Investigations on some technologically important polymer nanocomposite films and semi crystalline Polypyrrole films

The present work deals with investigations on some technologically important polymer nanocomposite films and semi crystalline polypyrrole films.The work presented in the thesis deals with the realization of novel polymer nanocomposites with enhanced functionalities and prospects of applications in the fields related to nanophotonics. The development of inorganic/polymer nanocomposites is a rapidly expanding multidisciplinary research area with profound industrial applications. The incorporation of suitable inorganic nanoparticles can endow the resulting nanocomposites with excellent electrical, optical and mechanical properties. The first chapter gives a general introduction to nanotechnology, nanocomposites and conducting polymers. It also emphasizes the significance of ZnO among other semiconductor materials, which forms the inorganic filler in the polymer nanocomposites of the present study. This chapter also gives general ideas on the properties and applications of conducting polymers with special reference to polypyrrole. The objectives of the present investigations are also clearly addressed in this chapter. The second chapter deals with the theoretical aspects and details of all the experimental techniques used in the present work for the synthesis of polymer nanocomposites and polypyrrole samples and their various characterizations. Chapter 3 is based on the preparation and properties of ZnO/Polystyrene nanocomposite film samples. The optical properties of these nanocomoposite films are discussed in detail.Chapter 4 deals with the detailed investigations on the dependence of the optical properties of ZnO/PS nanocomposite films on the size of the nanostructured ZnO filler material. The excellent UV shielding properties of these nanocomposite films form the highlight of this chapter. Chapter 5 gives a detailed analysis of the nonlinear optical properties of ZnO/PS nanocomposite films using Z scan technique. The effect of ZnO particle size in the composite films on the nonlinear properties is discussed. The present study involves two phases of research activities. In the first phase, the linear and nonlinear optical properties of ZnO/polymer nanocomposites are investigated in detail. The second phase of work is centered on the synthesis and related studies on highly crystalline polypyrrole films. In the present study, nanosized ZnO is synthesized using wet chemical method at two different temperatures

Hysteresis in a system driven by either generalized force or displacement variables: martensitic phase transition in single-crystalline Cu-Zn-Al

We report on experiments aimed at comparing the hysteretic response of a Cu-Zn-Al single crystal undergoing a martensitic transition under strain-driven and stress-driven conditions. Strain-driven experiments were performed using a conventional tensile machine while a special device was designed to perform stress-driven experiments. Significant differences in the hysteresis loops were found. The strain-driven curves show reentrant behavior yield point which is not observed in the stress-driven case. The dissipated energy in the stress-driven curves is larger than in the strain-driven ones. Results from recently proposed models qualitatively agree with experiments.

Molecular breakdown of different forms of natural rubber and its influence on properties of their mixes and vulcanizates

The forms of natural rubber studied were sheet [RSS 4 and RSS 5], ISNR 20 and EBC. In the case of the latter two forms samples from estate and nonestate sectors were included. The samples were collected from different locations at specified intervals, for a particular period. The effect of the extent of mastication on raw rubber properties as well as the properties of the compounds and vulcanizates also studied. The consistency in raw rubber properties and breakdown behavior of skim rubber were studied by collecting samples periodically from selected processing units. The effect of incorporation of skim with ISNR 20 has also been investigated

Studies On The Electrical Properties Of Some Crystalline Organic Compounds And Conducting Polymers

Solid electrolytes for applications like chemical sensing, energy storage, and conversion have been actively investigated and developed since the early sixties. Although of immense potential, solid state protonic conductors have been ignored in comparison with the great interest that has been shown to other ionic conductors like lithium and silver ion conductors. The non-availability of good, stable protonic conductors could be partly the reason for this situation. Although organic solids are better known for their electrical insulating character, ionic conductors of organic origin constitute a recent addition to the class of ionic conductors. However, detailed studies (N1 such conductors are scarce. Also the last decade has witnessed an unprecedented boom in research on organic "conducting polymers". These newly devised materials show conductivity spanning from insulator to metallic regimes, which can be manipulated by appropriate chemical treatment. They find applications in devices ranging from rechargeable batteries to "smart windows". This thesis mainly deals with the synthesis and investigations on the electrical properties of (i) certain organbc protonic conductors derived from ethylenediamine and (ii) substituted polyanilines

