Modification of the surface chemistry of materials used as implants in biomedical applications affords the ability to control cell adhesion, prevent inflammation and enhance integration with the host. Titanium and its alloys are strong and lightweight thereby making them desirable for applications such as hip and knee replacements, dental implants, and cardiac pacemaker implants. However, the lifetime of these implants is often limited by poor incorporation into the surrounding bone which results in loosening and wear. In order to overcome these limitations we have studied the modification of titanium substrates with a self-assembled monolayer that can be used to perform surface-initiated atom transfer radical polymerization (SI-ATRP) of a monomer to afford polymer brushes that effectively prevent the adhesion of cells. In addition, the polymer brushes afford the ability to tether a peptide sequence. Specific peptides containing adhesion sequences have been tethered to the polymer brushes. The resulting surfaces promote cell adhesion and osteoblast differentiation, thereby increasing bone tissue formation around the implant resulting in better incorporation of the implant.

Thesis(M. Com.(Economics)) -- University of Limpopo, 2019 / This study examined the determinants of learner performance by employing an education production function approach using the descriptive statistics, ordinary least squares (OLS) and quantile regression techniques in 2016. The study utilised the data obtained from SA-SAMS of Bankfontein combined school at Mpumalanga province. In the education production function, learner performance was estimated against variables such as age, gender, days absent and socio-economic status. The results of this study indicated that in the rural combined school, learner performance is strongly influenced by age, absenteeism and socio economic status. For instance, results revealed that absenteeism had a negative effect on learners‟ educational performance. An increase in absenteeism by 1 day led to a reduction in learner‟s examination score by approximately 0.1 percentage points during the chosen period. The “socioeconomic status” variable revealed a statistically significant and negative impact on learners‟ educational performance. The results demonstrate that poverty leads to poor educational performance as measured by examination scores. It is recommended that schools should manage learner diversity (age, gender and socio-economic factors), introduce learner motivation programmes, teacher performance improvement interventions, and improve organisational planning and development, parental involvement among others to retain learners at school. Furthermore, schools should enforce education policies that stipulate entry and exit age at different levels of schooling.

To expand the understanding of aging in the model organism Caenorhabditis elegans, global quantification of metabolite and protein levels in young and aged nematodes was performed using mass spectrometry. With age, there was a decreased abundance of proteins functioning in transcription termination, mRNA degradation, mRNA stability, protein synthesis, and proteasomal function. Furthermore, there was altered S-adenosyl methionine metabolism as well as a decreased abundance of the S-adenosyl methionine synthetase (SAMS-1) protein. Other aging-related changes included alterations in free fatty acid levels and composition, decreased levels of ribosomal proteins, decreased levels of NADP-dependent isocitrate dehydrogenase (IDH1), a shift in the cellular redox state, an increase in sorbitol content, alterations in free amino acid levels, and indications of altered muscle function and sarcoplasmic reticulum Ca2+ homeostasis. There were also decreases in pyrimidine and purine metabolite levels, most markedly nitrogenous bases. Supplementing the culture medium with cytidine (a pyrimidine nucleoside) or hypoxanthine (a purine base) increased lifespan slightly, suggesting that aging-induced alterations in ribonucleotide metabolism affect lifespan. An age-related increase in body size, lipotoxicity from ectopic yolk lipoprotein accumulation, a decline in NAD+ levels, and mitochondrial electron transport chain dysfunction may explain many of these changes. In addition, dietary restriction in aged worms resulting from sarcopenia of the pharyngeal pump likely decreases the abundance of SAMS-1, possibly leading to decreased phosphatidylcholine levels, larger lipid droplets, and ER and mitochondrial stress. The complementary use of proteomics and metabolomics yielded unique insights into the molecular processes altered with age in C. elegans.

No description available.

