Os nanomateriais e a questão ambiental

The increasing use of nanomaterials in several products in different areas such as electronics, cosmetics, food and drugs has attracted the attention of the scientific community due to unknown properties of these materials, such as the life cycle and the interaction with receptor organisms once they reach the environment. In this context, the present work shows an updated scenario of nanomaterials applications, characterization methods and toxicity evaluation, also addressing important aspects related to the development and application of nanotechnology under the environmental point of view.

Estudo da utilização de fibras em misturas betuminosas

A presente dissertação tem como objectivo principal aprofundar os conhecimentos sobre a incorporação de fibras em misturas betuminosas, em particular, sobre as misturas do tipo Stone Mastic Asphalt (SMA). Para este tipo de mistura betuminosa existe uma norma de produto europeia, a EN 13108-5:2006. Os ensaios tipo iniciais para efeitos de certificação CE das misturas estão contemplados na norma portuguesa NP EN 13108-20:2008, onde também são estipuladas as condições de ensaio. São descritos diversos tipos de fibras passíveis de serem utilizadas no fabrico da mistura betuminosa do tipo SMA, dando especial enfoque às misturas fabricadas com fibras celulósicas, uma vez que este tipo específico de mistura é frequentemente aplicado em camada de desgaste noutros países, com reconhecidas vantagens em termos de durabilidade e desempenho do pavimento. As misturas do tipo SMA são descritas, analisando-se métodos de formulação e métodos para a sua caracterização. Posteriormente, são apresentados e discutidos os trabalhos experimentais levados a cabo para um caso concreto. Os ensaios realizados permitiram caracterizar a mistura quanto à sensibilidade à água, ao seu módulo de rigidez e resistência à deformação permanente. Conclui-se que a mistura do tipo SMA com a incorporação de fibras analisada, apresenta bom comportamento à deformação permanente e boa resistência á acção da água, comparativamente às misturas betuminosas tradicionais aplicadas em camada de desgaste.

Development of human central nervous system 3D in vitro models for preclinical research

Neurological disorders are a major concern in modern societies, with increasing prevalence mainly related with the higher life expectancy. Most of the current available therapeutic options can only control and ameliorate the patients’ symptoms, often be-coming refractory over time. Therapeutic breakthroughs and advances have been hampered by the lack of accurate central nervous system (CNS) models. The develop-ment of these models allows the study of the disease onset/progression mechanisms and the preclinical evaluation of novel therapeutics. This has traditionally relied on genetically engineered animal models that often diverge considerably from the human phenotype (developmentally, anatomically and physiologically) and 2D in vitro cell models, which fail to recapitulate the characteristics of the target tissue (cell-cell and cell-matrix interactions, cell polarity). The in vitro recapitulation of CNS phenotypic and functional features requires the implementation of advanced culture strategies that enable to mimic the in vivo struc-tural and molecular complexity. Models based on differentiation of human neural stem cells (hNSC) in 3D cultures have great potential as complementary tools in preclinical research, bridging the gap between human clinical studies and animal models. This thesis aimed at the development of novel human 3D in vitro CNS models by integrat-ing agitation-based culture systems and a wide array of characterization tools. Neural differentiation of hNSC as 3D neurospheres was explored in Chapter 2. Here, it was demonstrated that human midbrain-derived neural progenitor cells from fetal origin (hmNPC) can generate complex tissue-like structures containing functional dopaminergic neurons, as well as astrocytes and oligodendrocytes. Chapter 3 focused on the development of cellular characterization assays for cell aggregates based on light-sheet fluorescence imaging systems, which resulted in increased spatial resolu-tion both for fixed samples or live imaging. The applicability of the developed human 3D cell model for preclinical research was explored in Chapter 4, evaluating the poten-tial of a viral vector candidate for gene therapy. The efficacy and safety of helper-dependent CAV-2 (hd-CAV-2) for gene delivery in human neurons was evaluated, demonstrating increased neuronal tropism, efficient transgene expression and minimal toxicity. The potential of human 3D in vitro CNS models to mimic brain functions was further addressed in Chapter 5. Exploring the use of 13C-labeled substrates and Nucle-ar Magnetic Resonance (NMR) spectroscopy tools, neural metabolic signatures were evaluated showing lineage-specific metabolic specialization and establishment of neu-ron-astrocytic shuttles upon differentiation. Chapter 6 focused on transferring the knowledge and strategies described in the previous chapters for the implementation of a scalable and robust process for the 3D differentiation of hNSC derived from human induced pluripotent stem cells (hiPSC). Here, software-controlled perfusion stirred-tank bioreactors were used as technological system to sustain cell aggregation and dif-ferentiation. The work developed in this thesis provides practical and versatile new in vitro ap-proaches to model the human brain. Furthermore, the culture strategies described herein can be further extended to other sources of neural phenotypes, including pa-tient-derived hiPSC. The combination of this 3D culture strategy with the implemented characterization methods represents a powerful complementary tool applicable in the drug discovery, toxicology and disease modeling.

