Resumo: O controle químico tem sido utilizado freqüentemente com baixa eficiência para o fungo Didymella bryoniae, causador da doença crestamento gomoso ou cancro da haste em meloeiro. Porém, alternativas de controle como uso da enxertia e manipulação da nutrição devem ser estudadas. Avaliou-se porta-enxertos e concentrações de potássio na resistência de meloeiro rendilhado a Didymella bryoniae em ambiente protegido. No primeiro experimento, quatro porta-enxertos (melão „Dinero‟, melancia „Ojakkyo‟, abóbora „Strong Tosa‟ e cabaça „Calabash TI-191‟) foram inoculados com discos de micélio (7 mm de diâmetro) de quatro isolados de Didymella bryoniae (Dbr 34, Dbr 36, Dbr 37 e Dbr 39) em caule previamente ferido. Baseado no tamanho da lesão, o porta-enxerto „Dinero‟ foi susceptível, „Strong Tosa‟ moderadamente resistente, „Ojakkyo‟ e „Calabash TI-191‟ resistentes e o isolado Dbr 37 se mostrou mais agressivo dentre os isolados. No segundo experimento, o híbrido de meloeiro „Bônus II‟ foi enxertado nos porta-enxertos „Dinero‟ e „Strong Tosa‟, inoculadas com o isolado Dbr 37 do fungo e submetidas a diferentes concentrações de potássio (0; 62,5; 125; 187,5; 250 mg L-1), tanto plantas enxertadas como pé-franco. As plantas do híbrido „Bônus II‟ enxertadas foram resistentes ao fungo e as pé-franco susceptíveis. As concentrações de potássio não influenciaram no tamanho da lesão e na sobrevivência das plantas, porém influenciaram na condutância estomática e transpiração das plantas. / Abstract: Chemical control of the fungus Didymella bryoniae, causal agent of gummy stem blight of melon, is frequently inefficient. Alternative methods as grafting on resistant rootstocks and nutrition handling must be studied. Different rootstocks and potassium concentrations were tested to control the disease on net melon grown under plastic house conditions. In a first experiment four rootstocks (melon „Dinero‟, watermelon „Ojakkyo‟, squash „Strong Tosa‟ and calabash „TI-191‟) were tested for resistance inoculated by disks mycelium (7 mm diameter) with four isolates ( Dbr 34, Dbr 36, Dbr 37 and Dbr 39) of D. bryoniae in stem previously injured. Based on lesion size „Dinero‟ proved to be susceptible to the fungus, „Strong Tosa‟ moderately resistant and „Ojakkyo‟ and „TI-191‟ resistant and the isolated Dbr 37 proved more aggressive among isolates. In a second experiment hybrid net melon „Bonus II‟ was grafted on rootstocks „Dinero‟ and „Strong Tosa‟, inoculated with isolate Dbr 37 of the fungus and submitted to different potassium concentration (0; 62,5; 125; 187,5; 250 mg L-1), inoculated both grafted plants as non grafted. Grafted plants of „Bonus II‟ were resistant to the fungus and the non grafted ones susceptible. Potassium concentrations did not influenced size of the lesion on the stem and also in the plants survival, however influence on stomatal conductance and transpiration plants. / Orientador: Rumy Goto / Coorientador: Edson Luiz Furtado / Coorientador: Dirceu Maximino Fernandes / Banca: César Júnor Bueno / Banca: Haydée Siqueira Santos / Mestre

Submitted by Deyse Queiroz (deysequeirozz@hotmail.com) on 2018-05-23T12:48:29Z No. of bitstreams: 1 DANIEL SOARES DE ABRANTES - DISSERTAÇÃO PPGSA PROFISSIONAL 2015..pdf: 4362123 bytes, checksum: 252907e323bf8081a6d7afc2b1361702 (MD5) / Made available in DSpace on 2018-05-23T12:48:29Z (GMT). No. of bitstreams: 1 DANIEL SOARES DE ABRANTES - DISSERTAÇÃO PPGSA PROFISSIONAL 2015..pdf: 4362123 bytes, checksum: 252907e323bf8081a6d7afc2b1361702 (MD5) Previous issue date: 2015 / O cultivo da goiabeira mostra-se como atividade econômica e social importante, visto ser uma das frutas tropicais de maior aceitação no Brasil, entretanto, a disponibilidade de água para a irrigação tem se tornado cada vez mais escassa, tanto em termos de quantidade como de qualidade especialmente, em regiões áridas e semiáridas onde a evaporação é maior que a precipitação. Nesse contexto, o uso de águas salinas na agricultura deve ser considerado como alternativa importante, pois muitas vezes, é a única água disponível ao agricultor. Neste sentido, objetivou-se com esta pesquisa, avaliar a produção de mudas enxertadas de goiabeira irrigadas com águas de distintos níveis salinos e sob doses de adubação nitrogenada. Instalou-se dois experimentos usando em um o porta-enxerto de goiabeira Crioula e no outro o porta enxerto Paluma e, tendo como enxerto, a cv. de goiabeira Paluma. Os distintos experimentos foram instalados em condição de casa de vegetação, do Centro de Ciências e Tecnologia Agroalimentar da Universidade Federal de Campina