Les mono-couches auto-assemblées (SAMs) sont des systèmes de choix pour le développement de plateformes moléculaires aux propriétés physico-chimiques contrôlées. Il s’agit de monocouches organisées de molécules bi-fonctionnelles. Ces molécules se composent d’une fonction terminale modulable, séparée d’un groupement d’ancrage par un espaceur adapté. Ainsi, les propriétés des SAMs peuvent être ajustées pour le développement de systèmes électroniques moléculaires ou de capteurs (bio)-chimiques. De plus, des structurations chimiques supplémentaires peuvent être induites par irradiation.Les méthodes d’irradiation les plus courantes impliquent des particules de haute énergie. Les dommages induits résultent de plusieurs mécanismes en compétition (ionisations, excitations, dissociations). Dans cette thèse, les électrons lents (0-20 eV) sont utilisés comme particules primaires, et les processus d’interaction électron-SAM sont étudiés afin d’identifier les résonances d’attachement électronique. Aux énergies concernées, des processus dissociatifs sélectifs et efficaces peuvent être mis à profit pour proposer des stratégies d’irradiation menant à des modifications chimiques contrôlées et optimisées.Des SAMs modèles de thiols sur or sont étudiées par une technique de spectroscopie vibrationnelle de forte sensibilité de surface, la spectroscopie de perte d’énergie d’électrons lents (HREELS). Elle permet à la fois de caractériser les SAMs et de sonder les processus d'interaction électron-molécule. Les résultats obtenus concernent les : 1) SAMs aromatiques modèles de terphénylthiol (HS-(C₆H₄)₂-C₆H₅), stabilisables par réticulation sous irradiation. Une caractérisation vibrationnelle poussée de la SAM avant et après irradiation, en portant une attention particulière au comportement des modes d’élongation ν(CH), a permis d’opposer les processus de réactivité induite à 1, 6 et 50 eV.2) SAMs d’acide mercaptoundécanoïque (HS-(CH₂)₁ ₀ -COOH), les fonctions acides terminales permettant par exemple le greffage de peptides. L’interface SAM / environnement (COO-/COOH, eau résiduelle) a été caractérisée grâce à la forte sensibilité des modes d’élongation ν(OH) aux liaisons hydrogène. La démarche mise en place peut être facilement transposée à d’autres systèmes. / Self-Assembled Monolayers (SAMs) are good candidates to develop molecular platforms with controlled physico-chemical properties. A SAM is an ordered monolayer of bi-functionnal molecules. These molecules consist of an adjustable terminal function, separated from a headgroup by a chosen spacer chain. Thus, SAMs properties can be adjusted for the development of molecular electronic systems or (bio)-chemical sensors. Furthermore, additional chemical structuration can be induced by irradiation.Most current methods of irradiation involve high energy particles. The induced damages result from several competitive mechanisms (ionisations, excitations, dissociations). In this thesis, low energy electrons (0-20 eV) are used as primary particles, and the interaction processes between electrons and SAMs are studied in order to identify electron attachment resonances. At the associated energies, selective and effective dissociative processes can be induced to propose irradiation strategies leading to controlled and optimized chemical modifications.Model SAMs of thiols on gold are studied by a vibrational spectroscopy technique of strong surface sensibility, high resolution electron energy loss spectroscopy (HREELS). It allows at the same time to characterize SAMs and to probe electron-molecule interaction processes. The result obtained deal with : 1) Aromatic model SAMs of Terphenyl-thiol (HS-(C₆H₄)₂-C₆H₅), which can be stabilized by cross-linking under irradiation. Induced reactive processes at 1, 6 and 50 eV were compared and opposed, thanks to an advanced vibrational characterization of the SAM before and after irradiation, and by paying a particular attention to the stretching mode ν(CH) behaviour.2) Mercaptoundecanoic acid SAMs (HS-(CH₂)₁ ₀ -COOH), whose terminal functions allow for example the peptide anchoring. The interface SAM / environment (COO-/COOH, residual water) was characterized thanks to the strong sensitivity of the stretching modes ν(OH) to hydrogen bonding. The approach that was developped can be easily transposed to other systems.

