893 resultados para Conjugated copolymers
Resumo:
La technique de trempage («dip-coating») est un procédé rapide et efficace pour former des films minces de copolymères à blocs (CPB) d’épaisseur et de nano-morphologies variées. Très peu d’études ont toutefois porté sur le trempage des CPB supramoléculaires et/ou photosensibles. Le trempage du CPB poly(styrène-b-4-vinyl pyridine) (PS-P4VP) a premièrement été étudié avec des petites molécules (PM) d’acide 1-naphtoïque (NCOOH) et de 1-naphtol (NOH) capables de former des ponts hydrogène (ponts H) avec le bloc P4VP dans 4 solvants (tétrahydrofurane (THF), p-dioxane, toluène et chloroforme). Le ratio d’incorporation (RI) molaire PM/VP dans les films trempés augmente avec la vitesse de retrait mais sa variation dépend fortement du solvant et de la PM utilisés. Le RI et la morphologie des films minces dépendent de la possibilité (ou non) du solvant à former des ponts H avec la PM et de sa sélectivité au bloc de PS menant (ou non) à des micelles de P4VP/PM en solution dont la rigidité influence l’état cinétique du système en film mince. La dépendance en une courbe en V de l’épaisseur des films en fonction la vitesse de retrait définit deux régimes, nommés régimes capillaire et de drainage. Ces régimes influencent différemment le RI et la morphologie finale. Nous nous sommes ensuite intéressés aux complexes de PS-P4VP avec des azobenzènes (AB) photosensibles, le 4-hydroxy-4’-butyl-azobenzène (BHAB) et le 4-hydroxy-4’-cyano-azobenzène (CHAB). Ces AB peuvent non seulement former des ponts H avec le bloc P4VP mais aussi s'isomériser entre les formes trans et cis sous illumination. Les expériences avec PS-P4VP/BHAB dans le THF et le toluène ont révélé que l'irradiation pendant le trempage permet de provoquer une transition entre les morphologies sphérique et cylindrique à basses vitesses de retrait. Ces transitions sont expliquées par l’augmentation du ratio molaire BHAB/VP pris dans les films sous illumination et par le plus grand volume des isomères BHAB-cis par rapport aux BHAB-trans. L'irradiation permet également de moduler l'épaisseur des films sans égard à la présence des AB. Finalement, des solutions de PS-P4VP/CHAB et PS-P4VP/BHAB dans le THF avec un CPB de masse molaire plus élevée ont été étudiées afin de comprendre l’effet d'un temps de demi-vie plus court de l’AB et de la présence de micelles en solution. Le photocontrôle morphologique perd de son efficacité avec le CHAB car l’augmentation du RI de CHAB dans les films illuminés par rapport aux films non irradiés est moins prononcée que pour les complexes de BHAB. Le choix du PS-P4VP est également important puisque la présence de micelles dans les solutions de THF du PS-P4VP(36,5k-16k), même si elle n’influence pas les RI BHAB/VP, fige davantage la morphologie sphérique en solution par rapport à une solution non-micellaire de PS-P4VP(24k-9,5k), limitant les possibilités de transition morphologique.
Resumo:
Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.
Resumo:
Les polymères hydrosolubles sont utilisés dans diverses industries pour permettre la floculation, soit une séparation solide-liquide de particules présentes en suspension colloïdale. Afin de réduire les impacts environnementaux de l’exploitation des sables bitumineux en Alberta, l’industrie est à la recherche de nouveaux moyens et procédés pour traiter les résidus miniers permettant de séparer les matières solides et de récupérer l’eau. L’objectif des travaux présentés est d’améliorer la floculation, la densification et la déshydratation de ces résidus miniers aqueux par de nouveaux polymères synthétiques. Des homopolymères d’acrylamide de différentes masses molaires ont été synthétisés pour étudier l’influence de la masse molaire sur l’efficacité de floculation. Le taux initial de sédimentation (TIS) est le paramètre qui fut utilisé afin de comparer l’efficacité de floculation des différents polymères. Il a été possible de confirmer l’importance de la masse molaire sur l’efficacité de floculation et de déterminer une masse molaire minimale d’environ 6 MDa pour des polyacrylamides, afin d’obtenir l’efficacité de floculation maximale de suspensions colloïdales principalement composées de kaolin. Afin d’étudier l’effet des charges sur l’efficacité de floculation, des polymères anioniques et cationiques ont été synthétisés. Une série de copolymères d’acrylamide et d’acide acrylique ont été synthétisés comme polymères anioniques et deux séries de copolymères ont été synthétisés comme polymères cationiques, soit des copolymères d’acrylamide et de chlorure de diallyldiméthylammonium et des copolymères de 4-vinyl pyridine et de 1-méthyl-4-vinyl pyridinium. Il a été démontré que les charges anioniques des polymères avaient peu d’influence sur l’efficacité de floculation et que leur comportement en présence de sels était différent de ce que prévoyait la littérature. Il a aussi été démontré que les charges cationiques des polymères n’améliorent pas l’efficacité de floculation. Par la suite, des séries de copolymères amphiphiles, avec des monomères d’acrylamide, de N-alkylacrylamides et d’acrylonitrile, ont été synthétisés, pour étudier l’effet du caractère amphiphile sur la déshydratation des résidus miniers. Le pourcentage de déshydratation nette est le paramètre qui fut utilisé afin de comparer l’efficacité de déshydratation des différents polymères. Il a été possible de développer des copolymères amphiphiles qui améliorent l’efficacité de déshydratation par rapport à des homopolymères d’acrylamide. Il ne fut pas possible de déterminer une tendance entre la balance hydrophile/hydrophobe des copolymères amphiphiles et l’efficacité de déshydratation.
