monrovia, USA), não se mostrou vantajosa, nas concentrações avaliadas, no que diz respeito ao aumento da resistência ao microcisalhamento dos bráquetes, na quantidade de compósito remanescente sobre o esmalte dentário e na prevenção da ocorrência de microinfiltração sob os mesmos.

A ligação entre concretos com cimento Portland de diferentes idades, composições e resistências é um dos problemas da tecnologia dos concretos estruturais. A continuidade desta ligação é prejudicada por uma diversidade de fatores que implicam desde a retomada de uma concretagem (junta fria) até a recuperação de estruturas de concreto deterioradas. Sob esse ponto de vista apresenta&#8722;se neste trabalho uma análise do comportamento de um sistema de reparos aplicados à recuperação de estruturas, ligações concretos velhos x concretos novos (caso das ampliações) e continuidades de concretagens. Um dos pontos mais frágeis de uma estrutura é a zona de interface, tanto dos materiais que a compõe quanto da transição entre os diferentes concretos. Utilizou&#8722;se como substrato corpos&#8722;de&#8722;prova prismáticos executados com concretos (fck=15MPa, 18MPa, 21MPa, 25MPa, 30MPa, 40MPa e 50MPa), que após ruptura completa através de ensaios de tração na flexão foi posteriormente executada ligação com concretos de reparo, e corpos&#8722;de&#8722;prova cilíndricos de concretos convencionais apresentando ninhos de concretagem. Com a finalidade de melhorar a zona de transição citada, utilizou&#8722;se como sistema de reparo, concretos de elevado desempenho executados com cimento Portland CP V ARI RS &#8722; NBR 5733&#8260;NBR 5737 &#8722; ABNT, agregados: miúdo de origem quartzosa, e graúdo de Dmáx &#8804; 6,3 mm de origem basáltica, adições de sílica ativa (Fe&#8722;Si) de 5%, 10% e 15% e aditivo superplastificante de pega normal em teores de 1,5%, 1,8% e 2,0%, após prévio tratamento, através de desbaste superficial e imprimação com pastas de cimento de elevado desempenho. A eficácia da ligação é percebida principalmente pelo fato de que em resultados de ensaios de tração na flexão do corpo&#8722;de&#8722;prova prismático recuperado a ruptura ocorreu, em quase 100% dos casos na região do concreto velho. Em ensaios de compressão axial com corpos&#8722;de&#8722;prova cilíndricos com ninhos de concretagem recuperados, percebeu&#8722;se através do modo de ruptura, que as transferências de tensões ocorreram normalmente através do sistema de reparo, sem que houvesse desvio de tensões, além de um acréscimo de resistência em alguns casos. / The bonding among Portland cement concrete of different ages, compositions and resistances is one of the technological problems of structural concretes. The continuity of this connection is harmed by a several factors from the re&#8722;starting of a casting (cold joint) to the recovery of deteriorated concrete structures. From this point of view this paper presents an analysis of the behavior of a repair system applied to the recovery of structures, new&#8722;to&#8722;old concrete bonding (amplification cases) and casting continuities. One of the most fragile points of a concrete structure is the interface zone, of both materials that compose it and the transition among the different concretes. Prismatic specimens executed with concretes (fck=15MPa, 18MPa, 21MPa, 25 MPa, 30 MPa, 40 MPa and 50 MPa), were used as substratum after a previous complete rupture through a flexural strength test for a further connection, with repair concrete as a bond link, and cylindrical specimens of conventional concretes presenting intentionally \"holes\". High&#8722;performance concretes with Portland cement CP V ARI RS (NBR 5733&#8260;NBR 5737 &#8722; ABNT), small quartz aggregates, basaltic coarse aggregates with Dmáx &#8804; 6,3mm, silica fume (Fe&#8722;Si) additions of 5%, 10% and 15%, and normal setting superplasticizer with contents of 1,5%, 1,8% and 2,0% were used as repair system to improve the transition zone mentioned. Such materials were used after the specimens had been treated superficially and primed with High&#8722;performance Portland cement paste. The effectiveness of the connection is noticed mainly by the fact that in results of the flexural strength test of recovered prismatic specimens, the rupture occurred in almost 100% of the cases in the area of the old concrete. In axial compression tests with cylindrical specimens presenting recovered \"holes\", the rupture way demonstrated that the transfers of tensions usually occurred through the repair system, with no tension deviation, and there was a resistance increase in some cases.

