Tesis sobre el tema "Wet adhesive"

Doctor of Philosophy
Department of Grain Science and Industry
X. Susan Sun
The ecological and public health liabilities related with consuming petroleum resources have inspired the development of sustainable and environmental friendly materials. Plant protein, as a byproduct of oil extraction, has been identified as an economical biomaterial source and has previously demonstrated excellent potential for commercial use. Due to the intrinsic structure, protein-based materials are vulnerable to water and present relatively low wet mechanical properties. The purpose of this study focuses on increasing protein surface hydrophobicity through chemical modifications in order to improve wet mechanical strength. However, most of the water sensitive groups (WSG), such as amine, carboxyl, and hydroxyl groups, are also attributed to adhesion. Therefore, the goal of this research is to reduce water sensitive groups to an optimum level that the modified soy protein presents good wet adhesion and wet mechanical strength. In this research, we proposed two major approaches to reduce WSG: 1). By grafting hydrophobic chemicals onto the WSGs on protein surface; 2). By interacting hydrophobic chemicals with the WSGs. For grafting, undecylenic acid (UA), a castor oil derivative with 11-carbon chain with a carboxyl group at one end and naturally hydrophobic, was used. Carboxyl groups from UA reacted with amine groups from protein and converted amines into ester with hydrophobic chains grafting on protein surface. The successful grafting of UA onto soy protein isolate (SPI) was proved by both Infrared spectroscopy (IR) and ninhydrin test. Wood adhesive made from UA modified soy protein had reached the highest wet strength of 3.30 ± 0.24 MPa with fiber pulled out, which was 65% improvement than control soy protein. Grafting fatty acid chain was verified to improve soy protein water resistance. For interaction approach, soy oil with three fatty acid chains was used to modify soy protein. Soy oil was first modified into waterborne polyurethanes (WPU) to improve its compatibility and reactivity with aqueous protein. The main forces between WPU and protein were hydrogen bonding, hydrophobic interactions, and physical entanglement. Our results showed that WPU not only increased protein surface hydrophobicity with its fatty acid chains but also enhanced the three-dimensional network structure in WPU-SPI adhesives. WPU modification had increased wet adhesion strength up to 3.81 ± 0.34 MPa with fiber pulled out compared with 2.01 ± 0.46 MPa of SPI. Based on IR and thermal behavior changes observed by DSC, it was inferred that a new crosslinking network formed between WPU and SPI. To exam if the UA and WPU technologies developed using soy protein are suitable for other plant proteins, we selected camelina protein because camelina oil has superior functional properties for jet fuels and polymers. Like soy protein, camelina protein is also highly water sensitive. However, simply applied UA and WPU to camelina protein following the same methods used for soy proteins, we did not obtain the same good adhesion results compared to what we achieved with soy protein. After protein structure analysis, we realized that camelina protein is more compact in structure compared to soy protein that made it weak in both dry and wet adhesion strength. Therefore, for camelina protein, we unfolded its compact structure with Polymericamine epichlorohydrine (PAE) first to improve flexible chains with more adhesion groups for future reaction with UA or WPU. PAE with charged groups interacted camelina protein through electrostatic interaction and promoted protein unfolding to increase reactivity within protein subunits and between protein and wood cells. Therefore, the wet adhesion strength of camelina protein was improved from zero to 1.30 ± 0.23 MPa, which met the industrial standard for plywood adhesives in terms of adhesion strength. Then the wet adhesion strength of camelina protein was further improved after applying UA and WPU into the PAE modified camelina protein. In addition, we also found PAE unfolding significantly improved the dry adhesion strength of camelina protein from 2.39 ± 0.52 to 5.39 ± 0.50 MPa with 100% wood failure on two-layer wood test. Camelina meal which is even more economical than camelina protein was studied as wood adhesive. Through a combination of PAE and laccase modification method, the wet adhesion strength of camelina meal was improved as high as 1.04 ± 0.19MPa, which also met industrial standards for plywood adhesives. The results of this study had proven successful modification of oilseed protein to increase water resistance and wet mechanical strength. We have gained in-depth understanding of the relationship between protein structure and wet adhesion strength. The successful modification of plant proteins meeting the industrial needs for bio-adhesives will promote the development of eco-friendly and sustainable materials.