Kromatografisen erotusfaasin huokoskoon karakterisointi

Työssä tutkittiin sulfonoitujen polystyreenidivinyylibentseenirunkoisten geeli-, meso- ja makrohuokoistenioninvaihtohartsien rakennetta käyttäen useita eri karakterisointimenetelmiä. Lisäksi työssä tutkittiin hartsien huokoskoon vaikutusta aminohappojen kromatografisessa erotuksessa. Työn pääpaino oli hartsien huokoskoon ja huokoisuuden määrittämisessä. Sen selvittämiseksi käytettiin hyväksi elektronimikroskopiaa, typpiadsorptiomittauksia, sekä käänteistä kokoekskluusiokromatografiaa. Parhaat tulokset saatiin käänteisellä kokoekskluusiokromatografialla, joka perustuu erikokoisten dekstraanipolymeerien käyttöön mallimolekyyleinä. Menetelmä sopii meso- ja makrohuokoisuuden tutkimiseen, mutta sen heikkoutena on erittäin pitkä mittausaika. Menetelmä antaa myös huokoskokojakauman, mutta yhden hartsin mittaaminen voi kestää viikon. Menetelmää muutettiin siten, että käytettiin määritettävää huokoskokoaluetta kuvaavien kahden dekstraanipolymeerin seosta. Kromatografiset ajo-olosuhteet optimoitiin sellaisiksi, että injektoidussa seoksessa olevien dekstraanien vastehuiput erottuivat toisistaan. Tällöin voitiin luotettavasti määrittää tutkittavan stationaarifaasin suhteellinen huokoisuus. Tätä työssä kehitettyä nopeaa käänteiseen kokoekskluusiokromatografiaan perustuvaa menetelmää kutsutaan kaksipistemenetelmäksi. Hartsien sulfonihapporyhmien määrää ja jakautumista tutkittiin määrittämällä hartsien kationinvaihtokapasiteetti sekä tutkimalla hartsin pintaa konfokaali-Raman-spektroskopian avulla. Sulfonihapporyhmien ioninvaihtokyvyn selvittämiseksi mitattiin K+-muotoon muutetusta hartsista S/K-suhde poikkileikkauspinnasta. Tulosten perusteella hartsit olivat tasaisesti sulfonoituneet ja 95 % rikkiatomeista oli toimivassa ioninvaihtoryhmässä. Aminohappojen erotuksessa malliaineina oli lysiini, seriini ja tryptofaani. Hartsi oli NH4+-muodossa ja petitilavuus oli 91 mL. Eluenttina käytettiin vettä, jonka pH oli 10. Paras tulos saatiin virtausnopeudella 0,1 mL/min, jolla kaikki kolme aminohappoa erottuivat toisistaan Finex Oy:n mesohuokoisella KEF78-hartsilla. Muilla tutkituilla hartseilla kaikki kolme aminohappoa eivät missään ajo-olosuhteissa erottuneet täysin.