Abstract : The objectives of this work were to prepare and characterize films of benzylic amide macrocycles and rotaxanes obtained by functionalisation of an acidterminated self-assembled monolayer (SAM) on gold, and thus to probe the aptitude of these surfaces for applications in the field of the nanotechnologies. We initially studied the self-assembled monolayer of 11-mercaptoundecanoic acid and focused on its composition, structure and organization. We show that the molecules of alcanethiol are oriented with the acid group pointing out from the surface. The film is highly ordered with defect density below 0.2%. We investigated the functionalisation process with the covalently bound Mac-OH macrocycle, with the physisorbed Mac-pyridine macrocycle and with the naphtalimide rotaxane. The latter is also anchored to the SAM through a non-covalent interaction. We focused on the comprehension of both quantitative as qualitative characteristics of the films, such as the degree of functionalisation, their stability with respect to external constraints, their order and homogeneity, their structure and their orientation. By combining techniques such as X-ray photoemission spectroscopy, infrared reflection-absorption spectroscopy, atomic force microscopy, electrochemical and contact angle measurements, we demonstrated that the films of macrocycles reach a high degree of functionalisation. The layers are homogeneous and a preferential orientation of the macrocycle molecules with the plan of the ring tilted with respect to the surface and with the alkyl chains pointing-out from the films is observed. In addition, we studied the possibility of using the macrocycle films for molecular recognition, employing the Fc-Gly-Gly molecule as a model target. Through similar experiments and analysis, films of naphtalimide rotaxane were proven to give a good functionalisation of SAM. The molecule adsorbs with a preferential orientation of the linear axis parallel to the surface and the macrocycle unit normal to it. We characterized the fluorescent properties of the molecule due to the naphtalimide group and showed that when adsorbed on a gold substrate the presence of the self-assembled monolayer prevents total quenching. <br> Résumé : Les objectifs de ce travail étaient de caractériser des films de macrocycles et de rotaxanes de type amide benzylique obtenus par la fonctionnalisation de monocouches auto-assemblées d'alcanethiols, ayant un groupe acide terminal, sur une surface d'or, et ainsi de mettre en évidence certaines des potentialités de ces surfaces en vue d'applications éventuelles dans le domaine des nanotechnologies. Nous avons d'abord étudié la monocouche auto-assemblée de l'acide 11-mercaptoundecanoïque et particulièrement les aspects tels que la composition, la structure et l'organisation du film et nous avons mis en évidence que les molécules d'alcanethiol sont orientées dans le film avec le groupe acide vers l'extérieur de la surface, de façon à pouvoir interagir avec les molécules à greffer, et que le degré d'ordre de la monocouche est très élevé, en montrant celle-ci une fraction de défauts inférieure au 0.2% de l'aire totale du film. L'étude de la fonctionnalisation successive avec le macrocycle Mac-OH, lié de façon covalente, et le macrocycle Mac-pyridine ainsi que la rotaxane naphtalimide, ancrés à travers une interaction non-covalente à la monocouche auto-assemblée, a porté une attention particulière à la compréhension d'aspects tels que le degré de recouvrement de la surface, la stabilité vis-à-vis de contraintes externes, l'ordre et l'homogénéité, ainsi que la structure des films et l'orientation des molécules. Grâce à la combinaison de techniques telles que l'XPS, l'IRAS, les techniques électrochimiques, les mesures d'angle de contact et l'AFM, nous avons mis en évidence que les films de macrocycle atteignent un recouvrement élevé et homogène de la monocouche autoassemblée et qu'une orientation des molécules de macrocycle, avec une inclinaison du plan de l'anneau par rapport à la surface et pointant leurs chaînes alkyles vers l'extérieure du film, est observée. Ensuite, nous avons abordé la possibilité d'impliquer les films de macrocycle en tant que récepteurs moléculaires d'une molécule modèle, la Fc-Gly-Gly. Par une caractérisation similaire, les films de la rotaxane naphtalimide ont montré d'atteindre un recouvrement élevé de la surface de la monocouche avec une orientation privilégiée des molécules avec l'axe parallèle et le macrocycle perpendiculaire à la surface pour pouvoir interagir, à travers les fonctions pyridine du macrocycle, avec la monocouche. De plus, nous avons caractérisé les propriétés fluorescentes de la molécule, résidantes dans son groupe naphtalimide, lorsqu'elle est adsorbée sur un substrat métallique, l'or, affectées par la présence de la monocouche auto-assemblée.