Grande, Campus de Pombal-PB, usandose o delineamento experimental de blocos casualizados, cujos tratamentos foram distribuídos em esquema fatorial 5 x 4 e quatro repetições, sendo cada parcela constituída por três plantas. Os tratamentos resultaram da combinação entre dois fatores: salinidade da água de irrigação (CEa) em cinco níveis sendo eles S1-0,3; S2-1,1; S3-1,9; S4-2,7 e S5-3,5 dS m-1 preparados mediante adição de cloreto de Na, Ca e Mg, mantendo-se uma proporção equivalente igual a 7:2:1, respectivamente, e quatro doses de nitrogênio N1 - 70%, N2 - 100%, N3 -130% e N4 - 160% da dose padrão (552 mg de N dm-3 ). O aumento da CEa, a partir de 0,3 dS m-1 afeta negativamente as variáveis de crescimento bem como a qualidade das mudas de goiabeira Paluma enxertadas sob os porta-enxertos Paluma e Crioula. Houve interação entre a salinidade da água de irrigação e doses de nitrogênio para o diâmetro do enxerto de goiabeira Paluma, sendo que a dose de 100% de N reduziu o efeito da salinidade da água de irrigação aos 70 DAT. Para as mudas de goiabeira Paluma tendo como porta-enxerto a cv. Crioula, a adubação nitrogenada nas doses 100% e 130% para o IQD, atenuaram os efeitos do estresse salino, obtendo-se os maiores valores sob o nível de CEa de 0,8 e 1,4 dS m-1 respectivamente. As mudas irrigadas com águas de CEa de até 1,9 dS m-1 atenderam os critérios para produção de muda padrão de goiabeira. A utilização de águas com CEa de até 2,2 e 2,0 dS m-1 , na irrigação de mudas de goiabeiras Paluma tendo como porta enxerto a cv. Crioula e cv. Paluma, respectivamente, promovem redução aceitável no crescimento das plantas de 10%. / The cultivation of guava shows up as an important economic and social activity, since it is one of largest acceptance of tropical fruits in Brazil, however, the availability of water for irrigation has become increasingly scarce, both in terms of quantity and quality especially in arid and semi-arid regions where evaporation is greater than precipitation. In this context, the use of saline water in agriculture should be considered as an important alternative because it is often the only water available to the farming community. In this sense, the aim of this research was to evaluate the production of grafted guava plants irrigated with differing levels of saline water and under nitrogen fertilization. He settled on a two experiments using the rootstock of guava Crioula and the other of rootstock and Paluma with the graft, the cv. And Paluma guava. The different experiments were conducted in greenhouse conditions, the Center for Science and Agrifood Technology, Federal University of Campina Grande, Campus de Pombal-PB, using the experimental randomized block design and treatments were distributed in factorial 5 x 4, is 4 replicates, each plot had three plants. The treatments resulted from the combination of two factors: irrigation water salinity (ECw) in five levels S1-0,3; S2- 1,1; S3-1,9; S4-2,7 and S5-3,5 dS m-1 prepared by adding chloride Na, Ca and Mg, maintaining an equivalent ratio equal to 7: 2: 1, respectively, and four nitrogen levels N1 - 70%, N2 - 100%, N3 -130% and N4 - 160% of standard dose (552 mg N dm-3 ). The increase in CEa, from 0,3 dS m-1 negatively affects the growth variables and the quality of Paluma guava plants grafted on rootstocks Paluma and Crioula. There was interaction between water salinity irrigation and nitrogen levels to the diameter of the graft paluma guava, wherein the dose of 100% N reduced the effect of salinity irrigation water at 70 DAT. For guava plants cv Paluma acting as rootstock. Crioula, nitrogen fertilization in doses 100% and 130% for IQD, mitigated the effects of salt stress, obtaining the highest values under ECw level of 0,8 and 1,4 dS m-1 respectively. The seedlings irrigated with ECw of water up to 1,9 dS m-1 met the criteria for the production of standard guava changes. The use of water with supper to 2,2 and 2,0 dS m-1 in irrigation guava seedlings Paluma acting as door graft for cv. Crioula and cv. Paluma respectively, promote acceptable reduction in growth of the plants 10%

