Studies on the Surface Properties and Catalytic Activity of Metal Chromites on Thermal Decomposition of Ammonium Perchlorate

Department of Applied Chemistry, Cochin University of Science and Technology

Photopyroelectric study of thermal properties and phase transitions in selected solids

This thesis presents in detail. the theoretical developments and calculations which are used for the simultaneous determination of thermal parameters, namely thermal diffusivity (a). thermal effusivity (e), thermal conductivity (K) and heat capacity (cr ) employing photopyroelectric technique. In our calculations. we have assumed that the pyroelectric detector is supported on a copper backing. so that there will be sufficient heat exchange between the heated pyroelectric detector and the backing so that the signal fluctuations are reduced to a minimum. Since the PPE signal depends on the properties of the detector that are also temperature dependent. a careful temperature calibration of the system need to be carried out. APPE cell has been fabricated for the measurements that can be used to measure the thermal properties of solid samples from ~ 90 K to ~ 350 K. The cell has been calibrated using standard samples and the accuracy of the technique is found to be of the order of± 1%.In this thesis, we have taken up work n photopyroelectric investigation of thermal parameters of ferroelectric crystals such as Glycine phosphite (NH3CH2COOH3P03), Triglycine sulfate and Thiourea as well as mixed valence perovskites samples such as Lead doped Lanthanum Manganate (Lal_xPb~Mn03) Calcium doped (Lal_xCaxMnOJ) and Nickel doped Lanthanum Stroncium Cobaltate (Lao~Sro5Ni,Col_x03).The three ferroelectric crystals are prepared by the slow evaporation technique and the mixed valence perovskites by solid state reaction technique.Mixed valence perovskites, with the general formula RI_xA~Mn03 (R = La. Nd or Pr and A = Ba, Ca, Sr or Pb) have been materials of intense experimental and theoretical studies over the past few years. These materials show . colossal magneloresis/ance' (CMR) in samples with 0.2 < x < 0.5 in such a doping region, resistivity exhibits a peak at T = T p' the metal - insulator transition temperature. The system exhibits metallic characteristics with d %T > Oabove Tp (wherep is the resistivity) and insulating characteristics with d % T < 0 above T p. Despite intensive investigations on the CMR phenomena and associated electrical properties. not much work has been done on the variation of thermal properties of these samples. We have been quite successful in finding out the nature of anomaly associated with thermal properties when the sample undergoes M-I transition.The ferroelectric crystal showing para-ferroelectric phase transitions - Glycine phosphite. Thiourea and Triglycine sulfate - are studied in detail in order to see how well the PPE technique enables one to measure the thermal parameters during phase transitions. It is seen that the phase transition gets clearly reflected in the variation of thermal parameters. The anisotropy in thermal transport along different crystallographic directions are explained in terms of the elastic anisotropy and lattice contribution to the thermal conductivity. Interesting new results have been obtained on the above samples and are presented in three different chapters of the thesis.In summary. we have carried investigations of the variations of the thermal parameters during phase transitions employing photopyroelectric technique. The results obtained on different systems are important not only in understanding the physics behind the transitions but also in establishing the potentiality of the PPE tool. The full potential of PPE technique for the investigation of optical and thermal properties of materials still remains to be taken advantage of by workers in this field.

Electrical properties and phase transitions in ethylenediammonium dinitrate

dc and ac electrical conductivities, dielectric constant and dielectric loss factor in single crystals of ethylenediammonium dinitrate (EDN) have been measured axiswise as a function of temperature. All the above properties exhibit anomalous variations at 404 K thereby confirming the occurence of a phase transition in EDN at this temperature. Electrical conductivity parameters have been evaluated and possible conduction mechanisms are discussed. The role of protons in electrical trasport phenomenon is established by chemical analysis.

Electrical conductivity, dielectric properties and phase transition in ethylenediammonium sulphate single crystals

D.C. and a.c. electrical conductivities, dielectric constant and dielectric loss factor in single crystals of ethylenediammonium sulphate, (H3NCH2CH2NH3)(SO4), have been measured axiswise as a function of temperature. Anomalous variations in all the above properties at 480 K indicate the occurrence of a phase transition in the above material at this temperature. The existence of such a phase transition is also confirmed by DSC measurements. Electrical conductivity results are analysed and the activation energies of conduction at different temperature regions have been evaluated from the logσ vs 103T−1 plot. Possible mechanisms for the electrical conduction process are discussed, the available results being in favour of a proton transport model.

