Studies on Fluorescence Efficiency and Photodegradation of Rhodamine 6G Doped PMMA Using a Dual Beam Thermal Lens Technique

In this paper we report the use of the dual beam thermal lens technique as a quantitative method to determine absolute fluorescence quantum efficiency and concentration quenching of fluorescence emission from rhodamine 6G doped Poly(methyl methacrylate) (PMMA), prepared with different concentrations of the dye. A comparison of the present data with that reported in the literature indicates that the observed variation of fluorescence quantum yield with respect to the dye concentration follows a similar profile as in the earlier reported observations on rhodamine 6G in solution. The photodegradation of the dye molecules under cw laser excitation is also studied using the present method.

Studies on Heat Diffusion in Selected Conducting Polymers using Probe Beam Deflection and Photoacoustic Techniques

In the present study, radio frequency plasma polymerization technique is used to prepare thin films of polyaniline, polypyrrole, poly N-methyl pyrrole and polythiophene. The thermal characterization of these films is carried out using transverse probe beam deflection method. Electrical conductivity and band gaps are also determined. The effect of iodine doping on electrical conductivity and the rate of heat diffusion is explored.Bulk samples of poyaniline and polypyrrole in powder form are synthesized by chemical route. Open photoacoustic cell configuration is employed for the thermal characterization of these samples. The effect of acid doping on heat diffusion in these bulk samples of polyaniline is also investigated. The variation of electrical conductivity of doped polyaniline and polypyrrole with temperature is also studied for drawing conclusion on the nature of conduction in these samples. In order to improve the processability of polyaniline and polypyrrole, these polymers are incorporated into a host matrix of poly vinyl chloride. Measurements of thermal diffusivity and electrical conductivity of these samples are carried out to investigate the variation of these quantities as a function of the content of polyvinyl chloride.

Electron Density Determination of Laser Induced Plasma from Polymethyl Methacrylate Using Phaseshift Detection Technique

Irradiation of a Polymethyl methacrylate target using a pulsed Nd-YAG laser causes plasma formation in the vicinity of the target. The refractive index gradient due to the presence of the plasma is probed using phase-shift detection technique. The phase-shift technique is a simple but sensitive technique for the determination of laser ablation threshold of solids. The number density of laser generated plasma above the ablation threshold from Polymethyl methacrylate is calculated as a function of laser fluence. The number density varies from 2×1016 cm-3 to 2×1017 cm-3 in the fluence interval 2.8-13 J · cm-2.

Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(methyl methacrylate) and methyl-2-cyanoacrylate have been studied for the first time to our knowledge. The optical-limiting response is attributed to reverse saturable absorption due to excited-state absorption. The performance of LaPc in a copolymer host is studied at different linear transmissions. The laser damage thresholds of all the samples are also reported.

Novel Approaches to Biodegradable Polymers: Synthesis and Biodegradation Studies

Biodegradable polymers have opened an emerging area of great interest because they are the ultimate solution for the disposal problems of synthetic polymers used for short time applications in the environmental and biomedical field. The biodegradable polymers available until recently have a number of limitations in terms of strength and dimensional stability. Most of them have processing problems and are also very expensive. Recent developments in biodegradable polymers show that monomers and polymers obtained from renewable resources are important owing to their inherent biodegradability, biocompatibility and easy availability. The present study is, therefore, mostly concemed with the utilization of renewable resources by effecting chemical modification/copolymerization on existing synthetic polymers/natural polymers for introducing better biodegradability and material properties.The thesis describes multiple approaches in the design of new biodegradable polymers: (1) Chemical modification of an existing nonbiodegradable polymer, polyethylene, by anchoring monosaccharides after functionalization to introduce biodegradability. (2) Copolymerization of an existing biodegradable polymer, polylactide, with suitable monomers and/or polymers to tailor their properties to suit the emerging requirements such as (2a) graft copolymerization of lactide onto chitosan to get controlled solvation and biodegradability and (2b) copolymerization of polylactide with cycloaliphatic amide segments to improve upon the thermal properties and processability.

Complex permittivity and conductivity of poly aniline at microwave frequencies

Dielectric properties of polyaniline at different frequencies were studied. Cavity perturbation technique was employed for the study. Poly aniline in the powder and pelletised forms were prepared under different environmental conditions. Different samples of poly aniline exhibit high conductivity. However. the conductivity of samples prepared under different environmental conditions is found to vary. All the samples in the powder form have high conductivity irrespective of the method of preparation. The high conductivity at microwave frequency makes it possible to be used for developing microwave components like filters.