Este estudo in vitro avaliou o efeito da adição de rodamina B dissolvida em etanol nas concentrações de 0,02mg/mL e 0,10mg/mL, nas propriedades mecânicas dos sistemas adesivos não simplificados considerados padrão-ouro. 96 coroas de terceiros molares humanos hígidos foram seccionadas transversalmente no terço oclusal para remoção do esmalte e exposição da dentina. Os espécimes foram divididos de acordo com os sistemas adesivos Adper Scotchbond Multi-Purpose (MP) - convencional de três passos ou Clearfil SE Bond (SE) - autocondicionante de dois passos: MP-C e SE-C (MP e SE controles); MP-C1 e SE-C1 (MP e SE com rodamina B 0,02mg/mL); MP-C2 e SE-C2: (MP e SE com rodamina B 0,10mg/mL). Para o teste de RU, os espécimes (n=10) foram submetidos ao desgaste com lixas de granulação 320 e 600. A dentina foi tratada de acordo com as instruções de cada fabricante dos sistemas adesivos e restaurada com resina composta FiltekTM Z250. Após o armazenamento em saliva artificial (7dias/37oC), os espécimes foram seccionados para obtenção de palitos com 0,64 mm2 de área média e submetidos ao teste de microtração em máquina de teste universal a 0,5 mm/min, que foram analisados após 7 dias e 6 meses. O modo de fratura dos espécimes foi analisado com estereomicroscópio digital (x200) e classificado em: adesiva, coesiva em dentina, coesiva em resina e mista. Para o teste de MS, as coroas seccionadas (n=6) foram planificadas com lixa de granulação 600. A dentina foi tratada de acordo com as instruções de cada fabricante dos sistemas adesivos e os espécimes foram mantidos secos em estufa a 37oC durante 48 horas. O teste de MS foi realizado utilizando ponta Knoop (Microdurômetro Shimadzu HMV-2), a 10x e carga estática de 25gF por 10 segundos. Os resultados obtidos foram analisados por análise de variância (ANOVA-2 critérios) e teste de Bonferroni para comparações múltiplas (p<0,05). A análise de acordo com o tempo foi realizada com o teste de t-student. Os valores médios de RU e desvio padrão (MPa±dp; 7 dias / 6 meses) foram: MP-C (41,95±2,38 / 22,76±3,66); MP-C1 (28,02±5,12 / 17,93±5,70); MP-C2 (26,28±5,55 / 14,30±5,68); SE-C (46,07±1,43 / 19,07±6,75); SE-C1 (37,49±13,31 / 18,54±6,71); SE-C2 (34,16±7,71 / 17,89±4,87). No tempo de 7 dias, os fatores sistema adesivo e concentração de rodamina B foram significantes. Após 6 meses, apenas o fator concentração de rodamina B foi significante. A falha de fratura predominante em todos os grupos foi adesiva. Os valores de MS (KHN) e desvio padrão foram: MP-C (8,97±3,85); MP-C1 (7,33±0,99); MP-C2 (7,17±2,45); SE-C (4,71±4,42); SE-C1 (4,42±0,56); SE-C2 (3,27±0,30). Na comparação entre os sistemas adesivos, eles diferiram entre si na condição controle e de 0,10mg/mL. Para cada adesivo, não houve diferença entre as distintas condições de acordo com a adição de rodamina B. Em função dos resultados apresentados, a adição de rodamina B nos sistemas adesivos não simplificados MP e SE, nas concentrações de 0,02mg/mL e 0,10mg/mL, deve ser incorporada com cautela para que não influencie nas propriedades mecânicas do material. / This in vitro study evaluated the effect of addition of rhodamine B dissolved in ethanol in concentrations of 0.02mg/mL and 0.10mg/mL, the mechanical properties of non-simplified adhesive systems. 96 crowns of human third molars were transversely sectioned on the oclusal third to remove the enamel and exposure the dentin. The specimens were divided according to the adhesive systems Adper Scotchbond Multi-Purpose (MP) 3-step-etch-andrinse or Clearfil SE Bond (SE) 2-step-self-ecthing: MP-C and SE-C (MP and SE controls); MP-C1 and SE-C1 (MP and SE with 0.02mg/mL rhodamine B); MP-C2 and SE-C2: (MP and SE with 0.10mg/mL rhodamine B). For the &#x3BC;TBS test, the specimens (n=10) were ground with 320- to 600-grit silicon carbide paper. The dentin was treated according to the instructions of each manufacturer and restored with composite resin FiltekTM Z250. The specimens were stored in artificial saliva (7 days/37oC), and then sectioned to obtain sticks with an average of 0.64 mm2 area and submitted to &#x3BC;TBS test at a universal testing machine at 0.5 mm/min, which were analyzed immediately after 7 days and 6 months. The mode of fracture of the specimens was analyzed with digital stereomicroscope (x200) and classified as: adhesive, cohesive in dentine, cohesive in resin and mixed. For the SM test, the sectioned