Orientador: Luis Roberto Marcondes Martins
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba
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Resumo: Essa tese avaliou um novo protocolo adesivo, que consiste no pré-tratamento dentinário com dimetilsulfóxido (DMSO) 50%, com o intuito de otimizar a durabilidade de interfaces adesivas produzidas pelos mecanismos de união convencional e autocondicionante envolvendo o substrato dentinário. Para isso, foram realizados dois estudos independentes para avaliar: (i) o efeito do uso do dimetilsufóxido (DMSO) na resistência de união imediata e na exposição de matriz colágena decorrente da hibridização dentinária na interface adesiva; e (ii) para avaliar o efeito do protocolo proposto na conversão monomérica na camada híbrida e na resistência de união após envelhecimento. Terceiros molares hígidos foram coletados e limpos, a face oclusal foi seccionada, expondo uma superfície dentinária de profundidade média, que foi saturada com uma solução aquosa de DMSO 50% (pH 8.2) após o condicionamento ácido para o sistema convencional de três passos (Adper Scothbond Multi-Purpose: 3M ESPE: SBMP) e previamente a aplicação do sistema autocondicionante de dois passos (Clearfil SE Bond: Kuraray; CF) no substrato mineralizado. Nos grupos controles, as amostras não foram tratadas com DMSO. Os segmentos restaurados com resina composta foram seccionados e submetidos ao ensaio de microtração após 24 h à 0,5 mm/min até a fratura (n=12) e no segundo estudo (n=10), após 1 ano e 2 anos. Foi realizada Two-way ANOVA para análise dos dados imediatos e no segundo estudo foi utilizada ANOVA medidas repetidas (proc mixed), ambos seguidos pelo Teste de Tukey (?=0.05). Foi realizado a análise histomorfométrica (n=12) para avaliação da extensão de matriz colágena exposta na interface adesiva por meio de microscopia ótica e coloração de Tricrômica de Masson após 24 h. Esses dados foram submetidos a Two-way ANOVA, seguido do Teste de Tukey (?=0.05). O grau de conversão monomérica (DC) na camada híbrida foi avaliado por espectroscopia micro-raman após 24 h (n=10), sendo submetidos a One-way ANOVA e Teste de Tukey (?=0.05). A interação entre protocolo adesivo e sistema adesivo influenciou significativamente a extensão de matriz colágena exposta (p<0,0001) e resistência de união imediata (p=0,0091). O protocolo adesivo com DMSO reduziu significativamente o grau de exposição de matriz colágena exposta (SBMP: 85,3% e CF: 61,5%), melhorando a qualidade da hibridização dentinária para ambos sistemas adesivos. Não houve influência negativa do DMSO na conversão monomérica do SBMP (p=0.892); já para o CF, houve aumento na conversão monomérica (p=0.033). O pré-tratamento com DMSO aumentou a resistência de união imediata do SBMP (p<0.0001). Considerando as amostras não tratadas, houve uma redução significativa (SBMP: 45,6% e CF: 36,8%) na resistência de união do SBMP (p<0.0001) e CF (p<0.0001) após dois anos de envelhecimento. Independentemente do tipo de adesivo, não houve diferença estatística na resistência de união entre valores imediatos e após 2 dois anos quando o DMSO foi empregado (p>0,05). A análise dos padrões de falha evidenciou uma tendência na redução no número de falhas adesivas após dois anos para as amostras tratadas com DMSO. Portanto, o protocolo adesivo proposto utilizando o DMSO é uma abordagem promissora para reduzir degradação da interface adesiva para os adesivos convencional e autocondicionante testados
Abstract: This work highlights a new bonding concept using 50% dimethyl sulfoxide (DMSO) as a dentin pre-treatment to optimize resin-dentin bonding for both etch-and rinse and self-etch adhesive systems after long-term aging. Two independent studies were performed: (i) to evaluate the effect of dimethyl sulfoxide wet-bonding technique on resin infiltration depths at the bonded interface and dentin bond strength; and (ii) to examine the effect of dentin pre-treatment with DMSO on the degree of conversion and dentin bond strength after long-term aging. Flat dentin surfaces derived from extracted sound human third molars were saturated with 50% DMSO (pH 8.2) after acid etching for a water-based etch-and-rinse adhesive system (Adper Scothbond Multi-Purpose: 3M ESPE; SBMP), and before acid primer application for a 10-MDP self-etch adhesive (Clearfil SE Bond: Kuraray; CF). In control groups, specimens were not treated with DMSO. The restored tooth segments were sectioned and submitted to microtensile bond strength test at 24 h (n=12), 1 year (n=10) and 2 years (n=10) at 0.5 mm/min until specimen fracture. One slab per tooth (n=12) was stained by Masson Trichrome and the extent of exposed collagen matrix at the bonded interface was evaluated using optical microscopy and a histomorphometric software at 24 h. Statistical analysis of the extension of collagen exposure was performed by two-way ANOVA followed by Tukey Test (?=0.05). The degree of conversion (DC) was measured inside the hybrid layer by micro-raman spectroscopy (n=10) at 24 h. DC statistical analysis was performed by One-way ANOVA and Tukey Test (?=0.05). Immediate microtesnile data was statistically analyzed Two-way ANOVA and aged data was analyzed by repeated measurres ANOVA (proc mixed). Post hoc multiple comparisons were performed by Tukey Test (?=0.05). The interaction between "dentin pre-treatment" and "adhesive system" significantly influence the extent of exposed collagen matrix (p<0.0001) and dentin bond strength (p=0.0091). The adhesive protocol with DMSO significantly reduced the extent of exposed collagen matrix (SBMP: 85.3% and CF: 61.5%), improving the quality of dentin hybridization for both adhesive systems. There was no negative influence of DMSO in monomer conversion for SBMP (p=0.892); nevertheless, there was an increase in monomer conversion (p=0.033) for CF. Dentin pretreatment with DMSO increased the immediate bond strength of SBMP (p<0.0001). Considering the untreated samples, there was a significant reduction (SBMP: 45.6% and CF: 36.8%) on the bond strength of SBMP (p<0.0001) and CF (p<0.0001) after two years of aging. Regardless of adhesive type, no significant reduction in bond strength at two years for DMSO-treated samples was observed. Fracture pattern analysis showed a tendency toward reduction in the number of adhesive failures when the DMSO-wet bonding was performed. Therefore, DMSO-wet bonding is a promising approach to reduce resin-dentin bond degradation of etch-and-rinse and self-etch adhesives
Doutorado
Dentística
Doutor em Clínica Odontológica

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.