Utilizando registros isotópicos (\'delta\' \'POT.18\'O e \'delta\'\'POT.13\'C) de alta resolução, razões de elementos-traço em relação ao cálcio e taxas de crescimento de espeleotemas, precisamente datados pelo método U-Th, foi feita uma reconstrução da intensidade do Sistema de Monções Sul-Americano (SMSA) nos últimos 1500 anos na região do município de Bonito, Mato Grosso do Sul. O estudo do sinal climático, interpretado por meio de variações geoquímicas dos espeleotemas, foi realizado com base em estudos e comparações com dados instr umentais de uma estação meteorológica de Bonito, com dados de monitoramentos do IAEA - GNIP de Campo Grande e Cuiabá e com informações de modelos computacionais que simulam a variação de \'delta\'\'POT.18\'O em relação à intensidade das monções na América do Sul, o qual e stá relacionado com variação regional de pluviosidade. Apesar destes dados mostrarem que o amount effect é um dos fatores determinantes na variação das razões isotópicas dos espeleotemas, outros fatores como o degree of rainout upstream e a fonte de umidade (Amazônia x oceano Atlântico sul) também devem ser considerados importantes. Assim, a interpretação das razões de \'delta\'\'POT.18\'O é atribuída à intensidade do sistema de monções e, desta forma, à atuação da Zona de Convergência do Atlântico Sul (ZACS), principalmente associada à propagação de chuvas da região Amazônica para o centro-oeste e sudeste brasileiro. O registro paleoclimático de Bonito mostrou excelente coerência com variados tipos de registros de outros locais da América do Sul, e também com dados do Hemisfério Norte, evidenciando a influência de eventos de escala secular como MCA e LIA na intensidade das monções na América do Sul. A boa correlação entre algumas razões de elementos-traço com a precipitação mostra que o \"amount effect\" não controla totalmente os registros isotópicos. Análises de estatísticas de séries temporais aplicadas aos registros isotópicos e aos registros de elementos-traço permitiram a observação de vários eventos de freqüêcia decadal a multidecadal influenciando as monções da América do Sul. Os principais destes eventos são a NAO (North Atlantic Oscillation) e a AMO (Atlantic Multidecadal Oscillation), os quais, pelas flutuações de TSM no Atlântico Norte, desencadeiam teleconexões que têm resultados no posicionamento da Zona de Convergência Intertropical (Intertropical Convergence Zone - ITCZ) e da ZACS. / High-resolution isotope records (\'delta\'\'POT.18\'O e \'delta\'\'POT.13\'C), growth rates, elemental ratios in precisely dated speleothems by U/Th method are used to reconstruct the intensity of the South American Monsoon System (SAMS) during the 1500 years in Bonito Region, Mato Grosso do Sul. The interpretations of geochemical variations in speleothems are based on comparative studies with instrumental climatic data and at isotope measurements in rain water at IAEA - GNIP stations in Campo Grande and Cuiabá, as well as from climate model studies using oxygen isotope ratios as tracers of monsoon rainfall intensity. Despite of these data suggest that the \"amount effect\" is a dominant factor controlling the isotope variations in preci pitation, the \"degree of rainout upstream\" is considered also important because the distal influence of SAMS and South Atlantic Convergence Zone (SACZ) along the moisture transport tra jectory from Amazon to SE Brazilian Coast. The other significant factor to isotope composition to precipitation, therefore to speleothems, is the difference in moisture source area from Amazon Region (summer monsoonal precipitation) and Atlantic Ocean (extratropical regime). Bonito\'s paleoclimate Record indicate very good coherence with other records in South America and Northern Hemisphere, particularly in the response to the global scale climate events such as Medieval Climate Anomaly (MCA) e Little Ice Age (LIA) on summer precipitation. In these events were evidenced dryer and wetter conditions, respectively, not just from the stable isotope ratios but also from Sr/Ca and Ba/Ca ratios. Time series statistical analysis in the isotope and trace -element records showed that the SAMS is largely influenced by decadal to multidecadal events. In this regard, the most influent climate modes are the NAO (North Atlantic Oscillation) and the AMO (Atlantic multi Decadal Oscillation), with significant influence on the precipitation variability. In both cases these changes in precipitation are resulted from teleconection with Atlantic Ocean, which impacts the location of ITCZ and consequently the SACZ activity in Central-West Brazil.

Organic molecules such as porphyrins and alkanethiols are currently being investigated for applications such as sensors, light-emitting diodes and single electron transistors. Porphyrins are stable, highly conjugated compounds and the choice of metal ion and substituents bound to the macrocycle as well as other effects such as chemical surrounding and cluster size modulate the electronic and photonic properties of the molecule. Porphyrins and their derivatives are relatively non-toxic and their very rich photo- and electro-chemistry, and small HOMO-LUMO gaps make them outstanding candidates for use in molecularly-enhanced electronic applications. For these studies, self-assembled tri-pyridyl porphyrin thiol derivatives have been fully characterized on Au(111) surfaces. A variety of surface characterization techniques such as Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS) have been implemented in order to obtain information regarding the attachment orientation based on the angle and physical height of the molecule, conductivity which is determined based on the apparent height and current-voltage (I-V) measurements of the molecule, conductance switching behavior due to conformational or other effects as well as the stability of the molecular ensembles. Specifically, the transport properties of free base and zinc coordinated tri-pyridyl porphyrin thiol molecular islands inserted into a dodecanethiol matrix on Au(111) were investigated using STM and cross-wire inelastic electron tunneling spectroscopy (IETS). The zinc porphyrin thiol islands observed by STM exhibited reversible bias induced switching at high surface coverage due to the formation of Coulomb islands of ca. 10 nm diameter driven by porphyrin aggregation. Low temperature measurements (~ 4 K) from crossed-wire junctions verified the appearance of a Coulomb staircase and blockade which was not observed for single molecules of this compound or for the analogous free base. Scanning probe lithography via nanografting has been implemented to directly assemble nanoscale patterns of zinc porphyrin thiols and 16-mercapotohexadecanoic acid on Au surfaces. Matrix effects during nanopatterning including solvent and background SAMs have been investigated and ultimately ~ 10 nm islands of zinc porphyrins have been fabricated which is the optimal size for the observed switching effect.