Photonic applications of biomaterials with special reference to biopolymers and microbes

This thesis Entitled Photonic applications of biomaterials with special reference to biopolymers and microbes. A detailed investigation will be presented in the present thesis related to direct applications of biopolymers into some selected area of photonics and how the growth kinetics of an aerial bacterial colony on solid agar media was studied using laser induced fluorescence technique. This chapter is an overview of the spectrum of biomaterials and their application to Photonics. The chapter discusses a wide range of biomaterials based photonics applications like efficient harvesting of solar energy, lowthreshold lasing, high-density data storage, optical switching, filtering and template for nano s tructures. The most extensively investigated photonics application in biology is Laser induced fluorescence technique. The importance of fluorescence studies in different biological and related fields are also mentioned in this chapter.

Modification of Linear Low Density Polyethylene for Improved Photo and Biodegradation

LLDPE was blended with poly (vinyl alcohol) and mechanical, thermal, spectroscopic properties and biodegradability were investigated. The biodegradability of LLDPE/PVA blends has been studied in two environments, viz. (1) a culture medium containing Vibrio sp. and (2) a soil environment over a period of 15 weeks. Nanoanatase having photo catalytic activity was synthesized by hydrothermal method using titanium-iso-propoxide. The synthesized TiO2 was characterized by X-Ray diffraction (XRD), BET studies, FTIR studies and scanning electron microscopy (SEM). The crystallite size of titania was calculated to be ≈ 6nm from the XRD results and the surface area was found to be about 310m2/g by BET method. SEM shows that nanoanatase particles prepared by this method are spherical in shape. Linear low density polyethylene films containing polyvinyl alcohol and a pro-oxidant (TiO2 or cobalt stearate with or without vegetable oil) were prepared. The films were then subjected to natural weathering and UV exposure followed by biodegradation in culture medium as well as in soil environment. The degradation was monitored by mechanical property measurements, thermal studies, rate of weight loss, FTIR and SEM studies. Higher weight loss, texture change and greater increments in carbonyl index values were observed in samples containing cobalt stearate and vegetable oil. The present study demonstrates that the combination of LLDPE/PVA blends with (I) nanoanatase/vegetable oil and (ii) cobalt stearate/vegetable oil leads to extensive photodegradation. These samples show substantial degradation when subsequent exposure to Vibrio sp. is made. Thus a combined photodegradation and biodegradation process is a promising step towards obtaining a biodegradable grade of LLDPE.

Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

Blue, Green and Orange-Red Light Emitting Polymers: Synthesis, Characterization and Prospects of Applications in Optoelectronic Devices

Light emitting polymers (LEPs) are considered as the second generation of conducting polymers. A Prototype LEP device based on electroluminescence emission of poly(p-phenylenevinylene) (PPV) was first assembled in 1990. LEPs have progressed tremendously over the past 20 years. The development of new LEP derivatives are important because polymer light emitting diodes (PLEDs) can be used for the manufacture of next-generation displays and other optoelectronic applications such as lasers, photovoltaic cells and sensors. Under this circumstance, it is important to understand thermal, structural, morphological, electrochemical and photophysical characteristics of luminescent polymers. In this thesis the author synthesizes a series of light emitting polymers that can emit three primary colors (RGB) with high efficiency

Synthesis And Characterization Ofpolystyrene Supportedcatalytically Active Poly(Amidoamine) Dendrimer-Palladium Nanoparticle Conjugates

Poly(amidoamine) dendrimers were synthesized on cross-linked aminomethyl polystyrene. Palladium complexes of supported dendrimers prepared by ligand exchange method were reduced to dendrimernanoparticle conjugates supported on polystyrene resin. The supported nanoparticles were used as heterogeneous catalysts for the Suzuki coupling between aryl boronic acids and aryl halides. Various factors affecting the catalysts performance were studied. Higher generation dendrimers gave well-defined nanoparticles without agglomeration and these particles showed good catalytic performance

Development and microwave characterization of selected biocompatible materials and conducting polymers