Thesis: S.M., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2016.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 82-87).
In nature, robust interfacial adhesion plays crucial roles in maintaining integration and functionality of various physiological structures including tendon and cartilage to bones and epidermis to dermis in mammalian skins. For instance, the bonding of tendon and cartilage to bone is extremely tough (e.g., interfacial toughness ~800 Jm-2 ), yet such tough interfaces have not been achieved between synthetic hydrogels and various types engineering solids including rigid nonporous solids and elastomers. In this study, we report a strategy to design extremely robust interfacial bonding of synthetic hydrogeis containing 90 % water to various types of rigid engineering solids, precious metals and commonly-used elastomers. The design strategy is to anchor the long-chain polymer networks of tough hydrogels covalently to various solid surfaces, which can be achieved by diverse surface chemical treatments. We discuss the mechanism behind the proposed design strategy to further understand the tough wet adhesion of hydrogels in engineering and biological situations. We also demonstrate multiple novel applications of robust hydrogel-solid hybrids for both rigid engineering solids and elastomers. We discuss details of such new class of applications and their potential usefulness in diverse fields.
by Hyunwoo Yuk.
S.M.

The thesis studies the relationship between inter-fiber forces present within a cellulose fiber web under varying external conditions. It particularly concentrates on the degree of fiber to fiber bonding and fiber entanglement as a function of moisture content. Finite element analysis of the fiber bonding is used in conjunction with the experimental results to analyze and explain the inter-fiber behaviors taking place within a sheet.

This thesis examines polyelectrolyte complex (PEC) preparation, adsorption behaviour, and potential use for control of wet and dry adhesion between surfaces. PEC formation was studied using a jet-mixing method not previously used for mixing polyelectrolytes. The PECs were formed using various mixing times, and the results were compared with those for PECs formed using the conventional polyelectrolyte titration method. The results indicated that using the jet mixer allowed the size of the formed PECs to be controlled, which was not the case with the polyelectrolyte titration method, and a two-step mechanism for PEC formation was suggested. Adsorption experiments comparing two types of PECs, both produced from PAA and PAH, but with different molecular weights, demonstrated that surface-induced aggregation occurred in the high-molecular-weight PECs, whereas the adsorption stopped at a low level in the low-molecular-weight PECs. It was suggested that the latter PECs consisted of two fractions of complexes and that the fraction with lower polymer density exerted a site-blocking effect, hindering further adsorption. It was also demonstrated that particle-PECs (PPECs), in which one polyion was replaced with a silica nanoparticle, could be prepared. The purpose of preparing PPECs was to create a PEC structure that could create a joint with a special failure pattern referred to as disentanglement behaviour. Using the colloidal probe AFM technique, the expected disentanglement could be detected in PPECs, though the joint strength was low. Adhesion experiments demonstrated significantly higher pull-off values with polymer–polymer complexes than with PPECs. However, there was large spread in the data, possibly due to the surface inhomogeneity. Experiments using low-molecular-weight PECs as a paper strength agent demonstrated that PECs can indeed increase paper strength. Comparing the PEC results with those for polyelectrolyte multilayers (PEMs) prepared from the same polyelectrolytes indicated that, since the PEM strategy enables higher adsorption levels than does the PEC strategy, greater absolute strength improvements could be achieved using PEMs. However, PEC treatment resulted in the greatest effect per adsorbed amount of polymer.
Denna avhandling behandlar tillverkning av polyelektrolytkomplex (PEC), deras adsorption och potentiella användning för att öka adhesionen mellan ytor i vått och torrt. PEC bildades med hjälp av jetmixningsmetoden, en metod som inte tidigare använts för PEC‑tillverkning. Resultaten av tillverkningen jämfördes med resultat för PEC bildade genom den tidigare ofta använda polyelektrolyt­titrerings­metoden. Jämförelsen visade att med jetmixningsmetoden kunde storleken på de bildade PECen styras med hjälp av blandningstiden, något som inte var möjligt med polyelektrolyttitreringsmetoden. Utifrån resultaten föreslås en två-stegsmekanism för PEC-bildandet. Adsorptionsexperiment med två typer av PEC, båda tillverkade av PAA och PAH fast med olika molekylvikter, visade att för högmolekylära PEC skedde en ytinducerad aggregation, medan adsorptionen stannade på en låg nivå för de lågmolekylära PECen. De senare PECen antogs bestå av två olika fraktioner, av vilka en fraktion med lägre polymerdensitet föreslogs ha en ytblockerande effekt, och därigenom hindrades vidare adsorption. Det visades också att partikel-PEC (PPEC), där ena polymerkomponenten bytts ut mot anjoniska nanopartiklar av kiseloxid, kunde tillverkas. Syftet var att skapa strukturer som kan åstadkomma ett brottmönster med uttrassling mellan ytor. Med hjälp av kolloidalprobs-AFM (atomkraftsmikroskopi) kunde det önskade uttrasslingsbeteendet påvisas, men fogstyrkan var låg. Adhesionsexperiment med polymer-polymer-PEC visade på högre styrkor än PPECen, men också stor spridning i data, troligen på grund av inhomogenitet i ytornas struktur. Experiment där lågmolekylära PEC använts som styrkekemikalie för papper visade att tillsats av PEC kan öka pappersstyrkan. Jämförelse med resultat för poly­elektrolytmultilager (PEM) av samma komponenter visade att eftersom högre adsorptionsnivåer kan uppnås med PEM så kan större styrkeökningar erhållas med PEM. Däremot visades att den högsta styrkeökningen per adsorberad mängd polymer erhölls med PEC-behandlingen.