Uusien polyuretaanimateriaalien kehittäminen

Polyuretaanielastomeerit ovat jaksottaisia sekapolymeerejä, jotka muodostuvat vuoroittaisista joustavien ketjujen segmenteistä ja hyvin polaarisista kovista segmenteistä. Kemiallinen rakenne ja ominaisuudet riippuvat käytetyistä reaktiokomponenteista. Pehmeän segmentin muodostaa polyoli ja kovan segmentin muodostaa yleensä di-isosyanaatti ja ketjunjatkaja. Polyuretaanielastomeerien valmistus tapahtuu valamalla, jolloin reaktiokomponentit ovat nestemäisiä. Työssä tutkittiin kahta perusmateriaalia ja yhden lisäaineen vaikutusta niiden ominaisuuksiin. Erityisesti kiinnitettiin huomiota dynaamisiin ja mekaanisiin ominaisuuksiin ja verrattiin aineita keskenään. Käytettyjä karakterisointimenetelmiä olivat kontaktikulmamittaukset, DMTA-mittaukset, dynaaminen rasittaminen pyörityslaitteella, elektronimikroskopia, hydrolyysitesti, vetotesti ja kulutustesti. Tutkittujen materiaalien pääasiallinen käyttökohde on pyörä- tai telapinnoitteena. Työn aikana kehitettiin pyörityslaite, jolla voitiin tutkia pinnoitemateriaalin käyttäytymistä halutuissa rasitusolosuhteissa. Lisäaineen vaikutus dynaamisiin ominaisuuksiin oli negatiivinen tai olematon, sillä DMTA-testien perusteella lisäaine kasvatti materiaalien häviötekijää (tan d). Pyöritystestien perusteella lisäaineella ei ollut vaikutusta hystereesiin eli pinnoitemateriaalin lämpenemiseen testin aikana. Uusi tutkittu materiaali osoittautui dynaamisissa kokeissa paremmaksi kuin vanha tuotantomateriaali. Lisäaine kasvatti molempien tutkittujen aineiden pintaenergiaa kontaktikulmamittausten perusteella. Tuotantoaineen vetomurtolujuus kasvoi lisäaineen vaikutuksesta, mutta uuden aineen vetomurtolujuus pieneni. Lisäaineella oli lievä hydrolyysiltä suojaava vaikutus tutkituilla perusaineilla. Uusi tutkittu perusmateriaali sieti hydrolyysiä paremmin kuin tuotantomateriaali, koska sen valmistuksessa käytettiin polyeetteripolyolia ja tuotantomateriaalissa polyesteripolyolia.

Pilarização de esmectita brasileira para fins catalíticos. Emprego de argila pilarizada na alquilação de benzeno com 1-dodeceno

Al-pillared clay was prepared with a Brazilian bentonite from the Campina Grande region (Paraíba, BRAZIL). It was intercalated at 298 K, during 48 hours, with a solution containing [Al3+] = 0.10 mol/L and molar ratio OH/Al = 2.0 prepared at 333 K, and was calcined at 773K. The catalytic activity was evaluated by alkylation of benzene with 1-dodecene. The characterization methods were: X-ray fluorescence and diffraction analysis; 27Al, 29Si and 23Na MAS NMR and textural analysis by N2 adsorption. The thermal stability of the natural clay was improved by the pillaring procedure, as well as the catalytic activity. The intercalated clay presented the highest initial rate of reaction among the systems tested.

Cerâmicas bioativas: estado da arte

Bioactive glasses undergo corrosion with leaching of alkaline ions when exposed to body fluids. This results in the spontaneous formation of a layer of hydroxyapatite (HA), the mineral component of natural bone, which in turn can induce bone growth in vivo. This paper describes the different types of bioactive glasses, the characterization methods currently used, and the main factors that influence their bioactivity. Nucleation and crystallization, the main mechanisms involved in the formation of hydroxyapatite, Ca10(PO4)6(OH)2, are discussed as a function of the chemical composition and the reactivity of the surface of the material. Finally, promising applications are considered.

Os nanomateriais e a questão ambiental

The increasing use of nanomaterials in several products in different areas such as electronics, cosmetics, food and drugs has attracted the attention of the scientific community due to unknown properties of these materials, such as the life cycle and the interaction with receptor organisms once they reach the environment. In this context, the present work shows an updated scenario of nanomaterials applications, characterization methods and toxicity evaluation, also addressing important aspects related to the development and application of nanotechnology under the environmental point of view.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Spectroscopic Studies of III-V Semiconductor Materials for Improved Devices

Defects in semiconductor crystals and at their interfaces usually impair the properties and the performance of devices. These defects include, for example, vacancies (i.e., missing crystal atoms), interstitials (i.e., extra atoms between the host crystal sites), and impurities such as oxygen atoms. The defects can decrease (i) the rate of the radiative electron transition from the conduction band to the valence band, (ii) the amount of charge carriers, and (iii) the mobility of the electrons in the conduction band. It is a common situation that the presence of crystal defects can be readily concluded as a decrease in the luminescence intensity or in the current flow for example. However, the identification of the harmful defects is not straightforward at all because it is challenging to characterize local defects with atomic resolution and identification. Such atomic-scale knowledge is however essential to find methods for reducing the amount of defects in energy-efficient semiconductor devices. The defects formed in thin interface layers of semiconductors are particularly difficult to characterize due to their buried and amorphous structures. Characterization methods which are sensitive to defects often require well-defined samples with long range order. Photoelectron spectroscopy (PES) combined with photoluminescence (PL) or electrical measurements is a potential approach to elucidate the structure and defects of the interface. It is essential to combine the PES with complementary measurements of similar samples to relate the PES changes to changes in the interface defect density. Understanding of the nature of defects related to III-V materials is relevant to developing for example field-effect transistors which include a III-V channel, but research is still far from complete. In this thesis, PES measurements are utilized in studies of various III-V compound semiconductor materials. PES is combined with photoluminescence measurements to study the SiO2/GaAs, SiNx/GaAs and BaO/GaAs interfaces. Also the formation of novel materials InN and photoluminescent GaAs nanoparticles are studied. Finally, the formation of Ga interstitial defects in GaAsN is elucidated by combining calculational results with PES measurements.