Studies on Surface Properties and Catalytic Activity of Some Chromites and Related Spinels

The prime intension of the present work was a synthetic investigation of the preparation, surface properties and catalytic activity of some transition metal substituted copper chromite catalysts. Homogeneous co-precipitation method is employed for the preparation of catalysts. Since the knowledge about the structure and composition of the surface is critical in explaining the reactivity and selectivity of a solid catalyst. a systematic investigation of the physico-chemical properties of the prepared systems was carried out. The catalytic activity of these systems has also been measured in several oxidation reactions of industrial as well as environmental relevance. The thesis is dedicated to several aspects of chromite spinels giving emphasis to its preparation, characterization and catalytic performance towards oxidation reactions.

Influence of Si, Sb and Sr Additions on the Microstructure, Mechanical Properties and Corrosion Behavior of AZ91 Magnesium Alloy

All the exciting work on developing new and better alloys has led older alloys, such as AZ9l , being abandoned by researchers. lt is believed that the full potential of AZ9l in automotive design has not been realized. Whatever works have been carried out on AZ9lalloy to improve its mechanical properties are insufficient in terms of its potential usage in auto industries. Due to the fact that AZ91 offers high room temperature mechanical properties and good castability, still this alloy is a primary choice for the auto component manufactures. Small improvement in its creep properties will have a huge impact in the transportation industries. Hence, in the present work, “Influence of Si, Sb and Sr Additions on the Microstructure, Mechanical Properties and Corrosion Behavior of AZ91 Magnesium Alloy”, an attempt has been made to improve the creep properties of AZ9l alloy through minor alloying elemental additions and to understand its strengthening mechanisms. The effect of alloying additions on the ageing and tensile properties of AZ9l is also studied. In addition to that, role of various intermetallics formed due to the alloying additions on the corrosion properties of AZ9l alloy is investigated.

Studies on the Production, Properties and Processability of Low Protein Latex

Latex protein allergy is a serious problem faced by users of natural rubber latex products. This is severe in health care workers, who are constantly using latex products like examination gloves, surgical gloves etc. Out of the total proteins only a small fraction is extractable and only these proteins cause allergic reactions in sensitized people. Enzymic deproteinisation of latex and leaching and chlorination of latex products are the common methods used to reduce the severity of the problem.Enzyme deproteinisation is a cubersome process involving high cost and process loss.Physical properties of such films are poor. Leaching is a lengthy process and in leached latex products presence of extractable proteins is observed on further storing. Chlorination causes yellowing of latex products and reduction in tensile properties.In this context a more simple process of removal of extractable proteins from latex itself was investigated. This thesis reports the application of poly propylene glycol (PPG) to displace extractable proteins from natural latex. PPG is added to 60 % centrifuged natural latex to the extent of 0.2 % m/rn, subssequently diluted to 30 % dry rubber content and again concentrated to obtain a low protein latex.Dilution of concentrated latex and subsequent concentration lead to a total reduction in non - rubber solids in the concentrate, especially proteins and reduction in the ionic concentration in the aqueous phase of the latex. It has been reported that proteins in natural rubber / latex affect its behaviour in the vulcanisation process. Ionic concentration in the aqueous phase of latex influence the stability, viscosity and flow behaviour of natural latex. Hence, a detailed technological evaluation was carried out on this low protein latex. In this study, low protein latex was compared with single centrifuged latex ( the raw material to almost every latex product), double centrifuged latex ( because dilution and second concentration of latex is accompanied by protein removal to some extent and reduction in the ionic concentration of the aqueous phase of latex.). Studies were conducted on Sulphur cure in conventional and EV systems under conditions of post ~ cure and prevulcanisation of latex. Studies were conducted on radiation cure in latex stage. Extractable protein content in vulcanised low protein latex films are observed to be very low. lt is observed that this low protein latex is some what slower curing than single centrifuged latex, but faster than double centrifuged latex. Modulus of low protein latex films were slightly low. In general physical properties of vulcanised low protein latex films are only siightly lower than single centrifuged latex. Ageing properties of the low protein latex films were satisfactory. Viscosity and flow behaviour of low protein latex is much better than double centrifuged latex and almost comparable to single centrifuged latex. On observing that the physical properties and flow behaviour of low protein latex was satisfactory, it was used for the preparation of examination gloves and the gloves were evaluated. It is observed that the properties are conforming to the Indian Standard Specifications. It is thus observed that PPG treatment of natural latex is a simple process of preparing low protein latex. Extractable protein content in these films are very low.The physical properties of the films are comparable to ordinary centrifuged latex and better than conventionally deprotenized latex films. This latex can be used for the production of examination gloves.