QC 20120508

Orientador: Renée Laufer Amorim
Resumo: As alterações na expressão de E-caderina, -catenina, APC e Caveolina-1 nas células epiteliais prostáticas têm sido estudados em humanos como mecanismos relacionados com progressão tumoral, invasão e metástase. Estas proteínas estão envolvidas no processo de adesão celular e ativação da via WNT canônica. No cão, a perda da expressão proteica de E-caderina e a translocação da -catenina da membrana para o citoplasma/núcleo foram descritas anteriormente em lesões prostáticas caninas. No entanto, nenhum estudo correlacionou alterações de expressão dessas proteínas com as proteínas APC e Caveolina-1. Devido ao prognóstico desfavorável do carcinoma prostático (CaP) no cão e a importância da identificação de novos marcadores prognósticos e preditivos, o presente estudo visou avaliar as expressões gênica e proteica de E-caderina, -catenina, APC e Caveolina-1 em diferentes lesões prostáticas caninas, além de avaliar o padrão de metilação do gene APC. Foram utilizados neste estudo 10 CaPs, 4 metástases de carcinoma prostático, 10 amostras de atrofia inflamatória proliferativa (PIA) e 10 próstatas normais de cães para análise imuno-histoquímica. Para a técnica de RT-qPCR forma utilizados 11 próstatas normais, 11 PIA, 17 CaPs e 3 metástases. Para análise de metilacão foram utilizadas seis próstatas normais, seis próstatas com PIA e 12 CaPs. Este estudo revelou aumento de expressão gênica e proteica de Caveolina-1 nas amostras de CaP e metástases, além de menor expressão nas amostras de ca... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Altered expression of E-cadherin, -catenin, APC and Caveolin-1 in prostate epithelial cells has been studied in humans as mechanisms related with tumor progression, invasion and metastasis. These proteins are envolved in cell-cell cohesion and participate in the activation of the canonical WNT pathway. In dogs, membranous E-cadherin loss and translocation of -catenin from the membrane to cytoplasm/nucleus were described previously in canine prostatic lesions. However, studies correlating these genes have not been reported their proteins with APC and Caveolin-1 expressions in canine prostatic lesions. Due to poor prognosis in canine prostate carcinoma (PC) and the need to develop new prognostic and predictive biomarkers, this study aimed to evaluate gene and protein expression of E-cadherin, -catenin, APC and Caveolin-1 in different canine prostatic lesions, and the methylation status of APC gene. We used 10 PC, 4 prostate metastasis, 10 proliferative inflammatory atrophy(PIA) and 10 canine normal prostates tissues for immunohistochemistry. For RT-qPCR we used 11 normal prostate, 11 PIA, 17 PC and 4 metastasis. For methylation analysis, we used six normal prostates, 6 PIA and 13 PC. This study revealed increased Caveolin-1 gene and protein expression in PC and metastasis and lower expression were found in tumors with lower Gleason score. Membranous E-cadherin and - catenin staining was observed in normal prostate samples whereas heterogenous loss was detected in other samples.... (Complete abstract click electronic access below)
Mestre

La gravure chimique par voie humide des matériaux est toujours utilisée dans certaines étapes spécifiques des procédés de fabrication de transistors pour la microélectronique. Cette gravure est effectuée en présence de masques de résine photosensible, qui définissent les zones à protéger de l'attaque chimique. Une des difficultés rencontrées lors de cette étape technologique est la dégradation du masque en résine et de l'interface résine/matériau à graver, qui entraine un endommagement du matériau sous-jacent. L'objectif de cette thèse est d'étudier les dégradations occasionnées lors de la gravure humide par une solution chimique de type SC1 (NH4OH/H2O2/ H2O) de la grille métallique TiN / Al / TiN d'un transistor pMOS pour les nœuds technologiques 28nm et inférieurs. Dans notre étude, l'empilement protégeant la grille métallique est constitué d'une bicouche résine photosensible à 248nm / revêtement antireflectif développable (dit dBARC). Une première partie du travail a consisté à mener une étude phénoménologique des facteurs impactant l'adhésion des polymères sur le TiN, et a mis en évidence la forte influence de l'état de surface du film de TiN avant l'étape de lithographie, et notamment son vieillissement. Une seconde partie a consisté à étudier les différentes solutions permettant une amélioration de la tenue des polymères à la gravure SC1. Il a été montré que si aucun traitement de surface du TiN ne permettait d'améliorer cette adhésion, une augmentation de la température de recuit du dBARC permettait quant à elle d'accroitre le greffage du carbone sur la couche de TiN et donc la tenue à la gravure de tout l'empilement. Enfin, une troisième étude a permis de mettre en évidence l'endommagement de la surface de TiN par diffusion du SC1 dans l'empilement dBARC / résine, et de proposer un mécanisme expliquant ce phénomène. La réalisation d'un dispositif expérimental de mesure, innovant, basé sur la spectroscopie infrarouge en mode de réflexions internes multiples (MIR) a par ailleurs permis de caractériser cette diffusion des espèces chimiques dans l'empilement polymérique et d'étudier les facteurs l'impactant