The 20th century witnessed the extensive use of microwaves in industrial, scientific and medical fields. The major hindrance to many developments in the ISM field is the lack of knowledge about the effect of microwaves on materials used in various applications. The study of the interaction of microwaves with materials demanded the knowledge of the dielectric properties of these materials. However, the dielectric properties of many of these materials are still unknown or less studied. This thesis is an effort to shed light into the dielectric properties of some materials which are used in medical, scientific and industrial fields. Microwave phantoms are those materials used in microwave simulation applications. Effort has been taken to develop and characterize low cost, eco-friendly phantoms from Biomaterials and Bioceramics. The interaction of microwaves with living tissues paved way to the development of materials for electromagnetic shielding. Materials with good conductivity/absorption properties could be used for EMI shielding applications. Conducting polymer materials are developed and characterized in this context. The materials which are developed and analyzed in this thesis are Biomaterials, Bioceramics and Conducting polymers. The use of materials of biological origin in scientific and medical applications provides an eco-friendly pathway. The microwave characterization of the materials were done using cavity material perturbation method. Low cost and ecofriendly biomaterial films were developed from Arrowroot and Chitosan. The developed films could be used in applications such as microwave phantom material, capsule material in pharmaceutical applications, trans-dermal patch material and eco-friendly Band-Aids. Bioceramics with better bioresorption and biocompatibility were synthesized. Bioceramics such as Hydroxyapatite, Beta tricalcium phosphate and Biphasic Calcium Phosphate were studied. The prepared bioceramics could be used as phantom material representing Collagen, Bone marrow, Human abdominal wall fat and Human chest fat. Conducting polymers- based on Polyaniline, are developed and characterized. The developed materials can be used in electromagnetic shielding applications such as in anechoic chambers, transmission cables etc

Effects of Different Feeding Regimes on the Digestibility and Faecal Excretion of Nitrogen, Soluble Carbohydrates and Fibre Fractions in Water Buffaloes kept under Subtropical Conditions

In the course of the ‘Livestock Revolution’, extension and intensification of, among others, ruminant livestock production systems are current phenomena, with all their positive and negative side effects. Manure, one of the inevitable secondary products of livestock rearing, is a valuable source of plant nutrients and its skillful recycling to the soil-plant interface is essential for soil fertility, nutrient - and especially phosphorus - uses efficiency and the preservation or re-establishment of environmentally sustainable farming systems, for which organic farming systems are exemplarily. Against this background, the PhD research project presented here, which was embedded in the DFG-funded Research Training Group 1397 ‘Regulation of soil organic matter and nutrient turnover in organic agriculture ’ investigated possibilities to manipulate the diets of water buffalo (Bubalus bubalis L.) so as to produce manure of desired quality for organic vegetable production, without affecting the productivity of the animals used. Consisting of two major parts, the first study (chapter 2) tested the effects of diets differing in their ratios of carbon (C) to nitrogen (N) and of structural to non-structural carbohydrates on the quality of buffalo manure under subtropical conditions in Sohar, Sultanate of Oman. To this end, two trials were conducted with twelve water buffalo heifers each, using a full Latin Square design. One control and four tests diets were examined during three subsequent 7 day experimental periods preceded each by 21 days adaptation. Diets consisted of varying proportions of Rhodes grass hay, soybean meal, wheat bran, maize, dates, and a commercial concentrate to achieve a (1) high C/N and high NDF (neutral detergent fibre)/SC (soluble carbohydrate) ratio (HH), (2) low C/N and low NDF/SC ratio (LL); (3) high C/N and low NDF/SC ratio (HL) and (4) low C/N and high NDF/SC (LH) ratio. Effects of these diets, which were offered at 1.45 times maintenance requirements of metabolizable energy, and of individual diet characteristics, respectively, on the amount and quality of faeces excreted were determined and statistically analysed. The faeces produced from diets HH and LL were further tested in a companion PhD study (Mr. K. Siegfried) concerning their nutrient release in field experiments with radish and cabbage. The second study (chapter 3) focused on the effects of the above-described experimental diets on the rate of passage of feed particles through the gastrointestinal tract of four randomly chosen animals per treatment. To this end, an oral pulse dose of 683 mg fibre particles per kg live weight marked with Ytterbium (Yb; 14.5 mg Yb g-1 organic matter) was dosed at the start of the 7 day experimental period which followed 21 days of adaptation. During the first two days a sample for Yb determination was kept from each faecal excretion, during days 3 – 7 faecal samples were kept from the first morning and the first evening defecation only. Particle passage was modelled using a one-compartment age-dependent Gamma-2 model. In both studies individual feed intake and faecal excretion were quantified throughout the experimental periods and representative samples of feeds and faeces were subjected to proximate analysis following standard protocols. In the first study the organic matter (OM) intake and excretion of LL and LH buffaloes were significantly lower than of HH and HL animals, respectively. Digestibility of N was highest in LH (88%) and lowest in HH (74%). While NDF digestibility was also highest in LH (85%) it was lowest in LL (78%). Faecal N concentration was positively correlated (P≤0.001) with N intake, and was significantly higher in faeces excreted by LL than by HH animals. Concentrations of fibre and starch in faecal OM were positively affected by the respective dietary concentrations, with NDF being highest in HH (77%) and lowest in LL (63%). The faecal C/N ratio was positively related (P≤0.001) to NDF intake; C/N ratios were 12 and 7 for HH and LL (P≤0.001), while values for HL and LH were 11.5 and 10.6 (P>0.05). The results from the second study showed that dietary N concentration was positively affecting faecal N concentration (P≤0.001), while there was a negative correlation with the faecal concentration of NDF (P≤0.05) and the faecal ratios of NDF/N and C/N (P≤0.001). Particle passage through the mixing compartment was lower (P≤0.05) for HL (0.033 h-1) than for LL (0.043 h-1) animals, while values of 0.034 h-1 and 0.038 h-1 were obtained for groups LH and HH. At 55.4 h, total tract mean retention time was significantly (P≤0.05) lower in group LL that in all other groups where these values varied between 71 h (HH) and 79 h (HL); this was probably due to the high dietary N concentration of diet LL which was negatively correlated with time of first marker appearance in faeces (r= 0.84, P≤0.001), while the dietary C concentration was negatively correlated with particle passage through the mixing compartment (r= 0.57, P≤0.05). The results suggest that manure quality of river buffalo heifers can be considerably influenced by diet composition. Despite the reportedly high fibre digestion capacity of buffalo, digestive processes did not suppress the expression of diet characteristics in the faeces. This is important when aiming at producing a specific manure quality for fertilization purposes in (organic) crop cultivation. Although there was a strong correlation between the ingestion and the faecal excretion of nitrogen, the correlation between diet and faecal C/N ratio was weak. To impact on manure mineralization, the dietary NDF and N concentrations seem to be the key control points, but modulating effects are achieved by the inclusion of starch into the diet. Within the boundaries defined by the animals’ metabolic and (re)productive requirements for energy and nutrients, diet formulation may thus take into account the abiotically and biotically determined manure turnover processes in the soil and the nutrient requirements of the crops to which the manure is applied, so as to increase nutrient use efficiency along the continuum of the feed, the animal, the soil and the crop in (organic) farming systems.