Nanostructured materials play a vital role in almost all aspects of science and technology in the 21st century. The materials include nanoparticles, nanofilms, biological membranes etc. whose physicochemical properties are size-dependent. Thin films have wide range of applications in various branches of science. One of the efficient methods to form miniaturized structures for device applications is to fabricate nanostructured films on different substrates. Surfactant assembly on metallic and non-metallic surfaces based on self assembly and Langmuir-Blodgett technique offers a unique way to form thin films at molecular levels. The process of formation of unimolecular assemblies gives the flexibility of tuning the properties of underlying substrates for various applications including wetting characteristics, lubrication, passivation, mimicking biological phenomena etc. Towards this direction, self assembled monolayers (SAMs) of alkanethiols on gold and silver surfaces have been studied comprehensively for the past two decades. The reported literature on short chain length thiol-based monolayers is however, limited since the formation using conventional methods yield poor quality monolayers. The short chain length monolayers are useful in various applications like tribology, layer-by-layer assemblies, biosensors etc. Hence, it is essential to reproducibly form SAMs of various chain lengths and understand their properties. The present study is related to the formation of SAMs of alkanethiols and diselenides on gold and silver surfaces to form ordered and well-oriented monolayers. Monolayers of varying chain lengths (CH3(CH2)nSH where n = 3, 5, 7, 9, 11, 15) have been formed on gold and silver surfaces using different methods, (1) adsorption from neat thiols; (2) adsorption under electrochemical control and (3) adsorption from alcoholic solutions of the thiols. The characteristics features of the SAMs have been followed based on three different aspects, (i) structure and stability of the methylene groups (ii) interfacial characteristics involving the end group and the solvent and (iii) metal-head group interactions. The structure and stability of the monolayers have been followed based on vibrational spectroscopy and electrochemistry under different environment including thermal perturbations. The stability of the SAMs at different temperatures and subsequent changes associated with the orientation / packing has been monitored both in the dry state using reflection absorption infrared spectroscopy (RAIRS) and under electrochemical conditions using cyclic voltammetry and impedance analysis. Monolayers adsorbed from neat thiols show superior quality in terms of stability and structural arrangement. Short chain thiols with n = 3, 5, 7 show substantial stability when the adsorption is carried out from neat thiols. Figure 1 shows the RAIR spectra of hexanethiol SAM on gold adsorbed by three different procedures. Monolayers adsorbed under potential control behave very similar to the monolayers adsorbed from neat thiol as for as stability and structural orientation are concerned. Monolayers prepared using conventional methods of adsorption from alcoholic solutions are of inferior quality in terms of stability and arrangement especially for the short chain lengths. This is likely to be due to the fact that monolayers prepared using conventional methods may have intercalated solvent molecules within the monolayer assembly that degrade the integrity of the SAM leading to poor quality. The blocking characteristics of the monolayers for diffusing redox couple have been followed by determining the heterogeneous electron transfer rate constant using electrochemical techniques. The spectroscopic data and the electrochemical data follow similar trend indicating the superior quality of monolayer adsorbed from neat thiol in terms of stability as compared to conventionally prepared monolayers. Figure 1. RAIR spectra of hexanethiol-SAMs on Au(111) surface at 25C. The monolayers are formed by adsorption (A) from neat thiol (B) under potential control and (C) from alcoholic solution of the thiol. Wavenumber (cm-1) The interfacial characteristics of the monolayers (effect of end group functionality on the solvent properties) have been monitored on the basis of capacitance, contact angle and atomic force microscopy- measurements. Well-organized monolayers behave like good capacitors with relatively low values of double layer capacitance in presence of a liquid electrolyte as compared to the expected values based on known thickness and dielectric constant of the SAMs. This behavior can be explained by invoking the depletion of water density at the methyl terminated SAM-water interface where the solvent properties are different from that of bulk. Variation of one such property, dielectric constant, has been