Materials wet etching is still used in some specific steps of the transistors manufacturing process in microelectronics. This etching is performed in the presence of photoresist masks that define the areas to be protected from the chemical etchants. One of the major problems encountered during this technology step is the degradation of both photoresist patterns and the photoresist / material interface, which leads to the underlying material's damaging. The goal of this thesis is to study these degradations, during the wet etching of the TiN / Al / TiN metal gate of a pMOS transistor using a SC1 chemical solution (NH4OH/H2O2/ H2O), for sub-28 nm technology nodes. In our study, the stack that protects the metal gate is a bilayer with a 248 nm photoresist and a developable anti-reflective coating (or dBARC). The first part of our work was to lead a phenomenology study of the various parameters impacting the polymers adhesion on TiN. It showed the strong influence of the TiN surface state before lithography, especially its ageing. In a second part, we studied various solutions to improve the polymers stack adhesion during the SC1 etching. No TiN surface treatment could enhance this adhesion, but we found that increasing the dBARC bake temperature lead to an increase of carbon grafting on TiN, which thus gave a better resistance of photoresist patterns to SC1 etching. Then in a third part, we highlighted the TiN surface damaging after SC1 diffusion through the resist bilayer and proposed a mechanism explaining this phenomenon. We also developed an innovative experimental device based on infrared spectroscopy in the Multiple Internal Reflections (MIR) mode to characterize the diffusion of chemical etchants in the polymers stack, and study the various parameters that may impact it

Abstract Wnt genes encode secreted signalling molecules that control embryonic development including organogenesis, while dysregulated Wnt signalling is connected to many diseases such as cancer. Specifically, Wnts control a number of cellular processes such as proliferation, adhesion, differentiation and aging. Many Wnt proteins activate the canonical β-catenin signalling pathway that regulates transcription of a still poorly characterized set of target genes. Wnts also transduce their signaling in cells via β-catenin-independent “non-canonical” pathways, which are not well understood. In this study, Wnt-11 signalling mechanisms in a mammalian model cell line and roles of Wnt-11 in heart development were analyzed in detail. In addition the aim was to identify new Wnt target genes by direct chromatin immunoprecipitation and Affymetrix GeneChip assays in the model cells exposed to Wnt-3a. Our studies reveal that Wnt-11 signalling coordinates the activity of key cell signalling pathways, namely the canonical Wnt/β-catenin, the JNK/AP-1, the NF-κB and PI3K/Akt pathways in the CHO cells. Analysis of the Wnt-11-deficient embryos revealed a crucial role in heart organogenesis. Wnt-11 signalling coordinates cell interactions during assembly of the myocardial wall and Wnt-11 localizes the expression of N-cadherin and β-catenin to specific cellular domains in the embryonic ventricular cardiomyocytes. Collectively these studies reveal that the mammalian Wnt-11 behaves as a non-canonical Wnt and that it is a critical factor in the coordination of heart development. Specifically, it controls components of the cell adhesion machinery. Analysis of the Wnt target genes revealed a highly context-dependent profile in the Wnt-regulated genes. Several new putative target genes were discovered. Out of the candidate Wnt target genes, Disabled-2 was identified as a potential new direct target for Wnt signalling.

La pharmacovigilance souffre d’une sous notification chronique des effets indésirables de la part des professionnels de santé. La FDA (US Food and Drug Administration), l’EMA (European Medicines Agency), et d’autres agences sanitaires, suggèrent que les réseaux sociaux pourraient constituer une source de données supplémentaire pour la détection de signaux faibles de pharmacovigilance. L’OMS (Organisation Mondiale de la Santé) a publié un rapport en 2003 exposant le problème que pose la non-observance au traitement sur le long terme et son caractère préjudiciable à l’efficacité des systèmes de santé au niveau mondial. Les données nécessaires à la mise au point d’un système d’extraction d’informations de santé depuis les forums de patients sont mise à disposition par la société́ Kappa Santé. La première approche proposée s’inscrit dans un contexte de détection de cas de pharmacovigilance à partir d’échanges entre patients sur des forums de santé. Nous proposons un filtre basé sur le nombre de mots séparant le nom du médicament évoqué dans le message du terme considéré́ comme un potentiel effet indésirable. Nous proposons une seconde approche basée sur les « topic models » afin de cibler les groupes de messages abordant les thèmes traitant de non-observance. En terme de pharmacovigilance, le filtre gaussien proposé permet d’identifier 50.03% des faux positifs avec une précision de 95.8% et un rappel de 50%. L’approche de détection de cas de non-observance permet l’identification de ces derniers avec une précision de 32.6% et un rappel de 98.5%
Pharmacovigilance suffers from chronic underreporting of drug's adverse effects from health professional's part. The FDA (US Food and Drug Administration), The EMA (European Medicines Agency), and other health agencies, suggest that social media could constitute an additional data source for detection of weak pharmacovigilance signals. The WHO (World Health Organization) published a report in 2003 outlining the problem of non-compliance with treatment over long term and its prejudicial effectiveness on health systems worldwide. The necessary data for development of an information extraction system from patient's forums are made available by the company Kappa Sante. The first proposed approach fits into a context of pharmacovigilance case detection from patient's online discussions on health forums. We propose a filter based on the number of words separating the name of the mentioned drug in the message from the term considered as a potential adverse effect. We propose a second approach based on topic models to target groups of messages addressing topics dealing with non-compliance. In terms of pharmacovigilance, the proposed Gaussian filter identifies 50.03% of false positives with a precision of 95.8% and a recall of 50%. The case detection approach of non-compliance allows the identification of messages describing this kind of behaviors with a precision of 32.6% and a recall of 98.5%

