No / This article describes how an insight into the chemical and physical cues that affect bacterial adhesion and biofilm formation can provide ideas for creating successful antifouling or antimicrobial surfaces. To facilitate the design of new materials, the role of physical and chemical properties on bacterial adhesion is reviewed. The current approaches to reduce bacterial adhesion to various polymeric surfaces are discussed, as well as how multidisciplinary research on surface design and engineering may have an impact on both fundamental and applied microbiological science and technology.

No / This chapter describes the current approaches to reduce bacterial adhesion to various biomaterial surfaces, focusing on nonfouling surfaces through patterning and hydrophobicity plasma-assisted surface treatment and deposition; incorporation of antimicrobials, antibiotics, antibiofilms, and natural extracts that are either immobilized or released; dual function antimicrobial surfaces; incorporation of nonpathogenic bacteria, bacteriophages, and biofilm dispersal agents but also reduced bacterial adhesion through tissue integration. To facilitate the design of new materials, the role of physical, chemical, and biological surface properties on bacterial adhesion is reviewed in each case, as an insight into the chemical and physical cues that affect bacterial adhesion and biofilm formation can provide ideas for creating successful antifouling or antimicrobial surfaces. The application of these surfaces is explored based on the clinical needs and the market gaps. How multidisciplinary research on surface design and engineering may have an impact on both fundamental understanding of bacterial adhesion to biomaterials and applied biomaterial science and technology is finally discussed.

Dentre as fibras vegetais estudadas como reforço para produção de compósitos cimentícios, as fibras de coco verde e sisal se destacam por suas características mecânicas de interesse industrial, baixo custo e baixa densidade. O objetivo deste trabalho é o estudo da funcionalização de fibras de coco verde e sisal, pela técnica de polimerização com plasma frio de metano, bem como a análise do efeito do tratamento, a fim de reduzir a hidrofilicidade natural das fibras, preservar suas propriedades mecânicas e aumentar sua durabilidade em meio alcalino. Fibras de coco verde e sisal foram tratadas com plasma frio de metano durante 4, 10 e 20 min. O experimento também incluiu ensaio de degradação das fibras, antes e após tratamento, em solução saturada de cimento Portland. Por meio de análise de molhabilidade e de espectroscopia de fotoelétrons excitados por raios X foi identificado que o tratamento tornou a superfície das fibras de sisal tratadas por 10 e 20 min menos hidrofílica, e das fibras de coco verde tratadas durante o mesmo tempo mais hidrofílica. Corroborando esses resultados, ensaio de arrancamento foi realizado em fibras de sisal tratadas por 20 min indicando boa aderência entre a fibra tratada e a matriz cimentícia. Após ensaio de degradação em solução cimentícia de ambas as fibras tratadas durante 10 e 20 min os resultados da espectroscopia na região do infravermelho por transformada de Fourier indicaram que o tratamento retardou o processo de degradação alcalina da hemicelulose e lignina das fibras de sisal, enquanto que para as fibras de coco verde a degradação das fibras sem tratamento foi igual ao daquelas sem com tratamento. Os ensaios mecânicos indicaram que as fibras de sisal tratadas tiveram maior resistência mecânica quando comparadas àquelas sem tratamento, e com relação às fibras de coco verde não houve diferença significativa entre fibras tratadas e sem tratamento. Além disso, não houve alteração do módulo de elasticidade das fibras de coco verde e sisal (sem tratamento e tratadas). Nesse contexto, os resultados obtidos indicaram que o tratamento com plasma frio de metano é eficaz para redução da hidrofilicidade da superfície das fibras de sisal, podendo vir a ser um tratamento promissor para minimizar a degradação alcalina da hemicelulose e lignina. / Among the studied plant fibres as reinforcement for the production of cement composites, green coconut and sisal fibres stand out for its mechanical characteristics of industrial interest, low cost, and low density. The aim of this work is to study of the plasma functionalization of green coconut and sisal fibres with methane cold plasma, as well as the analysis of the effect of this treatment in order to reduce the hydrophilicity of natural fibres, preserving its mechanical properties and increase its durability in alkaline medium. Green coconut and sisal fibres were treated with methane cold plasma for 4, 10 and 20 min. The experiment also included fibre degradation test before and after treatment in saturated solution of Portland cement. Wettability and XPS analyses indicated that the sisal fibres treated for 10 and 20 min presented surface more hydrophobic than green coconut fibres in the same treatment condition. Pullout test was performed in the sisal fibres treated by 20 min indicating good adherence between treated fibre and cement matrix. Both kinds of fibres were submited to degradation test imersed in the cementitious solution. The FTIR results indicated that the treatment retarded the alkaline degradation of the hemicellulose and lignin from sisal fibres whereas treated green coconut fibres showed the same degradation presented by untreated ones. The mechanical tests showed that the treated sisal fibres had higher mechanical strength compared to those without treatment, and regarding green coconut fibres there was no significant difference between treated and untreated fibres. Furthermore, there was no change in the modulus of elasticity of the green coconut and sisal fibre (treated and untreated). In this context, the results indicated that treatment with cold plasma of methane is effective in reducing the excessive hydrophilicity of the surface of sisal fibres and could be a promising treatment to minimize the alkaline degradation of hemicellulose and lignin.