The uniform dispersion of the nano fillers without agglomeration in a polymeric matrix is widely adapted for the purpose of mechanical properties enhancement. In the context to biomedical applications, the type and amount of nanoparticles can potentially influence the biocompatibility. In order to address these issues, High Density Polyethylene (HDPE) based composites reinforced with graphene oxide (GO) were prepared by melt mixing followed by compression moulding. In an attempt to tailor the dispersion and to improve the interfacial adhesion, polyethylene (PE) was immobilized onto GO sheets by nucleophilic addition-elimination reaction. A good combination of yield strength (ca. 20 MPa), elastic modulus (ca. 600 MPa) and an outstanding elongation at failure (ca. 70 %) were recorded with 3 wt % polyethylene grafted graphene oxide (PE-g-GO) reinforced HDPE composites. Considering the relevance of protein adsorption as a biophysical precursor to cell adhesion, the protein adsorption isotherms of bovine serum albumin (BSA) were determined to realize three times higher equilibrium constant (Keq) for PE-g-GO reinforced HDPE composites as compared to GO reinforced composites. In order to assess the cytocompatibility, osteoblast cells (MC3T3) were grown on HDPE/GO and HDPE/PE-g-GO composites, in vitro. The statistically significant increase in metabolically active cell was observed, irrespective of the substrate composition. Such observation indicated that HDPE with GO or PE-g-GO addition (upto 3 wt %) can be used as cell growth substrate. The extensive proliferation of cells with oriented growth pattern also supported the fact that tailored GO addition can support cellular functionality, in vitro. Taken together, the experimental results suggest that the PE-g-GO in HDPE can effectively be utilized to enhance both mechanical and cytocompatibility properties and can further be explored for potential biomedical applications.

Ce travail a consisté en l’étude par Spectroscopie Diélectrique de la mobilité moléculaire dans trois systèmes nanostructurés et confinés à base de polymère. La dynamique moléculaire des films de copolymères greffés à base d’Acétate de Cellulose (chaîne principale, peu mobile) et de poly(méthyl (diéthylène glycol) méthacrylate) (chaîne greffée, très mobile) a été analysée. Nous avons dans ce cas, observé une augmentation de la mobilité de la chaîne principale et une réduction de la mobilité des greffons. Ensuite nous avons mis en évidence les effets de confinement induits par la phase cristalline sur la phase amorphe des films de Poly(éthylène naphtalène - 2,6 - dicarboxylate) (PEN) cristallisés à différents temps et températures de cristallisation, en fonction de la morphologie des matériaux. Une forte influence de la température de cristallisation sur la dynamique moléculaire du PEN a pu être observée : la mobilité des chaînes dans le cas des échantillons cristallisés aux hautes températures de cristallisation s’est révélée être plus élevée que celle des échantillons cristallisés aux basses températures. Le troisième système choisi consiste en des nanocomposites à base de Polyamide 6 (PA6) et de Montmorillonite (MMT) ont été les derniers matériaux étudiés. Aucune influence significative des feuillets de MMT sur la mobilité des chaînes de PA6 n’a été observée dans ces systèmes. Cependant, les deux relaxations interfaciales observées sont très sensibles au taux de charge. / The aim of this work was to study the molecular dynamics in several polymeric nanostructured and confined systems. Thus, by means of Dielectric Spectroscopy, the molecular mobility of cellulose acetate (rigid chain) grafted poly(methyl (diethylène glycol) methacrylate) (very mobile chains) copolymers were studied. In this case, an increase of the mobility of the main chain and a reduction of the mobility of the grafted moieties have been observed. The confinement effects induced by the presence of the crystalline lamellae on the mobility of the chains belonging to the amorphous region, was also studied as a function of the morphology, in the case of the amorphous films of Poly(ethylene naphtalene - 2,6 - dicarboxylate) (PEN) which were crystallized at different crystallization temperatures during different crystallization times. A strong influence of the crystallization temperature on the molecular dynamics of PEN has been evidenced: in the case of the samples crystallized at high temperatures, the mobility of the chains was higher than in the case of the samples crystallized at low temperatures. Finally, the confinement effects induced by the Montmorillonite (MMT) platelets on the Polyamide 6 (PA6) matrix were studied in the PA6/MMT nanocomposites. No significant influence of the filler on the molecular mobility of the PA6 chains was observed. Nevertheless, as expected, the two interfacial relaxations were very sensitive to the filler content.