The main focus of this thesis is in understanding the role of phase separation and microstructure in determining the physical properties of manganites. We also aim to be able to tune certain material properties using appropriate control mechanisms. For this, an understanding of the local electronic properties of manganites is essential. We thus set out to study the local electronic states in manganites using a highly sensitive probe: the scanning tunneling microscope (STM). The chapter 1 of the thesis gives an introduction to manganites, and of how manganites are susceptible to various perturbations due to closely lying ground states and an intricate interplay of their charge, spin and lattice degrees of freedom. Chapter 2 of this thesis gives a detailed account of various experimental methods used in the current investigation. In particular, we describe the design and fabrication of a variable temperature ultra-high vacuum scanning tunneling microscope (UHV-STM) which was used to carry out spatially resolved measurements on various manganite systems. This chapter also describes sample fabrication techniques by which strain and microstructure of thin films can be controlled. Other characterization techiniques, such as tranport and magnetotransport measurements, are also described in detail. Chapter 3 presents our investigation of the role of microstructure and phase separation on the DOS and local electronic properties of manganite thin films. We describe various spatially resolved STM/STS measurements carried out on La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3 films having different micrsotructure and varying degrees of phase separation. We also present a theoretical model used in interpreting STS data to account for finite temperature effects and explain the existing data in this context. We use this model to gain insight into the behaviour of the DOS at EF near the MIT where thermal smearing can often give rise to misleading inferences. Chapter 4 presents our investigation on the density of states in a typical charge ordered manganite system, Pr1-xCaxMnO3. We describe STS measurements carried out on this system to study the occurrence and evolution of the charge ordering (CO) gap as a function if temperature as well as tunneling current. We report the observation of destabilization of the CO gap using tunnel current injection by an STM tip. Chapter 5 presents our investigation into the controlled and localized “nanoscale” phase separation in Pr1-xCaxMnO3 (PCMO) using an STM tip. The investigations were carried out on PCMO single crystal and PCMO epitaxial films. Our results raise the possibility of nano-fabrication of metallic nanoislands in a CO matrix using an STM tip. We demonstrate some examples of this and also raise the relevance of intrinsic phase separation in this context. We show that the “melting” of CO using tunnel current injection by an STM tip is analogous to the magnetic field-induced melting of CO on a microscopic scale. Chapter 6 summarizes the important results of this thesis work and suggests the scope for future experiments.

The thesis entitled “In situ crystallography and charge density analysis of phase transitions in complex inorganic sulfates” consists of six chapters. Structural changes exhibited by ferroic and conducting materials are studied as a function of temperature via in situ crystallography on the same single crystal. These unique experiments bring out the changes in the crystal system resulting in subtle changes in the complex polyhedra, distortions in bond lengths and bond angles, rotation of sulfate tetrahedral around metal atoms, phase separations and charge density features. The results provide new insights into the structural changes during the phase transition in terms of coordination changes, variable bond paths and variability in electrostatic potentials while suggesting possible reaction pathways hitherto unexplored. Chapter 1 gives a brief review of the basic features of structural phase transitions in terms of types of phase transitions, their mechanisms and related properties and outlines some of the key characterization techniques employed in structural phase transition studies like single crystal diffraction, thermal analysis, conductivity, dielectric relaxation, Raman spectroscopy and charge density studies. Chapter 2 deals with the group of compounds A3H(SO4)2, where A= Rb, NH4, K, Na which undergoes ferroelastic to paraelastic phase transitions with increase in temperature. Crystal structures of these compounds have been determined to a high degree of accuracy employing the same single crystal at room temperature at 100K and at higher temperatures. The data collection at 100K allows the examination of the ordered and disordered hydrogen atom positions. Rb3H(SO4)2 show two intermediate phases before reaching the paraelastic phase with increase in temperature. However, in case of (NH4)3H(SO4)2 and K3H(SO4)2, the paraelastic phase transition involves a single step. Chapter 3 deals with variable temperature in situ single crystal X-ray diffraction studies on fast super protonic conductors AHSO4, where A= Rb, NH4, K to characterize the structural phase transitions as well as the dehydration mechanism. The structure of KHSO4 at room temperature belongs to an orthorhombic crystal system with the space group symmetry