Abstract The embryonic urogenital system generates the metanephric kidneys, the gonads and the adrenal glands, and its development is based on sequential and reciprocal cell and tissue interactions. The mechanisms which regulate urogenital ontogeny are still poorly understood. In this thesis, the roles of Wnt-4 and ErbB4 functions in gonad and kidney development were analysed by using in vivo functional genomic technologies. Wnt-4 is crucial in female development since its absence leads to a partial female to male sex reversal. We found that Wnt-4 mediated the interactions between the somatic and the germ cells and played a role in meiosis which is regulated in part by the secreted signal retinoic acid (RA). Expression of certain meiosis-controlling genes (Stra8, Spo11) was inhibited in the Wnt-4 deficient germ cells, while certain pluripotency genes (Oct4, Fgf9, Sox2 and Dnmt3l) were activated similarly as in the wild-type male gonad. In addition to this, we noted that a gene encoding for a Cyp26b1 enzyme, which degrades RA in the embryonic testis, was ectopically expressed in the Wnt-4 deficient ovary. Microarray analysis was used to identify candidate Wnt-4 target genes by using the Wnt-4 knock-out mouse. Of these genes, Runx-1 may represent a novel signalling target to mediate Wnt-4 activity in the control female development The role of receptor-tyrosine kinase ErbB4 in kidney development was studied by using both in vivo gain and loss of function approaches. In the gain-of-function situation, we found that certain markers for the epithelial tubules and collecting ducts lost their polarized expression pattern. At the same time, the orientation of the cells in the kidney tubules was deregulated and an increase in cell proliferation was noticed. We suggest that the observed defects gave rise to an increase in the tubule diameter and to cyst formation in the kidney cortex. In the loss-of-function mouse, the lack of ErbB4 expression led to a similar phenotype as with the gain of function, and the renal functions of the mutant adult kidneys were compromised. In conclusion, the results point to specific roles for Wnt-4 and ErbB4 in the control of urogenital development. Wnt-4 appears to be crucial in sustaining proper female somatic cell and germ cell differentiation, and maintenance of gonad development during and after the sex determination event, while ErbB4 activity is critical for the regulation of tubular growth in embryonic kidney development
Tiivistelmä Sekä nisäkkään jälkimunuainen, lisämunuainen että sukurauhanen kehittyvät alkion urogenitaalialueen järjestelmästä ja solu- ja kudosvuorovaikutukset ohjaavat elinkehitysprosessia. Tapahtuman molekyylitason mekanismit ovat kuitenkin huonosti tunnettuja. Tässä väitöskirjatyössä tutkittiin Wnt-4 signaalin tehtäviä sukurauhasen ja ErbB4- proteiinin munuaisen kehityksessä. Wnt-4 signaali on keskeinen naisen sukupuolisuuden kehityksessä, koska signaalin puutos aiheuttaa alkion sukupuolen osittaisen kääntymisen naaraasta koiraaksi. Tarkastelimme aluksi sitä, välittääkö Wnt-4 itusolujen ja sukurauhasen somaattisten solujen vuorovaikutuksia ohjaten itusolujen meioosia, jota mm. A-vitamiini säätelee. Havaitsimme, että Wnt-4 geeni puuttuessa tietyt meioosia säätelevät geenit kuten Stra8 ja Spo11 olivat heikentyneet, kun taas solujen monikykyisyyteen liittyvät geenit kuten Oct4, Fgf9, Sox2 ja Dnmt3l aktivoituivat vastaavalla tavalla kuin havaitaan normaalisti koirasalkion kivesaiheessa. Tämän lisäksi havaitsimme, että Cyp26b1-geeni, joka johtaa A-vitamiinin hajoamiseen alkiossa ja estää normaalisti meioosin koirasalkion kivesaiheessa oli aktivoitunut munuaisrauhasaiheessa, jolta puuttuu Wnt-4 aktiivisuus. Tuloksemme osoittavat, että Wnt-4 säätelee osaltaan naarasalkion itusolujen meioosia. Tarkastelimme myös mikrosirututkimusten avulla niitä geenejä, joita Wnt-4 säätelee sukuelinaiheessa. Identifioimme useissa Wnt ja β-catenin signaalireittiin liittyvissä geeneissa muutoksia. Muuntuneet geenit voivat olla Wnt-4 signaalireitin kohdegeenejä. Näistä Runx-1 saattaa olla keskeinen Wnt signaalitien kohdegeeni, joka säätelee merkittävällä tavalla naaraan munarauhasen kehitystä. Väitöskirjan toisessa osassa tarkastelimme ErbB4-reseptorityrosiinikinaasin tehtäviä munuaisen kehityksen säätelyssä. ErbB4-geenin tehtäviä tutkittiin käyttäen hyväksi siirtogeenisiä malliorganismeja, joissa ErbB4-geenin määrä oli joko koholla tai ajastetusti inaktivoitu. ErbB4- geenin kokeellinen yliaktiivisuus muutti spesifisti tekijöitä, jotka säätelevät osaltaan jälkimunuaisen epiteeliputkien solujen orientaatiota ja solun jakautumista. Solujen orientaatiomuutoksen yhteydessä myös solujen jakautuminen häiriintyi. Oletuksemme on, että nämä epiteelikudoksessa tapahtuneet muutokset ovat syy, miksi kohotettu ErbB4-aktiviteetti muuttaa epiteeliputkien paksuutta ja pituutta erityisesti munuaisen pintakerroksissa. Havaitsimme myös, että ErbB4-geenin ajastettu poistaminen munuaisen epiteelikudoksessa johti hyvin samankaltaisiin, mutta vastakkaisiin muutoksiin kuin ErbB4-aktiviteetin kohottaminen. Muutokset johtivat myös muutoksiin munuaisen toiminnassa. Yhteenvetona toteamme, että näillä Wnt-4 ja ErbB4 solusignallointiin liittyvillä molekyyleillä on keskeinen tehtävä alkion munarauhasen ja munuaisen aiheen kehityksen säätelyssä. Wnt-4 ohjaa sekä itusolujen että somaattisten solujen erilaistumista ja samalla sukupuolen määräytymistä ja jatkokehitystä, kun taas ErbB4-signallointireseptorin tehtävä on avainasemassa munuaisen epiteeliputken kasvun säätelyssä