An EDTA-β-cyclodextrin adsorbent for the adsorption of rare earth elements and its application in preconcentration of ultratrace rare earth elements from seawater

The objectives of this work were synthesizing an EDTA-β-CD adsorbent and investigating its adsorption potential and applications in preconcentration of REEs from aqueous phase. The adsorption capacity of EDTA-β-CD was investigated. The adsorption studies were performed by batch techniques both in one- and multi-component systems. The effects of pH, contact time and initial concentration were evaluated. The analytical detection methods and characterization methods were presented. EDTA-β-CD adsorbent was synthesized successfully with high EDTA coverage. The maximum REEs uptake was 0.310 mmol g-1 for La(III), 0.337 mmol g-1 for Ce(III) and 0.353 mmol g-1 for Eu(III), respectively. The kinetics of REEs onto EDTA-β-CD fitted well to pseudo-second-order model and the adsorption rate was affected by intra-particle diffusion. The experimental data of one component studies fitted to Langmuir isotherm model indicating the homogeneous surface of the adsorbent. The extended Sips model was applicable for the isotherm studies in three-component system. The electrostatic interaction, chelation and complexation were all involved in the adsorption mechanism. The preconcentration of RE ions and regeneration of EDTA-β-CD were successful. Overall, EDTA-β-CD is an effective adsorbent in adsorption and preconcentration of REEs.

Determination of the thermal parameters of high-power batteries by local heat

A new approach to the determination of the thermal parameters of high-power batteries is introduced here. Application of local heat flux measurement with a gradient heat flux sensor (GHFS) allows determination of the cell thermal parameters in di_erent surface points of the cell. The suggested methodology is not cell destructive as it does not require deep discharge of the cell or application of any charge/discharge cycles during measurements of the thermal parameters of the cell. The complete procedure is demonstrated on a high-power Li-ion pouch cell, and it is verified on a sample with well-known thermal parameters. A comparison of the experimental results with conventional thermal characterization methods shows an acceptably low error. The dependence of the cell thermal parameters on state of charge (SoC) and measurement points on the surface was studied by the proposed measurement approach.

Nanostructure des particules polymériques : aspects physiques, chimiques et biologiques