Dentre as fibras vegetais estudadas como reforço para produção de compósitos cimentícios, as fibras de coco verde e sisal se destacam por suas características mecânicas de interesse industrial, baixo custo e baixa densidade. O objetivo deste trabalho é o estudo da funcionalização de fibras de coco verde e sisal, pela técnica de polimerização com plasma frio de metano, bem como a análise do efeito do tratamento, a fim de reduzir a hidrofilicidade natural das fibras, preservar suas propriedades mecânicas e aumentar sua durabilidade em meio alcalino. Fibras de coco verde e sisal foram tratadas com plasma frio de metano durante 4, 10 e 20 min. O experimento também incluiu ensaio de degradação das fibras, antes e após tratamento, em solução saturada de cimento Portland. Por meio de análise de molhabilidade e de espectroscopia de fotoelétrons excitados por raios X foi identificado que o tratamento tornou a superfície das fibras de sisal tratadas por 10 e 20 min menos hidrofílica, e das fibras de coco verde tratadas durante o mesmo tempo mais hidrofílica. Corroborando esses resultados, ensaio de arrancamento foi realizado em fibras de sisal tratadas por 20 min indicando boa aderência entre a fibra tratada e a matriz cimentícia. Após ensaio de degradação em solução cimentícia de ambas as fibras tratadas durante 10 e 20 min os resultados da espectroscopia na região do infravermelho por transformada de Fourier indicaram que o tratamento retardou o processo de degradação alcalina da hemicelulose e lignina das fibras de sisal, enquanto que para as fibras de coco verde a degradação das fibras sem tratamento foi igual ao daquelas sem com tratamento. Os ensaios mecânicos indicaram que as fibras de sisal tratadas tiveram maior resistência mecânica quando comparadas àquelas sem tratamento, e com relação às fibras de coco verde não houve diferença significativa entre fibras tratadas e sem tratamento. Além disso, não houve alteração do módulo de elasticidade das fibras de coco verde e sisal (sem tratamento e tratadas). Nesse contexto, os resultados obtidos indicaram que o tratamento com plasma frio de metano é eficaz para redução da hidrofilicidade da superfície das fibras de sisal, podendo vir a ser um tratamento promissor para minimizar a degradação alcalina da hemicelulose e lignina. / Among the studied plant fibres as reinforcement for the production of cement composites, green coconut and sisal fibres stand out for its mechanical characteristics of industrial interest, low cost, and low density. The aim of this work is to study of the plasma functionalization of green coconut and sisal fibres with methane cold plasma, as well as the analysis of the effect of this treatment in order to reduce the hydrophilicity of natural fibres, preserving its mechanical properties and increase its durability in alkaline medium. Green coconut and sisal fibres were treated with methane cold plasma for 4, 10 and 20 min. The experiment also included fibre degradation test before and after treatment in saturated solution of Portland cement. Wettability and XPS analyses indicated that the sisal fibres treated for 10 and 20 min presented surface more hydrophobic than green coconut fibres in the same treatment condition. Pullout test was performed in the sisal fibres treated by 20 min indicating good adherence between treated fibre and cement matrix. Both kinds of fibres were submited to degradation test imersed in the cementitious solution. The FTIR results indicated that the treatment retarded the alkaline degradation of the hemicellulose and lignin from sisal fibres whereas treated green coconut fibres showed the same degradation presented by untreated ones. The mechanical tests showed that the treated sisal fibres had higher mechanical strength compared to those without treatment, and regarding green coconut fibres there was no significant difference between treated and untreated fibres. Furthermore, there was no change in the modulus of elasticity of the green coconut and sisal fibre (treated and untreated). In this context, the results indicated that treatment with cold plasma of methane is effective in reducing the excessive hydrophilicity of the surface of sisal fibres and could be a promising treatment to minimize the alkaline degradation of hemicellulose and lignin.