Pbca and on heating to 463K it transforms to a C centered orthorhombic lattice, space group Cmca. The high temperature structure contain two crystallographically independent units of KHSO4 of which one KHSO4 unit is disordered at oxygen and hydrogen sites an shows a remarkable increase of sulfur oxygen bond distance – 1.753(4)Å. On heating to 475K, two units of disordered KHSO4 combine and loose one molecule of water to result in a structure K2S2O7 along with an ordered KHSO4 in a monoclinic system [space group P21/c]. On further heating to 485K two units of ordered KHSO4 combine, again to lose one water molecule to give K2S2O7 in a monoclinic crystal system [space group C2/c]. In the case of RbHSO4, both the high temperature structural phase transition and a serendipitous polymorph have been characterized by single crystal X-ray diffraction. The room temperature structure is monoclinic, P21/n, and on heating the crystal insitu On the diffractometer to 460K the structure changes to an orthorhombic system [space group Pmmn]. On keeping the crystallization temperature at 80°C polymorph crystals of RbHSO4 were grown. In case of NH4HSO4 both the room temperature and high temperature structures are structurally similar to those in RbHSO4, but the transition temperature is found to be 413K. Chapter 4 deals with the crystal structure, ionic conduction, dielectric relaxation, Raman spectroscopy phase transition pf a fast ion conductor Na2Cd(SO4)2. The structure is monoclinic, space group C2/c, and is built up with inter connecting CdO6 octahedra and SO4 tetrahedra resulting in a framework structure. The mobile Na atoms are present in the framework, resulting in a high ionic conductivity. The conductivity measurement shows two phase transitions one at around 280°C, which was confirmed later from DTA, dielectric relaxation, high temperature powder diffraction and Raman spectroscopy. Chapter 5 describes the structure and in situ phase separation in two different bimetallic sulfates Na2Mn1.167(SO4)2S0.33O1.1672H2O and K4Cd3(SO4)5.3H2O. These compounds were synthesized keeping them as mimics of mineral structures. The structure of Na2Mn1.167(SO4)2S0.33O1.1672H2O is trigonal, space group R . The stiochiometry can be viewed as a combination of Na2Mn(SO4)22H2O resembling the mineral Krohnkite with an additional (Mn0.167S0.333O1.167) motif. On heating the parent compound on the diffractometer to 500K and keeping the capillary at this temperature for one hour, a remarkable structural phase separation occurs with one phase showing a single crystal-single crystal transition and the other generating a polycrystalline phase. The resulting single crystal spots can be indexed in a monoclinic C2/c space group and the structure determination unequivocally suggests the formation of Na2Mn(SO4)2, isostructural to Na2Cd(SO4)z. The mechanism follows the symmetry directed pathway from the rhombohedral → monoclinic symmetry with the removal of symmetry subsequent to the loss of the two coordinated water molecules. In case of K4Cd3(SO4)5.3H2O the structure belongs to the space group P21/n at room temperature and on heating to 500K and holding the capillary at this temperature for 60 minutes as before, the CCD images can be indexed in a cubic P213 space group after the phase separation, generating K2Cd2(SO4)3, belonging to the well known Langbeinite family, while the other phase is expected to be the sought after K2Cd(SO4)2. The possible pathways have been discussed. Chapter 6 reports the charge density studies of phase transitions in a type II langbeinite, Rb2Mn2(SO4)3. The structure displays two different phases, cubic at 200K, orthorhombic at 100K respectively. After multiple refinements it is found that there are significant differences in the actual bond path (Rij) and the conventional bond length. In the cubic phase the distortions in sulfate tetrahedral are more than in the orthorhombic phase which could be the expected driving force for the phase transition to occur. Appendix contains reprints of the work done on the structures of the following: a) Rb2Cd3(SO4)3(OH)2.2H2O: structural stability at 500 K b) Structure of (NH4)2Cd3(SO4)4.5H2O c) Structure of Rb2Cd3(SO4)4.5H2O

With the age of hypersonic flight imminent just beyond the horizon, researchers are working hard at designing work-arounds for all the major problems as well as the minor quirks associated with it. One such issue, seemingly innocuous but one that could be potentially deadly, is the problem of interference heating due to surface protuberances. Although an ideal design of the external surfaces of a high-speed aircraft dictates complete smoothness to reduce drag, this is not always possible in reality. Control surfaces, sheet joints, cable protection pads etc. generate surface discontinuities of varying geometries, in the form of both protrusions as well as cavities. These discontinuities are most often small in dimension, comparable to the local boundary layer thickness at that location. Such protuberances always experience high rates of heat transfer, and therefore should be appropriately shielded. However, thermal shielding of the protrusions alone is not a full solution to the problem at hand. The interference caused to the boundary layer by the flow causes the generation of local hot spots in the vicinity of the protuberances, which