β-glucosidases from Aspergillus unguis NII 08123: Molecular characterization, properties and applications

Lignocellulosic biomass is probably the best alternative resource for biofuel production and it is composed mainly of cellulose, hemicelluloses and lignin. Cellulose is the most abundant among the three and conversion of cellulose to glucose is catalyzed by the enzyme cellulase. Cellulases are groups of enzymes act synergistically upon cellulose to produce glucose and comprise of endoglucanase, cellobiohydrolase and β-glucosidase. β -glucosidase assumes great importance due to the fact that it is the rate limiting enzyme. Endoglucanases (EG) produces nicks in the cellulose polymer exposing reducing and non reducing ends, cellobiohydrolases (CBH) acts upon the reducing or non reducing ends to liberate cellobiose units, and β - glucosidases (BGL) cleaves the cellobiose to liberate glucose completing the hydrolysis. . β -glucosidases undergo feedback inhibition by their own product- β glucose, and cellobiose which is their substrate. Few filamentous fungi produce glucose tolerant β - glucosidases which can overcome this inhibition by tolerating the product concentration to a particular threshold. The present study had targeted a filamentous fungus producing glucose tolerant β - glucosidase which was identified by morphological as well as molecular method. The fungus showed 99% similarity to Aspergillus unguis strain which comes under the Aspergillus nidulans group where most of the glucose tolerant β -glucosidase belongs. The culture was designated the strain number NII 08123 and was deposited in the NII culture collection at CSIR-NIIST. β -glucosidase multiplicity is a common occurrence in fungal world and in A.unguis this was demonstrated using zymogram analysis. A total 5 extracellular isoforms were detected in fungus and the expression levels of these five isoforms varied based on the carbon source available in the medium. Three of these 5 isoforms were expressed in higher levels as identified by the increased fluorescence (due to larger amounts of MUG breakdown by enzyme action) and was speculated to contribute significantly to the total _- β glucosidase activity. These isoforms were named as BGL 1, BGL3 and BGL 5. Among the three, BGL5 was demonstrated to be the glucose tolerant β -glucosidase and this was a low molecular weight protein. Major fraction was a high molecular weight protein but with lesser tolerance to glucose. BGL 3 was between the two in both activity and glucose tolerance.121 Glucose tolerant .β -glucosidase was purified and characterized and kinetic analysis showed that the glucose inhibition constant (Ki) of the protein is 800mM and Km and Vmax of the enzyme was found to be 4.854 mM and 2.946 mol min-1mg protein-1respectively. The optimumtemperature was 60°C and pH 6.0. The molecular weight of the purified protein was ~10kDa in both SDS as well as Native PAGE indicating that the glucose tolerant BGL is a monomeric protein.The major β -glucosidase, BGL1 had a pH and temperature optima of 5.0 and 60 °C respectively. The apparent molecular weight of the Native protein is 240kDa. The Vmax and Km was 78.8 mol min-1mg protein-1 and 0.326mM respectively. Degenerate primers were designed for glycosyl hydrolase families 1, 3 and 5 and the BGL genes were amplified from genomic DNA of Aspergillus unguis. The sequence analyses performed on the amplicons results confirmed the presence of all the three genes. Amplicon with a size of ~500bp was sequenced and which matched to a GH1 –BGL from Aspergillus oryzae. GH3 degenerate primers producing amplicons were sequenced and the sequences matched to β - glucosidase of GH3 family from Aspergillus nidulans and Aspergillus acculateus. GH5 degenerate primers also gave amplification and sequencing results indicated the presence of GH5 family BGL gene in the Aspergillus unguis genomic DNA.From the partial gene sequencing results, specific as well as degenerate primers were designed for TAIL PCR. Sequencing results of the 1.0 Kb amplicon matched Aspergillus nidulans β -glucosidase gene which belongs to the GH1 family. The sequence mainly covered the N-Terminal