Submitted by Milena Rubi (milenarubi@ufscar.br) on 2016-11-17T17:43:21Z No. of bitstreams: 1 RODRIGUES_Karina_2015.pdf: 7918406 bytes, checksum: 5c7eded70cc8a9dd00ce5c1b2d70d846 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2016-11-17T17:43:31Z (GMT) No. of bitstreams: 1 RODRIGUES_Karina_2015.pdf: 7918406 bytes, checksum: 5c7eded70cc8a9dd00ce5c1b2d70d846 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2016-11-17T17:43:39Z (GMT) No. of bitstreams: 1 RODRIGUES_Karina_2015.pdf: 7918406 bytes, checksum: 5c7eded70cc8a9dd00ce5c1b2d70d846 (MD5) / Made available in DSpace on 2016-11-17T17:43:54Z (GMT). No. of bitstreams: 1 RODRIGUES_Karina_2015.pdf: 7918406 bytes, checksum: 5c7eded70cc8a9dd00ce5c1b2d70d846 (MD5) Previous issue date: 2015-06-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this study, the wettability of porous anodic alumina (PAA) surfaces modified by plasma was investigated. The porous anodic alumina films were grown on aluminum substrate using a two step anodization procedure in oxalic acid solution under potentiostatic regime. The surfaces of PAA films were modified by plasma treatment or plasma deposition techniques. Prior to surface modification, the impurities were removed by a plasma cleaning procedure. Oxygen was used in plasma treatment in order to produce hydrophilic surfaces. On the other hand, the plasma deposition (in HMDSO or HMDSO + argon mixture) was performed to produce hydrophobic surfaces or less hydrophilic surface. Electropolished aluminum without PAA film were used as reference. The influence of substrate morphology on wettability was analyzed. The morphological characterization was performed by scanning electron microscopy (SEM). The microstructural analysis was carried out using Fourier Transformed Infrared Spectroscopy (FTIR). A goniometer was used to measure the contact angle and evaluate the wettability of electroplished aluminum and PAA films. The results showed that the wettability of the samples was affect by chemical interactions of functional groups on the surface deposited after plasma treatment. The effect of the porous surface morphology on wettability was not significant compared to the plasma treated films with new chemical interactions effects. / Neste trabalho foram investigadas as propriedades de molhabilidade das superfícies nanoestruturadas da alumina anódica porosa (AAP) modificadas por plasma. Os filmes de AAP foram produzidos sobre substrato de alumínio pelo método de anodização potenciostática em duas etapas em solução de ácido oxálico. Após a fabricação, as amostras foram submetidas a um tratamento a plasma (com oxigênio) ou a deposição a plasma (em HMDSO ou em uma mistura de HMDSO e argônio). Antes das modificações das superfícies, removeram-se as impurezas das amostras através de técnicas de limpeza a plasma. No tratamento a plasma, o gás oxigênio foi utilizado para a obtenção de superfícies hidrofílicas. Por outro lado, para tornar a superfície hidrofóbica ou menos hidrofílica, foram feitas duas séries de deposição a plasma, uma contendo uma mistura de argônio e HMDSO e outra série somente com HMDSO. O tratamento ou deposição a plasma também foram feitas em amostras de alumínio eletropolido, sem a camada de AAP, a fim de verificar a influência morfológica do substrato na molhabilidade. A caracterização morfológica dos filmes de AAP foi feita por microscopia eletrônica de varredura (MEV), onde foi verificada a formação dos poros na superfície. A caracterização microestrutural foi feita por espectroscopia de absorção no infravermelho por transformada de Fourier (FTIR) com o objetivo de verificar as alterações químicas na superfície. A molhabilidade foi analisada utilizando um goniômetro, equipamento que realiza medição direta do ângulo de contato. Os resultados mostram que a molhabilidade da superfície é afetada por interações químicas dos grupos funcionais na superfície dos filmes. Por outro lado, o efeito da morfologia sobre a molhabilidade da superfície não é significativo nas condições estudadas.