crowns (n=6) were flattened with 600-grit silicon carbide paper. The dentin was treated according to the manufacturers instructions for each adhesive system and the specimens were stored in dry condition at 37oC during 48 hours. The SM test was performed with Knoop indenter (Shimadzu HMV-2 hardness tester), at 10x and 25gF of load for 10 seconds. The results were analyzed by two-way analysis of variance tests and the Bonferroni test for multiple comparisons (p<0.05). The analysis regarding time was checked with t-student test. The mean &#x3BC;TBS and standard deviation (MPa±dp; 7 days / 6 months) were: MP-C (41.95±2.38 / 22.76±3.66); MP-C1 (28.02±5.12 / 17.93±5.70); MP-C2 (26.28±5.55 / 14.30±5.68); SE-C (46.07±1.43 / 19.07±6.75); SE-C1 (37.49±13.31 / 18.54±6.71); SE-C2 (34.16±7.71 / 17.89±4.87). In the immediate time, the adhesive system and rhodamine B concentration factors were significant. After 6 months, only the rhodamine B concentration was a significant factor. The predominant failure in all groups was adhesive. The values of SM and standard deviation were: MP-C (8.97±3.85); MP-C1 (7.33±0.99); MP-C2 (7.17±2.45); SE-C (4.71±4.42); SE-C1 (4.42±0.56); SE-C2 (3.27±0.30). In the comparison between the adhesive systems, they were significantly different for the conditions control and 0.10mg/mL. For each adhesive systems, there was no difference between the different conditions according to the addition of rhodamine B. Regarding the shown results, addition of rodhamine B in non-simplified adhesives MP and SE, in the concentrations of 0.02mg/mL e 0.10mg/mL must be carefully added to avoid implications to the mechanical properties of the materials.

Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2016-08-04T14:39:04Z No. of bitstreams: 1 João Pedro Gonçalves Trevizan_.pdf: 2398963 bytes, checksum: 7bbf859367acdb155c3b917d8275c41d (MD5) / Made available in DSpace on 2016-08-04T14:39:04Z (GMT). No. of bitstreams: 1 João Pedro Gonçalves Trevizan_.pdf: 2398963 bytes, checksum: 7bbf859367acdb155c3b917d8275c41d (MD5) Previous issue date: 2016-06-15 / itt Chip - Instituto Tecnológico de Semicondutores da Unisinos / PADIS - Programa Federal de Apoio a Indústria de Semicondutores / Este estudo avalia uma proposta de substituição de fio de ouro por fio de cobre no processo de wire bonding em memórias DRAM DDR3 encapsuladas no Brasil. A viabilidade técnica da aplicação desta tecnologia para este componente foi testada na prática em uma empresa coreana, com a produção de amostras e verificação das características de qualidade das mesmas. Após otimização de parametros da primeira solda por DOE, foi possível obter resultados dentro das especificações do processo e semelhantes aos obtidos com o fio de ouro. Após a confirmação da viabilidade técnica, foi verificado a viabilidade econômica deste projeto, calculando o custo de implementação e estimando o tempo para retorno do investimento através dos métodos de payback simples e descontado. Devido à necessidade de aquisição de máquinas soldadoras de custo elevado, o payback descontado resultou em seis anos e onze meses, o que representa um risco alto considerando o dinamismo do mercado de semicondutores e a eminente substituição do encapsulamento BOC pela tecnologia de flip chip / This study evaluates the proposal of gold wire for copper wire replacement in the wire bonding process used in DRAM DDR3 memory packaging in Brazil. The technical feasibility of applying this technology to the component has been verifyed in practice on a Korean company, with the production of samples and the examination of quality characteristics, such as bond pull force and bond shear strenght, intermetallic compound and bonding pad structure. After parameters optimization of the first bond by DOE, it was possible to obtain results within process specifications and similar to those obtained with the gold wire. After confirming the technical feasibility, the economic viability of this project was verified by calculating the cost of implementation and the necessary time to recover the investment, through the simple and discounted payback methods. Because of the need of purchasing costly wire bonding machines, the discounted payback resulted in six years and eleven months, which represents a high risk investment, considering the semiconductor market dynamism and the imminent replacement of BOC package by flip chip technology.