Two-dimensional Photonic Crystals Fabricated by Nanoimprint Lithography

We report on the process parameters of nanoimprint lithography (NIL) for the fabrication of two-dimensional (2-D) photonic crystals. The nickel mould with 2-D photonic crystal patterns covering the area up to 20mm² is produced by electron-beam lithography (EBL) and electroplating. Periodic pillars as high as 200nm to 250nm are produced on the mould with the diameters ranging from 180nm to 400nm. The mould is employed for nanoimprinting on the poly-methyl-methacrylate (PMMA) layer spin-coated on the silicon substrate. Periodic air holes are formed in PMMA above its glass-transition temperature and the patterns on the mould are well transferred. This nanometer-size structure provided by NIL is subjective to further pattern transfer.

Inverse Metabolic Engineering of Synechocystis PCC 6803 for Improved Growth Rate and Poly-3-hydroxybutyrate Production

Synechocystis PCC 6803 is a photosynthetic bacterium that has the potential to make bioproducts from carbon dioxide and light. Biochemical production from photosynthetic organisms is attractive because it replaces the typical bioprocessing steps of crop growth, milling, and fermentation, with a one-step photosynthetic process. However, low yields and slow growth rates limit the economic potential of such endeavors. Rational metabolic engineering methods are hindered by limited cellular knowledge and inadequate models of Synechocystis. Instead, inverse metabolic engineering, a scheme based on combinatorial gene searches which does not require detailed cellular models, but can exploit sequence data and existing molecular biological techniques, was used to find genes that (1) improve the production of the biopolymer poly-3-hydroxybutyrate (PHB) and (2) increase the growth rate. A fluorescence activated cell sorting assay was developed to screen for high PHB producing clones. Separately, serial sub-culturing was used to select clones that improve growth rate. Novel gene knock-outs were identified that increase PHB production and others that increase the specific growth rate. These improvements make this system more attractive for industrial use and demonstrate the power of inverse metabolic engineering to identify novel phenotype-associated genes in poorly understood systems.