Resumo:
In this article, we report the preparation of conducting natural rubber (NR) with polyaniline (Pani). NR was made into a conductive material by the compounding of NR with Pani in powder form. NR latex was made into a conductive material by the in situ polymerization of aniline in the presence of NR latex. Different compositions of Pani- NR semi-interpenetrating networks were prepared, and the dielectric properties of all of the samples were determined in microwave frequencies. The cavity perturbation techpique was used for this study. A HP8510 vector network analyzer with a rectangular cavity resonator was used for this study. S bands 2-4 GHz in frequency were used. Thermal studies were also carried out with thermogravimetric analysis and differential scanning calorimetry.
Resumo:
In this article, we report the preparation of conducting natural rubber (NR) with polyaniline (Pani). NR was made into a conductive material by the compounding of NR with Pani in powder form. NR latex was made into a conductive material by the in situ polymerization of aniline in the presence of NR latex. Different compositions of Pani- NR semi-interpenetrating networks were prepared, and the dielectric properties of all of the samples were determined in microwave frequencies. The cavity perturbation techpique was used for this study. A HP8510 vector network analyzer with a rectangular cavity resonator was used for this study. S bands 2-4 GHz in frequency were used. Thermal studies were also carried out with thermogravimetric analysis and differential scanning calorimetry.
Resumo:
The main objective of the present study is to have a detailed investigation on the gelation properties, morphology and optical properties of small π-conjugated oligomers. For this purpose we have chosen oligo(p-phenylenevinylene)s (OPVs), a class of molecules which have received considerable attention due to their unique optical and electronic properties. Though a large number of reports are available in the literature on the self-assembly properties of tailor made OPVs, none of them pertain to the design of nanostructures based on organogels. In view of this, we aimed at the creation of functional chromophoric assemblies of π-conjugated OPVs through the formation of organogels, with the objective of crafting nanoscopic assemblies of different size and shape thereby modulating their optical and electronic properties.In order to fulfill the above objectives, the design and synthesis of a variety of OPVs with appropriate structural variations were planned. The design principle involves the derivatization of OPVs with weak H-bonding hydroxymethyl end groups and with long aliphatic hydrocarbon side chains. The noncovalent interactions in these molecules were expected to lead the formation of supramolecular assembly and gels in hydrocarbon solvents. In such an event, detailed study of gelation and extensive analysis of the morphology of the gel structures were planned using advanced microscopic techniques. Since OPVs are strongly fluorescent molecules, gelation is expected to perturb the optical properties. Therefore, detailed study on the gelation induced optical properties as a way to probe the nature and stability of the selfassembly was planned. Apart from this, the potential use of the modulation of the optical properties for the purpose of light harvesting was aimed. The approach to this problem was to entrap an appropriate energy trap to the OPV gel matrix which may lead to the efficient energy transfer from the OPV gel based donor to the entrapped acceptor. The final question that we wanted to address in this investigation was the creation of helical nanostructures through proper modification of the OPV backbone With chiral handles.The present thesis is a detailed and systematic approach to the realization of the above objectives which are presented in different chapters of the thesis.
Resumo:
In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.
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In the present work different new approaches for the synthesis of Vitamin A are investigated. In these synthetic schemes, all the twenty carbon atoms of the target molecule are derived either fully from components isolated from common essential oils or partially from commercially available materials. By retrosynthetic analysis, Vitamin A molecule can be disconnected into a cyclic and a linear unit. Different methods for the synthesis of the linear and the cyclic components are described. The monoterpenes, geraniol and citral, major constituents of palmarosa and lemongrass oils, have the required basic carbon framework for consideration as starting materials for the synthesis of Vitamin A. The potential of these easily available naturally occurring compounds as promising starting materials for Vitamin A synthesis is demonstrated. Organoselenium and organosulfur mediated functional group transformations for the synthesis of the functionalised conjugated C10 linear components (ie., the dimethyloctatriene derivatives) are reported. The classical approaches as well as the attempted preparation of cyclic C10 and C13 units employed in the present study as intermediates for Vitamin A synthesis are described. The utility of commercially available materials namely 2-acetylbutyrolactone and levulinic acid in -the preparation of C5 intermediates for Vitamin A synthesis is demonstrated.