Com os sistemas adesivos autocondicionantes, o uso prévio do ácido fosfórico passou a ser dispensado em dentina. Assim, outras soluções foram propostas a fim de se promover uma limpeza da cavidade e otimizar um melhor embricamento do adesivo ao substrato. O objetivo deste estudo foi avaliar a influência de soluções químicas à adesão à dentina bovina, por meio da resistência ao microcisalhamento, de três sistemas adesivos autocondicionantes em função do tempo. Duzentos e quarenta incisivos bovinos foram incluídos, desgastados e polidos em série com lixas de carbeto de silício, obtendo uma superfície planificada de dentina de 10 mm de diâmetro. Os espécimes foram divididos aleatoriamente em 4 grupos, de acordo com a solução aplicada: SF- aplicação de soro fisiológico com 0,9% NaCl (grupo controle); HS- desproteinização com hipoclorito de sódio a 5%, por 2 minuto e HSAA- hipoclorito de sódio a 5%, por 2 minuto seguida da aplicação de ácido ascórbico (ascorbato) a 10%, por 1 minuto; CHX- aplicação de solução clorexidina a (2% por 1 minuto). Às superfícies preparadas foram aplicados três sistemas adesivos autocondicionantes, por grupo - Optibond All-in-One (KERR), Filtek P90-System Adhesive (3M-ESPE) e Adper SE (3M-ESPE), todas seguidas da inserção de resina composta (Filtek Z250 ou Filtek P90). Metade dos espécimes de cada grupo foram armazenados por 24 horas e metade por 6 meses. Após esses períodos, os espécimes foram submetidos ao teste de microcisalhamento, em uma máquina de ensaios universal (Emic, na velocidade de 0,5mm/min). Os dados foram avaliados estatisticamente através de análise de variância (ANOVA) a três critérios e testes de comparações múltiplas de Tukey ambos considerando a=0,05. O adesivo Filtek P90-System Adhesive foi o único que manteve a resistência adesiva após o envelhecimento, porém, os dois tratamentos de superfície contendo hipoclorito de sódio influenciaram negativamente. Já com a clorexidina não houve diferença estatisticamente significante comparada ao grupo controle. O adesivo OptiBond All- In-One (Kerr) foi influenciado positivamente pelo hipoclorito de sódio e hipoclorito de sódio mais ascorbato, no tempo de 24 horas. Sendo de iqual resultado com o envelhecimento em solução aquosa. Adper SE (3M-ESPE) sofreu influência dos tratamentos à base de hipoclorito de sódio. O melhor resultado, comparando dois tratamentos com hipoclorito, após o envelhecimento, foi obtido pelo tratamento com o hipoclorito de sódio mais ascorbato sendo estatisticamente idêntico ao grupo controle. Foi concluído que os tratamentos de superficie influenciam na resistência adesiva dos adesivos testados. A clorexidina possibilitou os melhores resultados em quase todos os testes. / With the Self-etching adhesives, acid-etching with phosphoric acid has to be dispensed in dentin. Than, other solutions have been proposed in order to promote the cavity cleaner and improvement in bonding effectiveness. The aim of this study was to investigate the microshear bond strength, with the influence of chemical solutions and time, in three adhesive systems used on bovine dentin. Two hundred and forty bovine incisors were included, and the surface was polished in series with silicon carbide paper, getting flattened dentin surface of 10 mm in diameter. The specimens were randomly divided into four groups, according to the applied solution: SF- saline solution with 0.9% NaCl (control group), HS-deproteinization with sodium hypochlorite at 5%, for 2 minutes and HSAA- sodium hypochlorite 5% for 2 minutes followed by the application of ascorbic acid (ascorbate) and 10% for 1 minute;CHXapplication of chlorhexidine solution (2% for 1 minute). Were applied to surfaces prepared three adhesive systems, per group - Optibond All-in-One (Kerr), Filtek-P90 System Adhesive (3M-ESPE) and Adper SE (3M-ESPE), all followed by the insertion of composite resin ( Filtek Z250 and Filtek P90). Half of the specimens of each group / treatment were stored for 24 hours and half for six months. After these periods were tested using the microshear in a universal testing machine (Emic, the speed of 0.5 mm / min). Results were submitted to three way ANOVA and TUKEY test multiple comparison both considering a = 0.05. The adhesive Filtek P90 System Adhesive was the one who kept the bond strength after aging, however, the two surface treatments containing sodium hypochlorite influenced negatively. With chlorhexidine, there was no statistically significant difference compared to the control group. The adhesive OptiBond All-in-One (Kerr) was affected by the sodium hypochlorite, sodium hypochlorite more ascorbate, at 24 hours. As a result of iqual with aging in aqueous solution. Adper SE (3M-ESPE) was influenced by the treatments using sodium hypochlorite. The best result, comparing two treatments with hypochlorite, after aging, was obtained by treatment with sodium hypochlorite more ascorbate was statistically identical to the control group. It was concluded that the influence of surface treatments on bond strength of adhesives tested. The chlorhexidine resulted in better results in almost every test.