Les dispositifs interconnectés moulés (« Molded Interconnected Devices », MID) sont constitués de supports polymères avec des pistes métalliques déposées à leur surface. Les objectifs de la thèse ont été d'optimiser les traitements de surface de polymères d'origine industrielle étudiés dans le contexte des MID pour obtenir des dépôts par métallisation electroless présentant une bonne adhérence. De plus, des procédés innovants de localisation de tels dépôts métalliques ont été développés. Durant ces travaux, la fonctionnalisation par plasma micro-ondes sous différentes atmosphères azotées et sous différentes conditions a été étudiée pour obtenir l'adsorption d'espèces palladiées (catalyseurs universels de la réaction de métallisation electroless). Des plans d'expériences ont été mis en oeuvre pour identifier un protocole type, développé sur PA12, pour obtenir des dépôts adhérents (Ni, Cu). Cette méthode a pu être globalement transposée avec succès sur d'autres polymères d'origine industrielle (ABS/PC, LCP). La seconde partie des travaux a consisté à développer des protocoles originaux basés sur des colloïdes de palladium directement synthétisés en surface d'un tampon en PDMS (lithographie douce) pour la réalisation de motifs métalliques par des procédés « top-down » et « bottomup ». Des analyses de surface AFM, SEM, TEM, XPS, ToF-SIMS et de mouillage ont permis de caractériser les différentes modifications de surface. Ces protocoles ont permis la réalisation de motifs métalliques MID adhérents jusqu'à 15 μm d'épaisseur et des motifs submicrométriques à haute résolution et haute densité avec des caractéristiques non encore obtenues à ce jour via cette technologie / Molded Interconnected Devices (MID) consist in polymer based substrates with metal tracks at their surface. The aim of this thesis was to optimize surface treatments applied to industrial polymers intended for MID applications, in order to obtain electroless metal coatings exhibiting a high practical adhesion. Furthermore, innovative processes to localize these metal coatings were developed. In this work, surface functionalization based on various operating parameters of microwave plasma using various nitrogen-based atmospheres were studied to obtain palladium (universal catalyst for electroless metallization) adsorption. Designs of experiments were used to identify an optimal set of parameters for PA12 surface treatment to obtain adherent metal coatings (Ni, Cu). These conditions were overall successfully transferred to other industrial polymers (ABS/PC, LCP). The second part of this work consisted in the development of innovative processes based on the use of palladium colloids directly synthetized at the surface of PDMS stamps (soft lithography) to achieve localized metallization using bottom-up and top-down approaches. AFM, SEM, TEM, XPS, ToF-SIMS and wettability measurements allowed to characterise the various surface modifications. These processes made possible 15 μm thick MID metal patterns with satisfactory practical adhesion as well as high resolution and high density sub-micrometric patterns with unseen properties for this technology

Surfaces of carbon fibre roving were modified by means of a low temperature plasma treatment to improve their bonding with mineral fines; the latter serving as an inorganic fibre coating for the improved mechanical performance of carbon reinforcement in concrete matrices. Variation of the plasma conditions, such as gas composition and treatment time, was accomplished to establish polar groups on the carbon fibres prior to contact with the suspension of mineral particles in water. Subsequently, the rovings were implemented in a fine concrete matrix and their pull-out performance was assessed. Every plasma treatment resulted in increased pull-out forces in comparison to the reference samples without plasma treatment, indicating a better bonding between the mineral coating material and the carbon fibres. Significant differences were found, depending on gas composition and treatment time. Microscopic investigations showed that the samples with the highest pull-out force exhibited carbon fibre surfaces with the largest areas of hydration products grown on them. Additionally, the coating material ingresses into the multifilament roving in these specimens, leading to better force transfer between individual carbon filaments and between the entire roving and surrounding matrix, thus explaining the superior mechanical performance of the specimens containing appropriately plasma-treated carbon roving.