Surface electron properties and catalytic activity of rare earth oxides

The rare earths have provided fascinating field for chemists confronted with problems of their separation and purification. The rare earths become available in relatively pure form in recent years due to the development of efficient separation methods, largely as a byproduct of the atomic energy programmes of various countries. The rare earths often called lanthanides from La (Z=57) to Lu (Z=7l) display subtle variation of properties through the series, while the differences become appreciable for the elements that are farther apart.

Electrical properties and phase transitions insome ammonium containing ferroelectrics

The thesis aims to present the results of the experimental investigations on the electrical properties like electrical conductivity, dielectric constant and ionic thermo~ currents in certain ammonium containing ferroelectric crystals viz. LiNH4SO4, (NH4)2SO4 and (NH4)5H(SO4)2. Special attention has been paid in revealing the mechanisms of electrical conduction in the various phases of these crystals and those asso~ ciated with the different phase transitions occurring in them, by making studies on doped, quenched and deuterated crystals. The report on the observation of two new phase transitions in (NH4) S O2 and of a similar one in ( NH4 ) H (2SO4 ) are included. The relaxation mechanisms of the impurity-vacancy complexes and the space charge phenomena in pure and doped crystals of LiNH4SO4 and (NH4)2SO4 and the observation of a new type of ionic thermo-current viz. Protonic Thermo-Current (PTC) in these crystals are also presented here.

Study of chemical properties and evaluation of collagen in mantle, epidermal connective tissue and tentacle of Indian Squid, Loligo duvauceli Orbigny

The chemical composition and evaluation of Indian squid (Loligo duvauceli) mantle, epidermal connective tissue and tentacle is investigated in this current study. It is observed that squid mantle contains 22.2% total protein; 63.5% of the total protein is myofibrillar protein. The unique property of squid myofibrillar protein is its water solubility. Squid mantle contains 12.0% total collagen. Epidermal connective tissue has highest amounts of total collagen (17.8%). SDS-PAGE of total collagen identified high molecular weight α-, β- and γ- sub-chains. Amino acid profile analysis indicates that mantle and tentacle contain essential amino acids. Arginine forms a major portion of mantle collagen (272.5 g/100 g N). Isoleucine, glutamic acid and lysine are other amino acids that are found in significantly high amounts in the mantle. Sulphur containing cystine is deficit in mantle collagen. Papain digest of mantle and epidermal connective tissue is rich in uronic acid, while papain digest, collagenase digest and urea digest of epidermal connective tissue has significant amounts of sialic acid (25.2, 33.2 and 99.8 μmol /100 g, respectively). PAS staining of papain digest, collagenase digest and urea digest also identify the association of hexoses with low molecular weight collagen fragments. Histochemical sectioning also emphasized the localized distribution of collagen in epidermal and dermal region and very sparse fibres traverse the myotome bundles

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

Causes and Effects of Chaos

Most of the recent literature on chaos and nonlinear dynamics is written either for popular science magazine readers or for advanced mathematicians. This paper gives a broad introduction to this interesting and rapidly growing field at a level that is between the two. The graphical and analytical tools used in the literature are explained and demonstrated, the rudiments of the current theory are outlined and that theory is discussed in the context of several examples: an electronic circuit, a chemical reaction and a system of satellites in the solar system.

Synthesis, Optical properties and Applications of Water Soluble Conjugated PPPs for Biosensors

In recent years, application of fluorescent conjugated polymers to sense chemical and biological analytes has received much attention owing to its technological significance. Water soluble conjugated polymers are interesting towards the developing sensors for biomolecules. In this present contribution, we describe the syntheses and characterization of a series of water soluble conjugated polymers with sulfonic acid groups in the side chain. Such anionic conjugated polymers are designed to interact with biomolecules such as cytochrome-C. All polymers are water soluble and showed strong blue emission. Significant quenching of the fluorescence from our functionalized PPP was observed upon addition of viologen derivatives or cytochrome -C.