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / This work investigates the possible use of chitosan beads and polyaniline grafted chitosan beads (PGCB) for the adsorption of copper ions from copper contaminated water. For this purpose chitosan flakes were converted to chitosan beads. However, a variable from a number of reaction variables (aniline concentration, chitosan concentration, temperature, acid concentration, reaction time and initiator concentration) was varied while others was kept constant, in an attempt to determine the best conditions for grafting of polyaniline onto chitosan beads. Percentage (%) grafting and % efficiency were key parameters used to determine such conditions. The chitosan beads and PGCB were characterized using physical techniques such as Fourier transformed infra red (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM). The beads were used as an adsorbent for copper ions removal. The effect of pH on the removal rate of copper (II) by PGCB was investigated on by varying the pH values from pH 3 to 8 at an initial concentration of 40 mg/l. The effect of contact time, initial concentration and temperature was also investigated. The Langmuir and Freundlich model were used to describe adsorption isotherms for chitosan beads and PGCB, with correlation coefficient (R2) as the determining factor of best fit model. The thermodynamics of adsorption of copper (II) onto PGCB was described by parameters such as standard Gibb’s free energy change (ΔGo), standard enthalpy change (ΔHo), and standard entropy change (ΔSo) while the pseudo first-order and pseudo second-order kinetic model was used to describe kinetic data for the PGCB, with R2 and chi- square test (  2) as the determinant factor of best fit model. From the desorption studies, the effect of eluants (HCl and HNO3) and contact time on percentage desorption of PGCB loaded copper (II) ion was investigated upon. In determining the reusability of the PGCB loaded copper (II) ion, three cycles of adsorption/desorption studies was carried out. The results obtained from determining the best conditions for grafting polyaniline onto chitosan beads revealed the following grafting conditions; [Aniline] 0.1 g/l, [temperature] 35oC, [chitosan] 0.45 g/l, [HCl] 0.4 g/l, [(NH4)2S2O8] 0.35 g/l, and [time] 1 h. These conditions were applied in the grafting of polyaniline onto chitosan beads. FTIR analysis showed increase intensity in the grafted beads which provided evidence of grafting, XRD measurement showed a decrease in crystallinity in the PGCB as against the partial crystalline nature of chitosan. In SEM analysis, evidence of grafting was revealed by the closed gap between the polysaccharide particles in the PGCB. From the investigation carried out on the effect of pH on the percentage removal of Cu(II) ions by PGCB, the optimal pH value was found to be pH 5 with a percentage removal of 100% and this value was used for all adsorption experiment. Also from the investigation performed on the effect of contact time and initial concentration, it was observed that there was a sharp increase in the amount of Cu(II) ions adsorbed by PGCB up until contact time of 30 min and thereafter, it increases gradually. From the experiment carried out on the effect of temperature on adsorption capacity, there was an increase in adsorption capacity with increase in temperature. Moreover, at temperatures of 25oC, 35 oC and 45oC the Langmuir model gave the best fit for the chitosan beads having R2 values that are equal and greater than 0.942 in contrast to Freundlich having R2 values that is equal and greater than 0.932. The maximum adsorption capacity (Qm) from Langmuir model at these temperatures were 30.3 mg/g, 47.6 mg/g and 52.6 mg/g respectively. Also, the Langmuir model gave the best fit for the PGCB having R2 values that are equal and greater than 0.956 in contrast to Freundlich model with R2 values that is equal and greater than 0.935. The Qm from Langmuir model at these temperatures were 80.3 mg/g, 90.9 mg/g and 100 mg/g respectively. The values of Qm for PGCB appears to be significantly higher when compared to that of chitosan beads and this makes PGCB a better adsorbent than chitosan beads. From the thermodynamic studies carried out on PGCB, the values of ΔGo were negative and this denotes that the adsorption of copper ions onto PGCB is favorable and spontaneous, the positive value of ΔHo shows the adsorption process is endothermic and the positive value of ΔSo illustrate increased randomness at the solid-liquid interface during the adsorption process. Also, from the kinetic studies carried out on the PGCB, the pseudo second-order kinetic model best described the kinetic data having R2 values that are equal and greater than 0.994 in contrast to the pseudo first-order kinetic model with R2 values that is equal and greater than 0.913. The  2 values for the pseudo first-order and pseudo second-order kinetic model were similar; however, there was a large difference for qe between the calculated (qeCal) values of the first-order kinetic model and experimental (qeExp) values. In the case of the pseudo second-order model, the calculated qe values agree very well with the experimental data. Desorption of the metal ions from PGCB was efficient. 