Resumo:
The search for new materials especially those possessing special properties continues at a great pace because of ever growing demands of the modern life. The focus on the use of intrinsically conductive polymers in organic electronic devices has led to the development of a totally new class of smart materials. Polypyrrole (PPy) is one of the most stable known conducting polymers and also one of the easiest to synthesize. In addition, its high conductivity, good redox reversibility and excellent microwave absorbing characteristics have led to the existence of wide and diversified applications for PPy. However, as any conjugated conducting polymer, PPy lacks processability, flexibility and strength which are essential for industrial requirements. Among various approaches to making tractable materials based on PPy, incorporating PPy within an electrically insulating polymer appears to be a promising method, and this has triggered the development of blends or composites. Conductive elastomeric composites of polypyrrole are important in that they are composite materials suitable for devices where flexibility is an important parameter. Moreover these composites can be moulded into complex shapes. In this work an attempt has been made to prepare conducting elastomeric composites by the incorporation of PPy and PPy coated short Nylon-6 fiber with insulating elastomer matrices- natural rubber and acrylonitrile butadiene rubber. It is well established that mechanical properties of rubber composites can be greatly improved by adding short fibers. Generally short fiber reinforced rubber composites are popular in industrial fields because of their processing advantages, low cost, and their greatly improved technical properties such as strength, stiffness, modulus and damping. In the present work, PPy coated fiber is expected to improve the mechanical properties of the elastomer-PPy composites, at the same time increasing the conductivity. In addition to determination of DC conductivity and evaluation of mechanical properties, the work aims to study the thermal stability, dielectric properties and electromagnetic interference shielding effectiveness of the composites. The thesis consists of ten chapters.
Resumo:
In the present study, the photochemical depolymerisation of NR in toluene, in presence of H202 and a homogenizing solvent (Methanol/Tetrahydro— furan) so as to get hydroxyl terminated liquid natural rubber (HTNR) has been carried out. The copolymeri— sation of this product with butane 1,4 diol and toluene 2,4 diisocyanate in presence of a catalyst, dibutyl tin dilaurate, to produce polyurethanes with HTNR soft segments is also reported. The preparation of block copolymers based on poly(ethylene oxide) with varying molecular weights and HTNR are also discussed along with a detailed study on their thermal and mechanical properties
Resumo:
Polyaniline thin films prepared by RF plasma polymerisation were irradiated with 92MeV Si ions for various fluences of 1 1011, 1 1012 and 1 1013 ions/cm2. FTIR and UV–vis–NIR measurements were carried out on the pristine and Si ion irradiated polyaniline thin films for structural evaluation and optical band gap determination. The effect of swift heavy ions on the structural and optical properties of plasma-polymerised aniline thin film is investigated. Their properties are compared with that of the pristine sample. The FTIR spectrum indicates that the structure of the irradiated sample is altered. The optical studies show that the band gap of irradiated thin film has been considerably modified. This has been attributed to the rearrangement in the ring structure and the formation of CRC terminals. This results in extended conjugated structure causing reduction in optical band gap
Resumo:
Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.
Resumo:
Electrically conductive organic and metalloorganic polymers are of great interest and they have applications in electronic, optical, photonic, photoelectric, electrochemical, and dielectric devices. Tetrameric cobalt phthalocyanine was prepared by conventional chemical method. The dielectric permittivity of the tetrameric cobalt phthalocyanine sample was evaluated from the observed capacitance values in the frequency range 100 KHz to 5 MHz and in the temperature range of 300 to 383°K. It is found that the system obeys the Maxwell Wagner relaxation of space charge phenomenon. Further, from the permittivity studies AC conductivity was evaluated. The values of AC conductivity and DC conductivity were compared. Activation energy was calculated. To understand the conduction mechanism Mott’s variable range hopping model was applied to the system. The T 1/4 behavior of the DC conductivity along with the values of Mott’s Temperature (T0), density of states at the Fermi energy N (EF), and range of hopping R and hopping energy W indicate that the transport of charge carriers are by three-dimensional variable range hopping
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The thesis entitled “Exploration of Novel Organic Reactions Catalyzed by Nucleophilic Heterocyclic Carbenes (NHCs)” embodies the results of the investigations carried out to explore the synthetic potential of N–heterocyclic carbenes (NHCs) as organocatalyst towards various electrophiles for the synthesis of heterocyclic and carbocyclic systems. Recent investigations in the generation of homoenolates by the addition of NHCs to conjugated aldehydes have made it possible to study the reactivity of this unique three carbon synthon.
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A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.