Cette étude présente une dimension économique, sociale et environnementale très importante. Elle rentre dans le cadre du projet Franco-Marocain PHC Toubkal (Ecopama, Volubilis 2012). Son objectif majeur est de valoriser les écorces Marocaine d’Acacia mollissima par une extraction verte permettant l’obtention des produits réactifs, des tanins condensés, qui seront utilisés dans le collage des panneaux de contreplaqués. Trois méthodes d’extraction ont été étudiées. Deux sont conventionnelles, une macération et une infusion ; ces deux techniques d’extraction sont simples, peu coûteuses. La troisième est une extraction assistée par micro-ondes ; c’est une technique innovante, rapide et peu consommatrice en solvant. La méthodologie des plans d’expériences est utilisée dans cette étude pour déterminer les facteurs les plus significatifs pour l’amélioration du rendement d’extraction des tanins condensés, optimiser les conditions d’extractions, réduire la proportion de solvant utilisé ainsi que le temps d’extraction. L’impact des conditions d’extraction et des méthodes d’extraction sur la teneur des tanins condensés sont étudiés pour la première fois pour les écorces d’Acacia mollissima du Maroc. Les extraits ont été caractérisés par des dosages colorimétriques, par des analyses structurales et thermiques. Les trois méthodes d’extraction ont été comparées. La teneur des extractibles est affectée par la proportion de solvant utilisé et le temps d’extraction. L’extraction assistée par micro-onde présente des teneurs en tanins condensés supérieure à l’extraction par des méthodes conventionnelles mais la teneur en sucre extraits est aussi élevée. Des formulations de colles à base de tanin et de lignosulfonate ont été élaborées en utilisant l’hexamine comme durcisseur. La colle biosourcée et ses constituants ont été caractérisés par analyse thermogravimétrique (ATG), et par calorimétrie différentielle à balayage (DSC). Les propriétés thermomécaniques et mécaniques des colles élaborées sont évaluées. L’optimisation des conditions de pressage des panneaux de contreplaqués, ainsi que le ratio tanin-lignosulfonate glyoxalé, ont été réalisées. La résistance des panneaux à l’eau froide et chaude est améliorée par l’addition de la résine époxy aux formulations de colle. Les propriétés mécaniques des panneaux de contreplaqués encollés ont été évalués par des tests normatifs et ont été comparés à celle des résines synthétiques commerciales (urée formaldéhyde et phénol formaldéhyde). La qualité de collage des panneaux élaborés a été évaluée. Les différentes colles présentent des caractéristiques physiques et thermiques satisfaisantes et acceptables pour les industries de collage des panneaux de bois. Des panneaux de contreplaqués avec de bonnes performances mécaniques et une excellente résistance à l’eau froide et bouillante ont été fabriqués. Ces colles présentent une qualité de collage qui se rapproche de celle des résines phénol-formaldéhyde, et peuvent être utilisées avec succès, pour une application industrielle des panneaux de contreplaqués, en milieu sec, humide et extérieur
This study has an important economical, social and environmental dimension. It was conducted within the framework Franco-Moroccan PHC Toubkal "Ecopama, Volubilis 2012". The desire to enhance Moroccan bark of Acacia mollissima by the use of green extraction and also to obtain reagent products, condensed tannins, was the main objective of this study. These tannins will be used in the bonding of plywood panels. Three extraction methods were studied. Two are conventional, maceration and infusion; witch is simple and cheap extraction method. The third is microwave assisted extraction which is a fast, innovative method using a small amount of solvent. The experimental design methodology was used to identify the significant factors to improve yield extraction of condensed tannins, to optimize extraction process, to reduce solvent proportion and time extraction. The impact of extraction conditions and extraction process were studied for the first time on condensed tannins contents extracted from Moroccan bark of Acacia mollissima. The extracts were characterized using colorimetric assays, structural and thermal analysis.The three types of extraction were compared. The extractibles contents were affected by solvent proportion and also time extraction. Microwave assisted extraction produced a higher condensed tannins than the conventional method but in the other hand the sugars extracted is more important. Tannin-lignosulfonate adhesives were produced using hexamine as a hardener. The biobased adhesive formulations and their compounds were compared using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and by determining the thermal and mechanical proprieties of the adhesives. Optimal tannin-glyoxalated lignosulfonates ratio and pressing conditions of plywood panels were measured. The resistance of plywood panels to the cold and hot water was improved by the addition of epoxy resin in adhesive formulations. Mechanical properties of plywood panels made with tannin-lignosulfonates-epoxy adhesives were evaluated using normative standard and compared to those of panels made with a commercial resins (urea formaldehyde and phenol formaldehyde). The bonding quality of plywood panels elaborated was evaluated. The various adhesives elaborated have satisfactory and acceptable physical and thermal characteristics for bonding panels used in wood industries. Plywood panels with good mechanical performance, good resistance to cold water and to boiling water, were produced. The bonding quality of the adhesives elaborated in laboratory scale presented approximate proprieties than the phenol-formaldehyde resins which can use with successfully in dry, wet and exterior industrial application of plywood panels