0.5 M HCl was successfully used in desorbing the beads loaded with copper ions and a percentage desorption of 97.1% was achieved at contact time of 180 min. PGCB were successfully re-used for adsorption/desorption studies were a Qm of 83.3 mg/g, 83.3 mg/g and 76.9 mg/g was achieved in the first, second and third cycle respectively.

Les recherches présentées dans ce mémoire ont été rendues possible grâce à la contribution financière du CRSNG, par à leur Programme de subventions à la découverte (SD) et leur Programme de bourses d’études supérieures du Canada au niveau de la maîtrise (BESC M); du FRQNT, par leur Programme de bourse de maîtrise (B1); et du CLS, par leur Graduate and Post-Doctoral Student Travel Support Program. / Le graphène est un nano-matériau très prometteur grâce à ses excellentes propriétés mécaniques, optiques et électriques. Toutefois, la plupart de ses applications les plus novatrices requièrent de l'altérer, mais la compréhension du graphène altéré est encore limitée. Certaines applications envisagées sont en optique infrarouge. Or, notre compréhension actuelle du graphène ne permet pas d’expliquer l’apparition des pics infrarouges qui sont observés dans les bicouches et dans les monocouches fonctionnalisées. Le comportement du graphène fonctionnalisé est particulièrement contre-intuitif, puisque l’ajout de greffons le rend plus transparent, et non pas plus opaque! Un modèle proposé par Bruno Rousseau, un étudiant post-doctorant du professeur Michel Côté à l'Université de Montréal, suggère une explication à ce phénomène: bien que les phonons du graphène ne puissent pas coupler directement avec la lumière, ils coupleraient indirectement avec celle-ci grâce à des collisions sur les électrons, qui eux, peuvent coupler avec les photons. Ce couplage indirect peut produire des interférences parfois constructives, parfois destructives, de telle sorte que ce mécanisme peut autant produire des pics d’absorbance que de transparence. Dans le cadre de ce mémoire, nous avons entrepris de vérifier expérimentalement la validité de ce modèle, et nous concluons qu’il semble prédire adéquatement le comportement de l’activité infrarouge des bicouches de graphène et des monocouches fonctionnalisées. Nous avons aussi étudié les méthodes par lesquelles nous synthétisions ces différents types de graphène afin de les optimiser. Enfin, nous avons déterminé des techniques, basées sur la spectroscopie Raman, permettant de bien caractériser l’intensité de l’altération causée par ces méthodes. / Graphene is a promising nanomaterials thanks to its excellent mechanical, optical and electrical properties. However, its most innovative applications require that it be altered, but the understanding altered graphene is still limited. Some applications are considered in infrared optics. However, our current understanding of graphene does not explain the appearance of the infrared peaks that are observed in bilayers and grafted monolayers. The behaviour of grafted graphene is especially baffling, since the addition of grafts makes it more transparent, not less! A model proposed by Bruno Rousseau, a postdoctoral student of Professor Michel Côté at Université de Montréal, suggests an explanation for this phenomenon: although the phonons of graphene cannot couple directly with light, they could couple indirectly through collisions with the electrons, which can couple with photons. This indirect coupling may produce constructive and destructive interference, depending on the conditions, so this mechanism can produce absorbance peaks as much as transparency peaks. In this master’s thesis, we have undertaken to experimentally verify the validity of this model, and we conclude that it seems to adequately predict the behaviour of the infrared activity of graphene bilayers and grafted monolayers. We also studied the methods by which we synthesized these different types of graphene to optimize them. Finally, we determined techniques based on Raman spectroscopy to characterize the intensity of the alteration induced by these methods.

