Electro-Optical Studies On Metal Phthalocyanines

Metal phthalocyanines have some unique optical properties which are exploited for dyeing fibers and films used in applicationslike dye lasing and optical information storage. Aggregation of dye molecules modifies their absorption and emission spectra with concomitant degradation in their energy transfer characteristics. MPcs as such have poor processability and are seldom used in solid matrices. The finest energy transfer characteristics are shown by the monomers of metal phthalocyanines. In the third chapter of this thesis the studies on two series of metal phthalocyanines are repoted

Development and parametric studies of pulsed nitrogen and d-switched nd:glass lasers and some of their applications

Laser engineering is an area in which developments in the existing design concepts and technology appear at an alarming rate. Now—a-days, emphasis has shifted from innovation to cost reduction and system improvement. To a major extent, these studies are aimed at attaining larger power densities, higher system efficiency and identification of new lasing media and new lasing wavelengths. Todate researchers have put to use all the ditferent Forms of matter as lasing material. Laser action was observed For the first time in a gaseous system - the He-Ne system. This was Followed by a variety of solidstate and gas laser systems. Uarious organic dyes dissolved in suitable solvents were found to lase when pumped optically. Broad band emission characteristics of these dye molecules made wavelength tuning possible using optical devices. Laser action was also observed in certain p-n junctions of semiconductor materials and some of these systems are also tunable. The recent addition to this list was the observation of laser action from certain laser produced plasmas. The purpose of this investigation was to examine the design and Fabrication techniques of pulsed Nitrogen lasers and high power Nd: Glass laserso Attempt was also made to put the systems developed into certain related experiments

Nd:Glass Laser-Induced Damage To Thin Films, Two-Photon Excited Fluorescence And Plasma Studies

Laser-induced damage is the principal limiting constraint in the design and operation of high-power laser systems used in fusion and other high-energy laser applications. Therefore, an understanding of the mechanisms which cause the radiation damage to the components employed in building a laser and a knowledge of the damage threshold of these materials are of great importance in designing a laser system and to operate it without appreciable degradation in performance. This thesis, even though covers three distinct problems for investigations using a dye Q-switched multimode Nd:glass laser operating at 1062 nm and emitting 25 ns (FWHM) pulses, lays its main thrust on damage threshold studies on thin films. Using the same glass laser two-photon excited fluorescence in rhodamine 6G and generation and characterisation of a carbon plasma have also been carried out.

" Studies on Laser induced Phatothermal Phenomena in Selected Organic Compounds and Fullerenes"

In the pre—laser era it was difficult to believe that the optical properties of a medium depend upon the intensity of the radiation incident on it. The basis for this conclusion is that the electric field strength associated with the conventional light sources used before the advent of lasers was much smaller than (103 V/cm) the field sttrengths of atomic or interatomic fields (2 107 —- 10” V/cm). The radiation with such low intensity is not able to affect atomic fields to the extent of changing optical parameters. The invention of laser in 1960 was a turning point. The high degree of coherence of the laser radiation provides high spatial concentration of optical power. With the availability of the femtosecond lasers it has become possible to get extremely high peak powers 2 1013 W/cmz). At such high fields, the relationship between electric ‘polarization P and the electric field strength E ceases to be linear and several nonlinear effects begin to occur. Nonlinear absorption, a branch of nonlinear optics, refers to the interaction between radiation and matter accompanied by absorption of more than one photon. Nonlinear absorption has acquired great importance after the invention of high power lasers. One of the objectives of the present work is to investigate the nonlinear absorption processes occurring in fullerene, selected organic solvents and laser dyes. Fullerenes and laser dyes were chosen because of their highly nonlinear behaviour. Fullerenes, the most beautiful among molecules, offer fascinating field of research owinglto their significant structural properties. As toluene, benzene and carbon disulphide are themost widely used solvents for fullerenes, it seems important to study the nonlinear properties of these liquids as well. Like fullerenes, laser dyes also possess highly delocalized 7r electrons which are responsible for their nonlinear absorption. Dye lasers were the fulfillment of an experimenter’s pipe dream - to have a laser that is easily tunable over a wide range of wavelengths. A better understandingof the photophysical properties of laser dyes can significantly enhance the development and technology of dye lasers. We studied the nonlinear absorption properties of two rhodamine dyes to have some insight into their nonlinear optical properties.

Investigations on Nonlinear and Radiative Properties of Certain Phatonic Materials

Light in its physical and philosophical sense has captured the imagination of human mind right from the dawn of civilization. The invention of lasers in the 60’s caused a renaissance in the field of optics. This intense, monochromatic, highly directional radiation created new frontiers in science and technology. The strong oscillating electric field of laser radiation creates a. polarisation response that is nonlinear in character in the medium through which it passes and the medium acts as a new source of optical field with alternate properties. It was in this context, that the field of optoelectronics which encompasses the generation, modulation, transmission etc. of optical radiation has gained tremendous importance. Organic molecules and polymeric systems have emerged as a class of promising materials of optoelectronics because they offer the flexibility, both at the molecular and bulk levels, to optimize the nonlinearity and other suitable properties for device applications. Organic nonlinear optical media, which yield large third-order nonlinearities, have been widely studied to develop optical devices like high speed switches, optical limiters etc. Transparent polymeric materials have found one of their most promising applicationsin lasers, in which they can be used as active elements with suitable laser dyes doped in it. The solid-matrix dye lasers make possible combination of the advantages of solid state lasers with the possibility of tuning the radiation over a broad spectral range. The polymeric matrices impregnated with organic dyes have not yet widely used because of the low resistance of the polymeric matrices to laser damage, their low dye photostability, and low dye stability over longer time of operation and storage. In this thesis we investigate the nonlinear and radiative properties of certain organic materials and doped polymeric matrix and their possible role in device development