Dopamine is an interesting biomolecule that functions as a neurotransmitter in the brain. It has been found able to stick to almost all surfaces due to its unique catecholamine structure. Under alkaline conditions, the catechol functional group oxidizes to quinone allowing dopamine to self-polymerize and form thin films on support surfaces. The facts that dopamine can be coated to virtually any materials and the amine and catechol functional groups support a variety of reactions with organic species make polydopamine an attractive multifunctional bioadhesive/coating. To date, most of research on polydopamine has been focusing on its applications as thin films and little attention has been paid to the adhesion aspect of the material. In the study, we evaluated the properties of self-polymerized dopamine thin films as a bioadhesive. The thesis consists of three consecutive studies: (i) characterization of the adhesion properties of polydopamine thin films; (ii) investigation of the mechanical properties of polydopamine thin films; and (iii) exploration of the potential of polydopamine thin films as a wet adhesive. Fundamental insights on the wettability, adhesion behaviours, and mechanical properties of polydopamine thin films for both wet and dry conditions were derived through sets of well-designed contact angle, contact adhesion, and contact deformation experiments. It was found that dopamine is able to coat plastic, ceramic and metal surfaces, and join or bond rigid substrates but might not be suitable for joining soft or flexible parts as polydopamine is fairly rigid and the bonding might be too slow and too rigid for practical applications if polydopamine is directly used as an adhesive. Based on the understanding, a new strategy for fabricating underwater adhesive was proposed and tested. In the strategy, polydopamine with ferric ion as the oxidant was utilized as a cross-linker to alginate solution, effectively turning the solution into a wet adhesive, which demonstrated better practical performances than other studies; the adhesive was able to produce a permanent tensile adhesive strength of 80 kPa joining aluminum and glass with macroscopic roughness at the interface within 2 hours of curing time. Inspired by the results from the contact deformation experiments, we were able to extend the JKR theory with the well-known plate theory to accommodate the deformation of nanometer thin films, obtaining their elasticity. We termed this extended theory the “thin film contact mechanics” and validated the theory against gold thin films and found it predicted the mechanical behaviours of the thin films fairly well.

碩士
國立清華大學
化學工程學系所
106
The purpose of the study is to increase the adhesion of the metal films on glass substrates by a wet metallization process. The process of the wet metallization uses the electroless Ni deposition (ELD) on glass substrates followed by electroplating (EP) Cu. To improve the adhesion of the metal films, titanium oxide is used as an adhesion promoter. Besides, in the part of electroless Ni deposition (ELD), the Pd nanoparticles are also modified with silane compound to improve the interaction between glass and Ni seed layer. There are three research parts in the study. The discussions of the first part of the study are about the analysis of the self-attaching Pd catalyst. In the lab, the amino silane compound surface treatment is used for long time. 3-2-(2-aminoethylamino) ethylamino propyl trimethoxysilane (ETAS) compound donates electrons to interact Pd catalyst capped with polyvinyl alcohol (PVA-Pd). In this study, we further integrate the silane compound to the Pd nanoparticles by adding ETAS to PVA-Pd aqueous solution. The ETAS contained PVA-Pd (ETAS-PVA-Pd) is capable to attach on glass surface by forming the Si-O covalent bond. The particles size of ETAS-PVA-Pd and the adsorption of the Pd catalyst on the glass are characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), water contact angle (W.C.A). The configuration of ETAS-PVA-Pd nanostructure as well as the effect of modification is explained by X-ray photoelectron spectroscopy (XPS). The average adhesion of ELD Ni-P film prepared by ETAS-PVA-Pd is 9.4 MPa, which is identical to the one using to separate ETAS treatment and then PVA-Pd adsorption. The adhesion of both processes has significantly outperformed the Ni-P film adhesion using commercial Sn/Pd or Ion-Pd system. However, the adhesion is still not high enough to the goal. The second part based on the first part focuses on using the TiO2 film as adhesion promoter. For the annealing effect, the graphs of scanning electron microscope(SEM) and AFM indicate the fracture changes from the interface of glass and TiO2 to the interface of TiO2 and Ni-Cu layer. On the other hand, the surface roughness and the structure of TiO2 factors corresponding to the adhesion are discussed. The adhesion of metal films increases to 305 gf/cm by adding the precursor titanium diisopropoxide bis (acetylacetonate) (TTDB) to the TiO2 suspension. The fracture of high adhesion of metal film is between the upper TiO2 structure and ELD Ni layer, which is proved by TEM and auger electron spectroscopy (AES) chemical analysis. In the last part of this study, we combine the above results and apply them on TGV interposer with wet metallization procedure for prospective study, and we propose some advice to achieve the goal of mass production.