Le protocole pour le greffage irréversible du copolymère amphiphile polystyrène-b-poly (acrylate de sodium) PS-b-PANa, sur un substrat de mica et de silice hydrophobe a été développé, en utilisant la méthode de greffage à partir de solution. Les propriétés de surface du bloc chargé ont été évaluées. L’effet de la force ionique sur le gonflement des chaînes a été investigué par ellipsométrie. Les forces d’interaction entre les surfaces recouvertes du copolymère ont été évaluées par la technique SFA. Les profils de force ont démontré être stables et nettement répulsifs en compression et décompression, montrant l’irréversibilité du greffage. Les forces de frottement entre les brosses de PANa sont élevées, mais aucune évidence d’endommagement de la surface n’a été observée. La comparaison entre le comportement à la surface des chaînes de l’acide polyacrylique PAA et celles du PANa, obtenues par deux méthodes de greffage différentes, est également investiguée. / A protocol for irreversibly grafting of amphiphilic copolymer polystyrene-b-poly (sodium acrylate) PS-b-PANa onto hydrophobized mica and silica was developed, using the grafting to approach. Surface properties of charge block were evaluated. The swelling of chains and force ionic effect were studied by ellipsometry. The interaction forces and frictional forces were evaluated by SFA technique. Forces profiles were stable and clearly repulsive in loading and receding, indicating an irreversible grafting. High friction forces onto PANa brushes were determinate without evidence of damage at the surface. The comparison between solution behavior of polyacrylic acid, PAA and PANa brushes, obtained via different grafting methods, was equally investigated.

The thesis describes the study of slow dynamics of confined polymers and soft colloids. We study the finite size effect on the dynamics of glassy polymers using newly developed interfacial microrheology technique. Systematic measurement have been performed to address the issue of reduction of glass transition under confinements. Slow and heterogeneous dynamics are the underlined observed behavior for dynamics in confined glassy polymers. The slow relaxation dynamics and dynamical heterogeneity in polymer grafted nanoparticles (PGNPs) systems were studied using advanced X - ray photon correlation spectroscopy (XPCS) techniques. Our studies presented in this thesis on dynamics of polymer grafted nanoparticle systems in melts and solution are the first attempt to study them experimentally. Thus our work shed the light about new technique to study confined system more accurately and explore new soft colloidal system to study fascinating dynamics and interesting phase behavior. In Chapter 1, we provide the theoretical background along with brief review of the literature for understanding the results presented in this thesis. The details of the experimental set up and their operating principle along with the details of the experimental conditions are provided in Chapter 2. In Chapter 3 we present our newly developed technique (interfacial microrhelogy) and its consequences to study the complex fluids at interface. Chapter 4 discusses the concentration and temperature dependent glassy dynamics in confined glassy polymers. In Chapter 5 we provide the structural and dynamical study of polymer grafted nanoparticles in melts and solutions. We provide the summary of our result and the future prospective of the work in Chapter 6. Chapter-1 provides the ground work and theoretical aspects for understanding the results presented in this thesis. It starts with the discussion about the slow dynamics of complex fluids and transit to dynamic behavior of polymer in confinement, glassy dynamics in confinements . This also discusses the basic aspects of studying viscoelastic properties using rheology, interface rheology, microrheology, interface microrheology techinques. In continuation it discusses structure and dynamics of different soft colloids investigated for last decade and then theoretical aspects of XPCS is discussed. Towards the end of this Chapter, we discuss the procedure to explain and understand systems dynamical heterogeneity near glass like phase transition. Chapter-2 contains the details of the experimental techniques which has been used for the study of confined polymers and soft colloids. Brief introduction to basic principles of the measurements followed by details of the material and methods have been provided. Chapter-3 we discuss the interafacial microrheology of different complex fluids