region of the matching peptide. All the three BGL proteins ie. BGL1, BGL3 and BGL5 were purified by chromatography an electro elution from Native PAGE gels and were subjected to MALDI-TOF mass spectrometric analysis. The results showed that BGL1 peptide mass matched to . β -glucosidase-I of Aspergillus flavus which is a 92kDa protein with 69% protein coverage. The glucose tolerant β -glucosidase BGL5 mass matched to the catalytic C-terminal domain of β -glucosidase-F from Emericella nidulans, but the protein coverage was very low compared to the size of the Emericella nidulans protein. While comparing the size of BGL5 from Aspergillus unguis, the protein sequence coverage is more than 80%. BGL F is a glycosyl hydrolase family 3 protein.The properties of BGL5 seem to be very unique, in that it is a GH3 β -glucosidase with a very low molecular weight of ~10kDa and at the same time having catalytic activity and glucose 122 tolerance which is as yet un-described in GH β -glucosidases. The occurrence of a fully functional 10kDA protein with glucose tolerant BGL activity has tremendous implications both from the points of understanding the structure function relationships as well as for applications of BGL enzymes. BGL-3 showed similarity to BGL1 of Aspergillus aculateus which was another GH3 β -glucosidase. It may be noted that though PCR could detect GH1, GH3 and GH5 β-glucosidases in the fungus, the major isoforms BGL1 BGL3 and BGL5 were all GH3 family enzymes. This would imply that β-glucosidases belonging to other families may also co-exist in the fungus and the other minor isoforms detected in zymograms may account for them. In biomass hydrolysis, GT-BGL containing BGL enzyme was supplemented to cellulase and the performances of blends were compared with a cocktail where commercial β- glucosidase was supplemented to the biomass hydrolyzing enzyme preparation. The cocktail supplemented with A unguis BGL preparation yielded 555mg/g sugar in 12h compared to the commercial enzyme preparation which gave only 333mg/g in the same period and the maximum sugar yield of 858 mg/g was attained in 36h by the cocktail containing A. unguis BGL. While the commercial enzyme achieved almost similar sugar yield in 24h, there was rapid drop in sugar concentration after that, indicating probably the conversion of glucose back to di-or oligosaccharides by the transglycosylation activity of the BGl in that preparation. Compared this, the A.unguis enzyme containing preparation supported peak yields for longer duration (upto 48h) which is important for biomass conversion to other products since the hydrolysate has to undergo certain unit operations before it goes into the next stage ie – fermentation in any bioprocesses for production of either fuels or chemicals.. Most importantly the Aspergillus unguis BGL preparation yields approximately 1.6 fold increase in the sugar release compared to the commercial BGL within 12h of time interval and 2.25 fold increase in the sugar release compared to the control ie. Cellulase without BGL supplementation. The current study therefore leads to the identification of a potent new isolate producing glucose tolerant β - glucosidase. The organism identified as Aspergillus unguis comes under the Aspergillus nidulans group where most of the GT-BGL producers belong and the detailed studies showed that the glucose tolerant β -glucosidase was a very low molecular weight protein which probably belongs to the glycosyl hydrolase family 3. Inhibition kinetic studies helped to understand the Ki and it is the second highest among the nidulans group of Aspergilli. This has promoted us for a detailed study regarding the mechanism of glucose tolerance. The proteomic 123 analyses clearly indicate the presence of GH3 catalytic domain in the protein. Since the size of the protein is very low and still its active and showed glucose tolerance it is speculated that this could be an entirely new protein or the modification of the existing β -glucosidase with only the catalytic domain present in it. Hydrolysis experiments also qualify this BGL, a suitable candidate for the enzyme cocktail development for biomass hydrolysis