mapped using force measurement based on AFM. Dielectric constant of water changes from the bulk value of 78 to a low value as given in figure 2. This cross-over occurs within a span of 1-3 nm depending on the chain length of the thiol. Of the three procedures used, the ones based on the use of neat thiol and electrochemical adsorption result in well-oriented alkyl chains followed by highly oriented methyl terminal groups. This is responsible for the high hydrophobic nature of the interface and the subsequent observation of interfacial water properties. The SAMs prepared from ethanol fail to show the hydrophobic effects. Hydrophilic monolayers (NH2 terminated monolayers) fail to show depletion of water density at the interface indicating the importance of end group functionality in altering the interfacial characteristics of the monolayer. Figure 2. Spatial variation of dielectric permittivity of water at the hexanethiol SAM - water interface. The SAM is formed on gold (111) surface; (a) from ethanolic solution of the thiol (b) under electrochemical control (c) from neat thiol. The origin on the x-axis is the position of the methyl groups of SAM and the direction towards right side is in to the bulk water. The well-oriented SAMs have been used to follow the adsorption of a biopolymer. Zein protein is a prolamine of maize and is projected to be a biocompatible coating for food products and food containers. Hence, it is essential to prepare impermeable coatings of zein with different surface wetting properties. The adsorption of zein on highly ordered SAMs with hydrophobic or hydrophilic end group functionality has been studied and the orientation of the protein followed using spectroscopy, microscopy and electrochemistry. It is observed that zein shows higher affinity towards hydrophilic than hydrophobic surfaces with small foot print size on the Figure 3. Orientation of zein protein on hydrophilic and hydrophobic SAM as deciphered from the experimental data. hydrophilic surface resulting in large surface coverage. Figure 3 shows the schematics of zein deposits on hydrophilic and hydrophobic SAM surfaces determined based on spectroscopy, quartz crystal microbalance and electrochemical studies. The AFM shows cylindrical, rod-like and disc-like features of zein on hydrophilic surfaces that form the base units for the growth of cylindrical structures of zein. The published literature on the studies on SAMs on silver surfaces reveals that there is no consensus on the structure of the monolayers on silver. This may be due to the difficulty in getting pristine oxide-free surfaces in the case of silver and this is likely to affect the monolayer quality. Hence, it is decided to prepare SAMs of alkanethiols on silver and study their characteristics. Subtle differences between the monolayers adsorbed from neat thiol and from alcoholic solutions of thiols have been observed in terms of stability and permeability. Atomic force microscopic studies illustrate the presence of depletion of water at the SAM-aqueous interface. Diselenide-based monolayers have been formed on gold to understand the head group-substrate interactions on the monolayer properties. The disorder observed on short chain diselenide-based monolayers formed from alcoholic solutions can be eliminated by adsorption from neat compounds as described for the thiols. A preliminary account on the stability of SAMs under hydrodynamic conditions has been given based on rotating disc electrode voltammetry. It is observed that the SAMs get well-ordered when the electrode is rotated at a fast rate leading to the hypothesis that the monolayer assembly gets annealed as a function of the rotation rate. The thesis is planned as follows: Chapter 1 gives general introduction about organic thin films with particular emphasis on self-assembled monolayers on gold and silver, their characteristics in terms of stability, interfacial properties and adsorption behaviour. Chapter 2 deals with the experimental methodologies and schematics used for the preparation and characterization of the monolayers. Chapter 3 is on the contribution of alkyl spacer to the stability of the monolayers studied using spectroscopy and electrochemistry. Chapter 4 deals with the interfacial properties of the SAMs in presence of aqueous medium. In order to emphasize the importance of the terminal functional groups, adsorption of zein has been demonstrated on surfaces of controlled wettablity. Chapter 5 explains the formation and stability of monolayers of short and long chain alkyl diselenides on gold surfaces. Chapter 6 gives the structural and interfacial characteristics of alkanethiol monolayers on silver surfaces. The stability and subsequent changes of alkanethiol monolayers under hydrodynamic conditions has been discussed in the appendix section.(For fig pl refer pdf file.)