To increase the survival rate from infectious- and noncommunicable diseases, reliable diagnostic during the preliminary stages of a disease onset is of vital importance. This is not trivial to achieve, a highly sensitive and selective detection system is needed for measuring the low concentrations of biomarkers available. One possible route to achieve this is through biosensing based on plasmonic nanostructures, which during the last decade have demonstrated impressive diagnostic capabilities. These nanoplasmonic surfaces have the ability to significantly enhance fluorescence- and Raman signals through localized hotspots, where a stronger then normal electric field is present. By further utilizing a periodic sub-wavelength nanohole array the extraordinary optical transmission phenomena is supported, which open up new ways for miniaturization. In this study a nanoplasmonic chip (NPC) composed of a nanohole array —with lateral size on the order of hundreds of nanometer— covered in a thin layer of gold is created. The nanohole array is fabricated using soft nanoimprint lithography on two resists, hydroxypropyl cellulose (HPC) and polymethyl methacrylate (PMMA). An in depth analysis of the effect of thickness is done, where the transmittance and Raman scattering (using rhodamine 6G) are measured for varying gold layers from 5 to 21 nm. The thickness was proved to be of great importance for optimizing the Raman enhancement, where a maximum was found at 13 nm. The nanohole array were also in general found beneficial for additionally enhancing the Raman signal. A transmittance minima and maxima were found in the region 200-1000 nm for the NPCs, where the minima redshifted as the thickness increased. The extraordinary transmission phenomena was however not observed at these thin gold layers. Oxygen plasma treatment further proved an effective treatment method to reduce the hydrophobic properties of the NPCs. Care needs be taken when using thin layers of gold with a PMMA base, as the PMMA structure could get severely damaged by the plasma. HPC also proved inadequate for this projects purpose, as water-based fluids easily damaged the surface despite a deposited gold layer on top.

Plasma-based surface modifications offer many interesting possibilities for the production of high value-added polymeric materials. In this work, different plasma-based synthetic concepts were employed to endow poly(ethylene terephthalate) (PET) fabrics with accessible amine functionalities. These concepts were compared to find out the appropriate engineering methods, which can be further accepted by textile industries to overcome the limited reactivity of PET fabric surfaces, while the bulk characteristics are kept unaffected. Amine functionalities were introduced onto the surface of PET fabrics using either low-pressure ammonia plasma treatment or coating oxygen plasma-treated PET fabric with cationic polyelectrolytes. Two different cationic polyelectrolytes were used in this study namely poly(diallyldimethylammonium chloride) as an example of strong polyelectrolytes and poly(vinyl amine-co-vinyl amide) as an example of weak polyelectrolytes. The modified surfaces were characterized by a combination of various surface-sensitive techniques such as X-ray photoelectron spectroscopy (XPS), electrokinetic measurements and time-dependent contact angle measurements. Furthermore, the amine functionalities introduced by different surface modifications were used for the subsequent immobilization of various classes of anionic dyes to evaluate the efficiency of different surface modifications. Color strength (K/S) and fastness measurements of colored fabrics were also explored. Their results can be taken as a measure of the extent of the interaction between different modified surfaces and anionic dyes. Finally, it was demonstrated that anchoring poly(vinyl amine-co-vinyl amide) layer onto PET fabric surfaces modified with low-pressure oxygen plasma is an efficient approach to improve coloration behavior and to overcome different problems related to PET fabrics coloration, such as coloration of PET/wool blend fabric with a single class of dyes. This is a crucial step towards the substrate independent surface coloration, which becomes dependent on the properties of the top layer rather than chemical structure of the fibers.

Plasma-based surface modifications offer many interesting possibilities for the production of high value-added polymeric materials. In this work, different plasma-based synthetic concepts were employed to endow poly(ethylene terephthalate) (PET) fabrics with accessible amine functionalities. These concepts were compared to find out the appropriate engineering methods, which can be further accepted by textile industries to overcome the limited reactivity of PET fabric surfaces, while the bulk characteristics are kept unaffected. Amine functionalities were introduced onto the surface of PET fabrics using either low-pressure ammonia plasma treatment or coating oxygen plasma-treated PET fabric with cationic polyelectrolytes. Two different cationic polyelectrolytes were used in this study namely poly(diallyldimethylammonium chloride) as an example of strong polyelectrolytes and poly(vinyl amine-co-vinyl amide) as an example of weak polyelectrolytes. The modified surfaces were characterized by a combination of various surface-sensitive techniques such as X-ray photoelectron spectroscopy (XPS), electrokinetic measurements and time-dependent contact angle measurements. Furthermore, the amine functionalities introduced by different surface modifications were used for the subsequent immobilization of various classes of anionic dyes to evaluate the efficiency of different surface modifications. Color strength (K/S) and fastness measurements of colored fabrics were also explored. Their results can be taken as a measure of the extent of the interaction between different modified surfaces and anionic dyes. Finally, it was demonstrated that anchoring poly(vinyl amine-co-vinyl amide) layer onto PET fabric surfaces modified with low-pressure oxygen plasma is an efficient approach to improve coloration behavior and to overcome different problems related to PET fabrics coloration, such as coloration of PET/wool blend fabric with a single class of dyes. This is a crucial step towards the substrate independent surface coloration, which becomes dependent on the properties of the top layer rather than chemical structure of the fibers.