Modification of Polypropylene/Polystyrene blend using Nanoclay and Sisal Cellulose nano fiber

Cochin University of Science and Technology

Femtosecond imaging-mode laser-induced breakdown spectroscopy

Many nonlinear optical microscopy techniques based on the high-intensity nonlinear phenomena were developed recent years. A new technique based on the minimal-invasive in-situ analysis of the specific bound elements in biological samples is described in the present work. The imaging-mode Laser-Induced Breakdown Spectroscopy (LIBS) is proposed as a combination of LIBS, femtosecond laser material processing and microscopy. The Calcium distribution in the peripheral cell wall of the sunflower seedling (Helianthus Annuus L.) stem is studied as a first application of the imaging-mode LIBS. At first, several nonlinear optical microscopy techniques are overviewed. The spatial resolution of the imaging-mode LIBS microscope is discussed basing on the Point-Spread Function (PSF) concept. The primary processes of the Laser-Induced Breakdown (LIB) are overviewed. We consider ionization, breakdown, plasma formation and ablation processes. Water with defined Calcium salt concentration is used as a model of the biological object in the preliminary experiments. The transient LIB spectra are measured and analysed for both nanosecond and femtosecond laser excitation. The experiment on the local Calcium concentration measurements in the peripheral cell wall of the sunflower seedling stem employing nanosecond LIBS shows, that nanosecond laser is not a suitable excitation source for the biological applications. In case of the nanosecond laser the ablation craters have random shape and depth over 20 µm. The analysis of the femtosecond laser ablation craters shows the reproducible circle form. At 3.5 µJ laser pulse energy the diameter of the crater is 4 µm and depth 140 nm for single laser pulse, which results in 1 femtoliter analytical volume. The experimental result of the 2 dimensional and surface sectioning of the bound Calcium concentrations is presented in the work.

High Density Single Crystalline GaN Nanodot Arrays Fabricated Using Template-Assisted Selective Growth

High density, uniform GaN nanodot arrays with controllable size have been synthesized by using template-assisted selective growth. The GaN nanodots with average diameter 40nm, 80nm and 120nm were selectively grown by metalorganic chemical vapor deposition (MOCVD) on a nano-patterned SiO2/GaN template. The nanoporous SiO2 on GaN surface was created by inductively coupled plasma etching (ICP) using anodic aluminum oxide (AAO) template as a mask. This selective regrowth results in highly crystalline GaN nanodots confirmed by high resolution transmission electron microscopy. The narrow size distribution and uniform spatial position of the nanoscale dots offer potential advantages over self-assembled dots grown by the Stranski–Krastanow mode.

Femtosecond laser processing of crystalline silicon

This paper reports the surface morphologies and ablation of crystalline silicon wafers irradiated by infra-red 775 nm Ti:sapphire femtosecond laser. The effects of energy fluences (below and above single-pulse modification) with different number of pulses were studied. New morphological features such as pits, cracks formation, Laser-Induced Periodic Surface Structures (LIPSS) and ablation were observed. The investigation indicated that there are two distinct mechanisms under femtosecond laser irradiation: low fluence regime with different morphological features and high fluence regime with high material removal and without complex morphological features.

Ordinary People in Extraordinary Times: The Citizenry and the Breakdown of Democracy by Nancy Bermeo

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Factors affecting foster care breakdown in Spain

La ruptura del acogimiento familiar se ha definido como aquella situación en la que alguna de las partes implicadas causa una terminación de la intervención antes de haber alcanzado los objetivos establecidos en el plan de caso. Este trabajo presenta un estudio llevado a cabo en una muestra española de 318 casos cerrados de niños que fueron acogidos en familia ajena y extensa. Los datos se obtuvieron a través de la revisión exhaustiva de los expedientes de protección y acogimiento, complementada con entrevistas a los técnicos encargados de cada caso. La tasa de ruptura del conjunto de la muestra fue de 26,1%, si bien fue significativamente diferente en familia extensa (19,7%) que en familia ajena (31,2%). Los resultados de este estudio indican que las variables relacionadas con la ruptura dependen de la modalidad del acogimiento, en familia ajena o extensa. En el primer caso destacamos las variables relacionadas con las características del niño, especialmente los problemas de conducta y escolares, con especial relevancia en el grupo de 9-12 años, y el haber estado en acogimiento residencial previamente. En cambio, en extensa resulta más importante la problemática en los padres (prisión, salud mental) y el tener una medida de tutela. También el hecho de que se realice el acogimiento tras pasar por hogares de acogida resulta trascendental. Finalmente, la disponibilidad de recursos económicos e incluso los estudios de los acogedores parecen ser variables relacionadas con la ruptura de la acogida