Au cours de ces travaux de thèse, nous avons exploré de nouvelles applications des proazaphosphatranes et de leurs dérivés, en particulier leur confinement dans une cage moléculaire. Dans la première partie, une bibliographie présente la littérature concernant (i) la découverte et les applications de proazaphosphatranes, (ii) les catalyseurs confinés dans des cages covalentes et (iii) la liaison halogène - une interaction non covalente émergente-. Par la suite, l’utilisation de proazaphosphatranes comme organocatalyseur très efficace pour la réaction de Strecker est décrit. Ensuite, un système FLP (paire de Lewis frustrée) comprenant un proazaphosphatrane encagé comme base de Lewis et du TiCl4 comme acide de Lewis a été utilisé pour catalyser la réaction de MBH (Morita-Baylis-Hillman). Finalement, un azaphosphatrane chloré a été synthétisé, et ses propriétés de reconnaissance vis à vis de différents anions halogénures, par liaison halogène, a été étudié. / In this dissertation, our goal is to explore new applications of proazaphosphatranes and their derivatives, especially in a confined space. In the first part, a comprehensive literature review regarding 1) discovery and application of proazaphosphatranes, 2) confined covalent cages based organo- and metal-catalysts, and 3) halogen bonding – an emergent noncovalent interaction has been demonstrated. Subsequently, proazaphosphatrane as highly efficient organocatalyst for the Strecker reaction is discussed. And a FLP (frustrated Lewis pair) system comprising an encaged proazaphosphatrane as Lewis base and TiCl4 as Lewis acid for MBH (Morita–Baylis–Hillman) reaction is reported. In the end, chlorinated azaphosphatrane is synthesized and studied in the recognition of different halide anions by halogen bonding, exhibiting a preferable affinity for chloride over bromide and iodide.

Proton-transfer reactions are one of the most fundamental chemical reactions. However, the chemical dynamics of these processes remain elusive due to the difficulty of modeling these reactions. Establishing an experimental model system and using infrared absorption and two-dimensional infrared (2D IR) spectroscopies as means for detection, the chemical dynamics of the protonation states that are involved in a ground-electronic-state proton-transfer reaction in solution can be determined. In this study, experimental models are established with formic acid and nitrogenous bases in a low dielectric solvent. A hydrogen bond forms between the acid and the base, which will allow for the proton to transfer between the two molecules to form the neutral and the ion-pair protonation states. The carbon-deuterium (C-D) stretch and the carbonyl (C=O) stretch of the formic acid molecule are used as the reporter groups for the 2D IR measurements. The results of the C-D stretch demonstrate that there is a high sensitivity to the deprotonation, vibrational coupling, and vibrational dynamics trends that are linked to the solute-solvent interactions. The results of the C=O stretch demonstrate a sensitivity to the deprotonation and conformational disorder in which the position of the C=O changes the dynamics of the protonation state. Although, a proton-transfer is not detected, the experimental model system provides an understanding of the features that govern the chemical dynamics of proton-transfer reactions.