Utilizando registros isotópicos (\'delta\' \'POT.18\'O e \'delta\'\'POT.13\'C) de alta resolução, razões de elementos-traço em relação ao cálcio e taxas de crescimento de espeleotemas, precisamente datados pelo método U-Th, foi feita uma reconstrução da intensidade do Sistema de Monções Sul-Americano (SMSA) nos últimos 1500 anos na região do município de Bonito, Mato Grosso do Sul. O estudo do sinal climático, interpretado por meio de variações geoquímicas dos espeleotemas, foi realizado com base em estudos e comparações com dados instr umentais de uma estação meteorológica de Bonito, com dados de monitoramentos do IAEA - GNIP de Campo Grande e Cuiabá e com informações de modelos computacionais que simulam a variação de \'delta\'\'POT.18\'O em relação à intensidade das monções na América do Sul, o qual e stá relacionado com variação regional de pluviosidade. Apesar destes dados mostrarem que o amount effect é um dos fatores determinantes na variação das razões isotópicas dos espeleotemas, outros fatores como o degree of rainout upstream e a fonte de umidade (Amazônia x oceano Atlântico sul) também devem ser considerados importantes. Assim, a interpretação das razões de \'delta\'\'POT.18\'O é atribuída à intensidade do sistema de monções e, desta forma, à atuação da Zona de Convergência do Atlântico Sul (ZACS), principalmente associada à propagação de chuvas da região Amazônica para o centro-oeste e sudeste brasileiro. O registro paleoclimático de Bonito mostrou excelente coerência com variados tipos de registros de outros locais da América do Sul, e também com dados do Hemisfério Norte, evidenciando a influência de eventos de escala secular como MCA e LIA na intensidade das monções na América do Sul. A boa correlação entre algumas razões de elementos-traço com a precipitação mostra que o \"amount effect\" não controla totalmente os registros isotópicos. Análises de estatísticas de séries temporais aplicadas aos registros isotópicos e aos registros de elementos-traço permitiram a observação de vários eventos de freqüêcia decadal a multidecadal influenciando as monções da América do Sul. Os principais destes eventos são a NAO (North Atlantic Oscillation) e a AMO (Atlantic Multidecadal Oscillation), os quais, pelas flutuações de TSM no Atlântico Norte, desencadeiam teleconexões que têm resultados no posicionamento da Zona de Convergência Intertropical (Intertropical Convergence Zone - ITCZ) e da ZACS. / High-resolution isotope records (\'delta\'\'POT.18\'O e \'delta\'\'POT.13\'C), growth rates, elemental ratios in precisely dated speleothems by U/Th method are used to reconstruct the intensity of the South American Monsoon System (SAMS) during the 1500 years in Bonito Region, Mato Grosso do Sul. The interpretations of geochemical variations in speleothems are based on comparative studies with instrumental climatic data and at isotope measurements in rain water at IAEA - GNIP stations in Campo Grande and Cuiabá, as well as from climate model studies using oxygen isotope ratios as tracers of monsoon rainfall intensity. Despite of these data suggest that the \"amount effect\" is a dominant factor controlling the isotope variations in preci pitation, the \"degree of rainout upstream\" is considered also important because the distal influence of SAMS and South Atlantic Convergence Zone (SACZ) along the moisture transport tra jectory from Amazon to SE Brazilian Coast. The other significant factor to isotope composition to precipitation, therefore to speleothems, is the difference in moisture source area from Amazon Region (summer monsoonal precipitation) and Atlantic Ocean (extratropical regime). Bonito\'s paleoclimate Record indicate very good coherence with other records in South America and Northern Hemisphere, particularly in the response to the global scale climate events such as Medieval Climate Anomaly (MCA) e Little Ice Age (LIA) on summer precipitation. In these events were evidenced dryer and wetter conditions, respectively, not just from the stable isotope ratios but also from Sr/Ca and Ba/Ca ratios. Time series statistical analysis in the isotope and trace -element records showed that the SAMS is largely influenced by decadal to multidecadal events. In this regard, the most influent climate modes are the NAO (North Atlantic Oscillation) and the AMO (Atlantic multi Decadal Oscillation), with significant influence on the precipitation variability. In both cases these changes in precipitation are resulted from teleconection with Atlantic Ocean, which impacts the location of ITCZ and consequently the SACZ activity in Central-West Brazil.