and advantages of the techniques is discussed in Chapter 3. This includes discussion about the technique sensitivity at the surface using quantum dots (QDs) as a probe and about the configuration of the QDs at/on monolayer. Later on establishment of the technique has been demonstrated through easurements on arachidic acid, poly(methylmethacrylate) (PMMA), poly(vinylacetate) (PVAc), poly(methylacrylate) (PMA) monolayers. The extracted subdiffusive nature of QDs in on monolayers through mean square displacement has been explained using fractional Brownian motion model. Towards the end of the chapter we discuss about the extraction of real and imaginary elastic modulus from mean square displacement data using generalized Stokes-Einstein relation for the quasi two dimensional systems and explains about the possible viscoelastic transition in the different monolayers. The concentration and temperature dependent glassy dynamics of confined polymers (PMMA) are discussed in Chapter-4. We demonstrate the microscopic nature of spatio-temporal variation of dynamics of glassy polymers confined to a monolayer of 2 3 nm thickness as a function of surface density and temperature. It illustrates the systems dynamical heterogeneity and explain the observed large reduction of glass transition temperature in confined system through finite size effect. In Chapter 5 we discuss the result based on systematic studies of dynamics of PGNPs in melts and solutions. In addition it also illustrates the structural anisotropy and anomalous dynamical transitions in binary mixture of PGNPs and homopolymers in good solvent condition. It provides temperature and wave vector dependent XPCS measurements on polymer grafted nanoparticles with the variation of functionality. The functionality ( f ) dependent nonmonotonic relaxation in melts of PGNPs and solvent quality dependent non monotonic relaxation of PGNPs system have been elaborated in the continuation. We present possible phase behavior of PGNPs system in good solvent with addition of homopolymer of two different molecular weight. Chapter 6 contains the summary and the future perspective of the work presented.

Des glycopolymères greffés et dibloc, amphiphiles et photosensibles, à base de poly(acrylate d'o-nitrobenzyle) (PNBA) hydrophobe et photoclivable et de dextrane hydrophile ont été préparés avec succès en utilisant notammennt une réaction d'Huisgen (Cycloaddition Azoture-Alcyne catalysée par le Cuivre (I) - CuAAC chimie click). Dans un premier temps, la polymérisation de l'acrylate d'o-nitrobenzyle a été contrôlée avec succès grâce aux développements récents de la polymérisation radicalaire vivante par transfert d'un seul électron (SET-LRP). Nous avons alors obtenu un PNBA fonctionnalisé à son extrémitié par un brome. Ce brome a ensuite été substitué par un groupe azido. En parallèle, le dextrane a été modifié pour y introduire plusieurs fonctions alcyne (dextrane alcyne) ou une seule sur son extrémité réductrice (dextrane α-alcyne). Nous avons ensuite fait réagir ces dérivés de dextrane avec le PNBA-N3 pour obtenir respectivement les glycopolymères greffés et dibloc. Tous les glycopolymères ont été caractérisés par chromatographie d'exclusion stérique (SEC), Résonnance Magnétique Nucléaire 1H, 13C, 2D DOSY 1H et par spectrométrie FT-IR. Dans un deuxième temps, nous avons optimisé les conditions pour obtenir des nanoparticules peu disperses à partir des précédents glycopolymères. Dans certains cas, des nanoparticules ont également été obtenues en utilisant le dextrane alcyne et le PNBA-N3 dans un procédé d'émulsion/évaporation de solvant organique. La stabilité de toutes les nanoparticules vis-à-vis de solutions aqueuses de diverses forces ioniques ou d'un tensioactif compétitif a été étudiée. Enfin, l'effet de la lumière sur ces nanoparticules photosensibles a été mis en évidence à l'aide de la lampe UV. Plus précisément, nous avons pu suivre la destruction des nanoparticules par spectroscopie de fluorescence et diffusion de lumière dynamique en encapsulant le Rouge du Nil (sonde fluorescente) au sein de ces particules / Photosensitive grafted and diblock amphiphilic glycopolymers based on hydrophobic photosensitive poly(o-nitrobenzyl acrylate) (PNBA) and hydrophilic dextran were successfully prepared via grafting onto techniques through a Huisgen-type Copper(I) catalyzed Azide-Alkyne Cycloaddition (CuAAC click chemistry). Firstly, recent developments in the single-electron transfer–living radical polymerization (SET–LRP) provided us an access to control the