Les nanotechnologies appliquées aux sciences pharmaceutiques ont pour but d’améliorer l’administration de molécules actives par l’intermédiaire de transporteurs nanométriques. Parmi les différents types de véhicules proposés pour atteindre ce but, on retrouve les nanoparticules polymériques (NP) constituées de copolymères “en bloc”. Ces copolymères permettent à la fois l’encapsulation de molécules actives et confèrent à la particule certaines propriétés de surface (dont l’hydrophilicité) nécessaires à ses interactions avec les milieux biologiques. L’architecture retenue pour ces copolymères est une structure constituée le plus fréquemment de blocs hydrophiles de poly(éthylène glycol) (PEG) associés de façon linéaire à des blocs hydrophobes de type polyesters. Le PEG est le polymère de choix pour conférer une couronne hydrophile aux NPs et son l’efficacité est directement liée à son organisation et sa densité de surface. Néanmoins, malgré les succès limités en clinique de ces copolymères linéaires, peu de travaux se sont attardés à explorer les effets sur la structure des NPs d’architectures alternatives, tels que les copolymères en peigne ou en brosse. Durant ce travail, plusieurs stratégies ont été mises au point pour la synthèse de copolymères en peigne, possédant un squelette polymérique polyesters-co-éther et des chaines de PEG liées sur les groupes pendants disponibles (groupement hydroxyle ou alcyne). Dans la première partie de ce travail, des réactions d’estérification par acylation et de couplage sur des groupes pendants alcool ont permis le greffage de chaîne de PEG. Cette méthode génère des copolymères en peigne (PEG-g-PLA) possédant de 5 à 50% en poids de PEG, en faisant varier le nombre de chaînes branchées sur un squelette de poly(lactique) (PLA). Les propriétés structurales des NPs produites ont été étudiées par DLS, mesure de charge et MET. Une transition critique se situant autour de 15% de PEG (poids/poids) est observée avec un changement de morphologie, d’une particule solide à une particule molle (“nanoagrégat polymére”). La méthode de greffage ainsi que l’addition probable de chaine de PEG en bout de chaîne principale semblent également avoir un rôle dans les changements observés. L’organisation des chaînes de PEG-g-PLA à la surface a été étudiée par RMN et XPS, méthodes permettant de quantifier la densité de surface en chaînes de PEG. Ainsi deux propriétés clés que sont la résistance à l’agrégation en conditions saline ainsi que la résistance à la liaison aux protéines (étudiée par isothermes d’adsorption et microcalorimétrie) ont été reliées à la densité de surface de PEG et à l’architecture des polymères. Dans une seconde partie de ce travail, le greffage des chaînes de PEG a été réalisé de façon directe par cyclo-adition catalysée par le cuivre de mPEG-N3 sur les groupes pendants alcyne. Cette nouvelle stratégie a été pensée dans le but de comprendre la contribution possible des chaines de PEG greffées à l’extrémité de la chaine de PLA. Cette librairie de PEG-g-PLA, en plus d’être composée de PEG-g-PLA avec différentes densités de greffage, comporte des PEG-g-PLA avec des PEG de différent poids moléculaire (750, 2000 et 5000). Les chaines de PEG sont seulement greffées sur les groupes pendants. Les NPs ont été produites par différentes méthodes de nanoprécipitation, incluant la nanoprécipitation « flash » et une méthode en microfluidique. Plusieurs variables de formulation telles que la concentration du polymère et la vitesse de mélange ont été étudiées afin d’observer leur effet sur les caractéristiques structurales et de surface des NPs. Les tailles et les potentiels de charges sont peu affectés par le contenu en PEG (% poids/poids) et la longueur des chaînes de PEG. Les images de MET montrent des objets sphériques solides et l'on n’observe pas d’objets de type agrégat polymériques, malgré des contenus en PEG comparable à la première bibliothèque de polymère. Une explication possible est l’absence sur ces copolymères en peigne de chaine de PEG greffée en bout de la chaîne principale. Comme attendu, les tailles diminuent avec la concentration du polymère dans la phase organique et avec la diminution du temps de mélange des deux phases, pour les différentes méthodes de préparation. Finalement, la densité de surface des chaînes de PEG a été quantifiée par RMN du proton et XPS et ne dépendent pas de la méthode de préparation. Dans la troisième partie de ce travail, nous avons étudié le rôle de l’architecture du polymère sur les propriétés d’encapsulation et de libération de la curcumine. La curcumine a été choisie comme modèle dans le but de développer une plateforme de livraison de molécules actives pour traiter les maladies du système nerveux central impliquant le stress oxydatif. Les NPs chargées en curcumine, montrent la même transition de taille et de morphologie lorsque le contenu en PEG dépasse 15% (poids/poids). Le taux de chargement en molécule active, l’efficacité de changement et les cinétiques de libérations ainsi que les coefficients de diffusion de la curcumine montrent une dépendance à l’architecture des polymères. Les NPs ne présentent pas de toxicité et n’induisent pas de stress oxydatif lorsque testés in vitro sur une lignée cellulaire neuronale. En revanche, les NPs chargées en curcumine préviennent le stress oxydatif induit dans ces cellules neuronales. La magnitude de cet effet est reliée à l’architecture du polymère et à l’organisation de la NP. En résumé, ce travail a permis de mettre en évidence quelques propriétés intéressantes des copolymères en peigne et la relation intime entre l’architecture des polymères et les propriétés physico-chimiques des NPs. De plus les résultats obtenus permettent de proposer de nouvelles approches pour le design des nanotransporteurs polymériques de molécules actives.

A structural investigation relating to the pozzolanic activity of rice husk ashes

Various factors determine the applicability of rice husk ash (RHA) as a pozzolanic material. The amount and accessibility of reactive sites is thought to be a key factor. A structural study of RHA samples in relation to their reactivity has been performed; Silica in RHA formed by burning rice husk in a laboratory furnace under continuous supply of air have been characterized as a function of incineration temperature, time and cooling regime. The characterization methods included chemical analyses, conductivity measurements, microscopic analysis, X-ray diffraction (XRD) and 29Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR). In line with earlier observations, the analyses show that the highest amounts of amorphous silica occur in samples burnt in the range of 500 °C–700 °C. The 29Si NMR data allow direct identification of the reactive silanol sites in the RHA samples. De-convolution of the NMR spectra clearly shows that the quickly cooled RHA resulting from burning rice husk for 12 h at 500 °C has the highest amount of silanol groups. This sample also induced the largest drop in conductivity when added to a saturated calcium hydroxide solution giving an indication of its reactivity towards lime. Therefore, this RHA is the favorable sample to be used as pozzolanic cement additive

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.