should be properly mapped and adequately addressed. The work presented in this thesis aims at locating and measuring the heat flux values at these hot spots near the protrusions, and possibly formulating empirical correlations to predict the hot spot heat flux for a given set of flow conditions and protrusion geometry. Experimental investigations were conducted on a flat plate model and a cone model, with interchangeable sharp and blunt nose tips, with attached 3D protuberances. Platinum thin-film sensors were placed around the protrusion so that the heat fluxes could be measured in its vicinity and the hottest spot located. These experiments were carried out at five different hypersonic free stream flow conditions generated using two shock tunnels, one of the conventional type, and the other of the free-piston driven type. The geometry of the protrusions, i.e., the height and the deflection angle, was also parametrically varied to study its effect on the hot spot heat flux. The results thus obtained for the flat plate case were compared to existing correlations in the open literature from a similar previous study at a much higher Reynolds number range. Since a mismatch was observed between the results of the current experiments and the existing correlations, a new empirical correlation has been developed to predict the hot spot heat flux, that is valid within the range of flow conditions studied here. A similar attempt was made for the case of the cone model, for which no previous correlations exist in the open literature. However, a global correlation covering the entire range of flow conditions used here could not be formed. A correlation that is valid for just one out of the five flow conditions used here is presented for the cones with sharp and blunt nose tips separately. Schlieren flow visualization was carried out to obtain a better understanding of the shock structures near the protuberances on both models. For most cases, where the protrusion height and deflection angle were large enough to cause flow separation immediately upstream of the protuberance, a separation shock was manifested which deflected some part of the boundary layer above the protuberance, while the rest of the fluid in the boundary layer entered a recirculating region in the separated zone before escaping to the side. Some preliminary computational analysis was conducted which confirmed this qualitatively. However, the quantitative match of surface heat flux between the simulations and experiments were not encouraging. Schlieren visualization revealed that for the flat plate case, the foot of the separation shock was located at a distance of 10.5 to 12 times the protrusion height ahead of it, whereas in the case of the sharp cone, it was at a distance of 9 to 10.5 times the protrusion height. The unsteady nature of the separation shock was also captured and addressed. Some preliminary experiments on boundary layer tripping were also conducted, the results of which have been presented here. From this analysis, it has become evident that a single global correlation cannot be formed which could be used for a wide range of flow conditions to predict the hot spot heat flux in interference interactions. The entire range of conditions that may be encountered during hypersonic flight has to be broken down into sections, and the interference heating pattern should be studied in each of these sections individually. By doing so, a series of different correlations can be formed at the varying flow conditions which will then be available for high-speed aircraft designers.

Cell cycle regulation is an important part for the detection and destruction of mutated and dysregulated cells as it is a natural protection against degenerative diseases and cancer. The ability of the body to detect and destroy these cells is a vital part in maintaining homeostasis in the body. Once cells have circumvented this line of defence, dismantling these cells would become very difficult.  Research into new ways to target and destroy mutated cells are constantly evolving in hopes of being able to control and direct lysis of target cells using therapeutic drugs. One of the possibilities for such a method are Cholesterol Dependent Cytolysins (CDC), specific proteins found in bacteria. These proteins are dependent on the ability to bind to cholesterol in cell-walls to form pores that lyse and effectively destroy cells.   This project aims to study the structure and mechanistic details of pore formation by CDC mitilysin using cryogenic electron microscopy (cryo-EM). Mitilysin was purified by affinity chromatography and its pore formation ability was confirmed by calcein release assay and hemolysis assay. The pore structures of mitilysin were observed by transmission electron microscopy (TEM) using liposomes composed of both 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and cholesterol as model membranes. Detergent screening directed separation of pores from liposomes; so that they could be visualized by cryo-EM. While these steps were optimized and proven successful, they were time-consuming. An initial 3D-model of pore-structures was rendered, but no molecular characteristics could be determined at the end of the allotted time. The study does lay the ground steps for obtaining the complete structure of mitilysin pores.