“Fabrication and characterization of polymer optical fibers for photonic device applications

Although the main application of optical fibers are in the field of telecommunication, optical fiber based sensors of various designs are becoming valuable devices for wide industrial applications. The advantages of optical fiber-based sensors include high sensitivity, insensitivity to electromagnetic radiation; spark free, light weight and minimal intrusiveness due to their relatively small size and deployment in harsh and hostile environments. It has been proved that POI-7 based sensors can be employed to detect a great variety of parameters including temperature, humidity, pressure, refractive index etc. The proposed thesis presented in six chapters deals with the work carried on dye doped and undoped POF for photonic device applications such as amplifier, laser and sensor

Thermal characterization of methylene blue intercalated montmorillonites by photoacoustic technique

Thermal diffusivity (TD) measurement on commercial K-10 and KSF montmorillonites was carried out by photoacoustic technique. The TD of the montmorillonites after methylene blue adsorption changed with the dye concentration. The repeatedly adsorbed samples showed a lesser TD than the single adsorbed samples. After methylene blue adsorption the acid leached K-10 samples showed well defined changes in TD when compared to the ordered KSF samples

Synthesis and Properties of Polyurethanes of Hexamethylene Di-Isocyanate with Multifunctional Chromophores in the Main Chain

Various polyurethanes containing photoactive bis(azo) and bis(o-nitrobenzyl) groups in the main chain were synthesized by polyaddition reactions of diols such as bis(4-hydroxyphenylazo)-2,20-dinitrodiphenylmethane, 4-hydroxy-3-methylphenylazo- 40-hydroxyphenylazo-2,20-dinitrodiphenylmethane and bis(4-hydroxy-3- methylphenylazo)-2,20-dinitrodiphenylmethane with hexamethylene di-isocyanate (HMDI), in dimethyl acetamide (DMAc) in the presence of di-n-butyltin dilaurate (DBTDL) as catalyst. All of them were characterized by IR, UV-vis, 1H NMR and 13C NMR spectra and also by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC).

Silver-doped photopolymer media for holographic recording

Incorporation of silver ions into a dye-sensitized poly(vinyl alcohol)/acrylamide photopolymer is observed to give better performance compared to other metal-ion-doped photopolymer holographic recording media. Plane-wave transmission gratings were recorded in the photopolymer films using a He–Ne laser, and various holographic parameters were optimized so as to explore maximum potential of the material for various holographic applications. Silver-doped films showed good energy sensitivity, and gratings recorded in optimized film exhibited a diffraction efficiency of more than 75%. The potential of the material for holographic data storage applications is also studied using peristrophic multiplexing

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

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.

Investigations on TiO2 Based Nanocomposites as Potential Photonic Materials

This Study overviews the basics of TiO2with respect to its structure, properties and applications. A brief account of its structural, electronic and optical properties is provided. Various emerging technological applications utilising TiO2 is also discussed.Till now, exceptionally large number of fundamental studies and application-oriented research and developments has been carried out by many researchers worldwide in TiO2 with its low-dimensional nanomaterial form due to its various novel properties. These nanostructured materials have shown many favourable properties for potential applications, including pollutant photocatalytic decomposition, photovoltaic cells, sensors and so on. This thesis aims to make an in-depth investigation on different linear and nonlinear optical and structural characteristics of different phases of TiO2. Correspondingly, extensive challenges to synthesise different high quality TiO2 nanostructure derivatives such as nanotubes, nanospheres, nanoflowers etc. are continuing. Here, different nanostructures of anatase TiO2 were synthesised and analysed. Morphologically different nanostructures were found to have different impact on their physical and electronic properties such as varied surface area, dissimilar quantum confinement and hence diverged suitability for different applications. In view of the advantages of TiO2, it can act as an excellent matrix for nanoparticle composite films. These composite films may lead to several advantageous functional optical characteristics. Detailed investigations of these kinds of nanocomposites were also performed, only to find that these nanocomposites showed higher adeptness than their parent material. Fine tuning of these parameters helps researchers to achieve high proficiency in their respective applications. These innumerable opportunities aims to encompass the new progress in studies related to TiO2 for an efficient utilization in photo-catalytic or photo-voltaic applications under visible light, accentuate the future trends of TiO2-research in the environment as well as energy related fields serving promising applications benefitting the mankind. The last section of the thesis discusses the applicability of analysed nanomaterials for dye sensitised solar cells followed by future suggestions.