Current hydrophilic resin adhesives undergo hydrolytic degradation and show a decrease in bond strength over time. Nanoleakage and ultrastructure studies suggest that inadequately infiltrated collagen leads to enzymatic degradation and resin-dentin bond failure. Adequate degree of conversion (DC) of resin adhesives is also critical to resin-dentin bond strength and durability. The long-term goal of this dissertation is the realization of durable resin-dentin bond. It is hypothesized that ethanol-wet bonding technique (EW) may effectively facilitate the infiltration of hydrophobic monomers into hydrophilic acid-etched dentin by maintaining interfibrillar spacing, stiffening collagen matrix, and improving adhesive resin-demineralized dentin matrix miscibility. Chlorhexidine (CHX), Matrix Metalloproteinase-inhibitor (MMP-inhibitor), should further preserve collagen integrity and resin-dentin bond strength. Moreover, efficient photoinitiator systems that broaden light absorptivity and provide more reactive radicals may enhance polymerization. In this dissertation, a clinically-relevant EW protocol, 3×15s absolute ethanol rinsing, provided significantly higher microtensile bond strength (πTBS) of a hydrophobic resin (70%BisGMA/30%TEGDMA) to dentin as compared to water-wet bonding (WW). All groups showed no significant drop of πTBS after 1-year storage except EW without CHX application, showing marginally significant reduction in πTBS (p=0.0558) suggesting MMP-inhibition by CHX in EW. These results were consistent with subsequent experiments. EW maintained interfibrillar width and hybrid layer thickness for resin infiltration and retention. Monomer molar concentration across the hybrid layer was significantly higher in EW than WW. An application of 2% CHX diacetate further preserved collagen banding in EW. WW showed more generalized spotted nanoleakage, while EW presented localized reticular nanoleakage. The use of Irgacure 819 (BAPO) alone and in combination with benzoyl peroxide (BPO) or camphorquinone (CQ) increased DC of hydrophobic and hydrophilic resins over resins containing the CQ/amine (4E) control. Only BAPO and BAPO/BPO demonstrated significantly higher immediate shear bond strength than CQ/4E. Within the limitations of these studies, EW improved resin-dentin bond durability by maintaining collagen interfibrillar spaces for efficient infiltration of a hydrophobic BisGMA/TEGDMA resin resulting in significantly higher πTBS and monomer molar concentrations with less nanoleakage distribution within the hybrid layer than WW. CHX further maintained collagen integrity and πTBS in EW. BAPO is a potential alternative photoinitiator of dental resins.

Adsorption processes are utilized in both medicine and industry. It is important to have an understanding of adsorption processes to better predict the outcomes and discern potential difficulties. The primary objective of this research is to further the understanding of the nature and extent of the adsorption process in solution, which is a function of the chemical composition of the adsorbates, adsorbents, and solvent. This was accomplished by employing experimental studies as well as thermodynamic calculations and molecular dynamic simulations. Four activated carbons were used as the model adsorbents in this study. And, barbital, phenobarbital and primidone were used to elucidate the structural features of the adsorbates that were most responsible for the interaction with activated carbons. A Two-Mechanism Langmuir-Like Equation (TMLLE) was proposed to describe the independent presence of two adsorption mechanisms: non-site-specific adsorption and site-specific adsorption. The analyses of data generated by both previous investigators and current studies, suggest that the TMLLE allows an accurate analysis of the adsorption process. Based on the parameters in the TMLLE, the Modified Crisp Model and the van’t Hoff Model were employed to determine the Gibbs free energy changes for both site-specific adsorption and non-site-specific adsorption. Comparing the Gibbs free energy changes calculated by the Modified Crisp Model and the van’t Hoff Model (site-specific adsorption case), it is concluded that 5 water molecules are displaced by a phenobarbital molecule on the surface of activated carbons. And, for non-site-specific adsorption, it is concluded that 12 water molecules are displaced by a phenobarbital molecule on the nonpolar (hydrocarbon) part of the activated carbon surface. The adsorption of phenobarbital from solution by activated carbons has been simulated by employing Molecular Dynamic (MD) Modeling. The predicted differential Gibbs free energy values for site-specific adsorption at pH 2-9 were consistent with the thermodynamic calculations. And, the present MD simulations provide a good basis for the further understanding and quantitatively assessment of the adsorption driven by hydrophobic bonding. The conclusions reached in the current studies are expected to be applicable to a wide range of similar adsorption processes.