o-nitrobenzyl acrylate polymerization and we obtained PNBA with bromide end function. Then, this bromide end function was replaced by azido (N3) group. In a parallel way, we modified dextran by introducing several alkyne groups all long the polysaccharide chain (alkynated dextran) or only one group at the reducing end-chain (α-alkyne dextran). In the second step, alkynated dextran and α-alkyne dextran were reacted with PNBA-N3 by CuAAC to obtain grafted or diblock glycopolymers. All glycopolymers were characterized by Size Exclusion Chromatography, 1H, 13C, 2D DOSY 1H NMR and FT-IR spectroscopy. Secondly, conditions to formulate nanoparticles from the previous glycopolymers were optimized. In some case, we also carried out an emulsion/evaporation process using dextran alkynated and PNBA-N3 to produce nanoparticles. Then, stability of nanoparticles were studied over rang of ionic strengths as well as stability in presence of a competitive surfactant. Finally, the effect of light on these photosensitive nanoparticles was studied using UV-lamp. More precisely, we loaded these nanoparticules by Nile Red fluorescent dye and followed thier destruction by using fluorescence spectroscopy and Dynamic Light Scattering

Ce travail a consisté en la synthèse et la caractérisation de nouveaux polycondensats poly(urée-imide)s (PUIs) greffés par une réaction de chimie "click" avec des nombres de greffons variables. Deux familles de matériaux ont été obtenues à partir d'un même PUI et de greffons de structures différentes mais de mêmes masses molaires : poly(méthoxy (diéthylène glycol) méthacrylate) (PMDEGMA) synthétisé par polymérisation radicalaire par transfert d’atome (ATRP) ; poly(hydroxyéthyl acrylate) (PHEA) préparé par Single Electron Transfer Living Radical Polymerization (SET-LRP). Ces matériaux ont ensuite été étudiés pour la purification du biocarburant éthyl tert-butyl éther (ETBE) par le procédé membranaire de pervaporation. Pour la séparation correspondante du mélange azéotropique ETBE/éthanol, les polycondensats avec des greffons PMDEGMA ont conduit à d’excellentes performances en extrayant l’éthanol de manière très sélective. La stratégie de greffage a permis d’augmenter fortement le flux tout en maintenant une excellente sélectivité et de pallier ainsi la limitation classique des polycondensats linéaires pour lesquels flux et sélectivité varient fortement de manière opposée. Les propriétés de ces polycondensats greffés ont été corrélées à leur morphologie particulière étudiée par MDSC et Synchrotron SAXS. Les greffons PHEA avec des groupes hydroxyle ont permis d'augmenter encore l'affinité pour l'éthanol. Cette affinité ayant dépassé les espérances avec des membranes trop gonflées par le mélange cible, les propriétés de sorption et de perméation de la seconde famille de copolymères greffés ont finalement étudiées pour le transport de l'eau, autre domaine de la perméabilité à forts enjeux industriels / This work deals with the synthesis and characterization of new graft step-growth copolymers poly(urea-imide)s (PUIs) by ‘click’ chemistry with variable graft amounts. Two families of materials were obtained from the same PUI and polymer grafts with different structures and the same molecular weights : poly(methoxy (diethylene glycol) methacrylate) (PMDEGMA) prepared by Atom Transfer Radical Polymerization (ATRP); poly(hydroxyethyl acrylate) (PHEA) obtained by Single Electron Transfer Living Radical Polymerization (SET-LRP). These materials were then investigated for the purification of the ethyl tert-butyl ether (ETBE) biofuel by the pervaporation membrane process. For the corresponding separation of the azeotropic mixture ETBE/ethanol, the copolymers with the PMDEGMA grafts showed excellent performances with very selective ethanol extraction. The grafting strategy enabled to increase the flux strongly while maintaining an excellent selectivity and thus overcame the classical limitation of linear step-growth copolymers, for which flux and selectivity strongly vary in opposite ways. The properties of the graft copolymers were correlated to their particular morphology characterized by MDSC and Synchrotron SAXS. The PHEA grafts with their hydroxyl groups enabled to further increase affinity for ethanol. This affinity having gone beyond expectation with a too strong membrane swelling in the targeted mixture, the sorption and permeability properties of the second series of graft copolymers were finally investigated for water transport, i.e. another permeability field with strong industrial stakes