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- Title
- STUDIES ON CONNECTIVE AND NEUROLOGICAL TISSUES IN RELATION TO DISEASE
- Creator
- Madhurapantula, Rama Sashank
- Date
- 2015, 2015-12
- Description
-
The structure of connective tissue is of great importance for homeostasis of the cells present within it. Pathologies leading to changes in...
Show moreThe structure of connective tissue is of great importance for homeostasis of the cells present within it. Pathologies leading to changes in the structure of the extracellular matrix (ECM), in particular collagen have been shown to play a pivotal role in the progression of various diseases. Similarly, changes in the structure of specific elements in neurological tissues, such as myelin, have been shown to elicit adverse responses to injury. This thesis explores two main aspects: 1) the structural changes brought about by high sugar concentrations, much similar to that found in diabetic patients, to the structure of type I collagen and 2) possible effects of traumatic brain injury (TBI) to the structure of neurons in rat brains. Specific changes in the structure and packing of collagens in various tissues could be potential therapeutic targets to control the progression of related diseases. However, the information available on the nature, specificity and the relevance of these changes at a molecular level are largely unknown and have been explored only sparsely. The result of non-enzymatic glycosylation i.e. glycation, is the formation of sugar- mediated crosslinks within the native structure of type I collagen. The chemistry behind these crosslinks, also known as Advanced Glycation Endproducts (AGEs), has been known for decades. However, the exact locations or regions of high propensity for the formation of these crosslinks within the packing structure of collagen are largely unknown. The results presented in this thesis inform on the location of possible crosslinks using the principle of Multiple Isomorphic Replacement (MIR) to and correlate the effects of crosslinks to the structural and functional sites present on the D-periodic arrangement of collagen into fibrils. An extension to this is the study of the effects of povidone-iodine on the packing structure of collagen. Iodine is used as a common disinfectant in surgery and first aid. Prolonged treatment with iodine is detrimental to the structure of collagen underlying the wound site (surgical or otherwise). This is particularly important in large surface area wounds, as seen in open-heart, hip and joint replacement surgeries and amputations. Diabetic patients are more prone to injuries to limb extremities and a common procedure to stop infections from spreading to the rest of the body is amputation of the limb and constant treatment with low doses of iodine immediately following surgery for a certain length of time. The results presented in this thesis demonstrate specific disintegration of collagen fibrils in rat tail tendons, from a short iodine treatment. This is detrimental for cellular activity, more so in processes like wound healing. TBI results in the loss of neurological control and/or function of various parts of the body, governed by this region. The results presented herein, inform and support the finding that neuroplasticity, in the hemisphere opposite to that where injury was delivered, compensates for the functional deficits as a result of TBI. The data presented here can be used in developing rehabilitation regimens for TBI patients on case-to-case basis to restore most of the functional deficits observed thereof, and also as a factor of predicting the onset of secondary neurological disorders (for instance amyloid related pathologies) at a later stage in life.
Ph.D. in Biology, December 2015
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- Title
- Structural Studies of Degradation Mechanism of Lithium Rich Manganese, Nickel, and Iron Based Cathodes
- Creator
- Aryal, Shankar
- Date
- 2018
- Description
-
Layered oxide compounds are superior with respect to discharge voltage and discharge specific capacity compared to other families of cathodes....
Show moreLayered oxide compounds are superior with respect to discharge voltage and discharge specific capacity compared to other families of cathodes. Therefore, LiCoO2 and LiMnxNiyCozO2, are the most commonly used cathodes since the commercialization of lithium ion battery. Recently, Li rich Ni, Mn, and Co oxide composite cathodes have been introduced with some improvements. As Co is toxic and expensive, attempts have been made to replace Co with cheap and environmentally friendly Fe. This dissertation reports that comparable discharge specific capacity and discharge voltage can be achieved by replacing Co with Fe and optimizing the composition of Mn, Ni, and Fe. However, the capacity and voltage fading on cycling are still remaining challenges. Structural change on electrochemical cycling is the main reason behind this fading. X-ray absorption spectroscopy (XAS), the specific element probe technique to study local structure and X-ray diffraction (XRD) to study the crystallographic phase information are utilized to understand the degradation/aging mechanism. A series of Li rich Mn, Ni, and Fe oxide composite cathode materials Li1.2Mn(0.30+x)Ni(0.40-x)Fe0.10O2 for x = 0, 0.05, 0.10, 0.15, 0.20 and 0.25 were prepared using a sol-gel synthesis method. Rhombohedral and monoclinic crystal phases are found in Li rich Mn, Ni, and Fe composite oxide materials, but pure rhombohedral phase cannot be obtained without excess Li in the stoichiometric LiMO2 form. The pure monoclinic phase Li2MnO3 is also synthesized to confirm its presence in the composite oxide cathodes. Particle size and surface morphology are studied with scanning electron microscopy. The composite cathodes are cycled to over 100 cycles at 0.3C, for C = 250 mAhg-1 rate. XAS before and after 100 electrochemical cycles of Li rich Mn-Ni-Fe based cathodes is reported for the first time. The determination of fractional contents of monoclinic and rhombohedral phases in the composite oxide cathodes is not possible by powder XRD analysis, however, Li2MnO3 content decreases on decreasing Mn content and on increasing Ni content. The composition with higher Ni content has a higher degree of cation mixing. The synergistic effect of rhombohedral and monoclinic phases in Li rich Mn, Ni, and Fe based cathode is critical for stable electrochemical performance. The Li1.2Mn0.50Ni0.20Fe0.10O2 cathode showed the most stable cyclability performance (194 mAhg-1 first discharge capacity with 94 % capacity retention after 100 cycles at 0.3C rate) however, Li1.2Mn0.40Ni0.30Fe0.10O2 (220 mAhg-1 first discharge capacity with 57 % capacity retention) and Li1.2Mn0.55Ni0.15Fe0.10O2 (241 mAhg-1 first discharge capacity with 68 % capacity retention) cathodes showed higher 1st discharge capacity but poor cyclability under the same charge/discharge cycling.The XAS at Mn K-edge is used to explain the mechanism of Li2MnO3 activation for the improved electrochemical performance of Li rich Mn, Ni, and Fe oxide composite cathode, however Li2MnO3 contributed differently in different compositions. Synchrotron XRD and XAS measurements probed the lattice size expansion, which decreases the chemical potential of Li ions in the cathode on cycling leading to lower discharge voltage after cycling.
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- Title
- DOPING OF SODIUM CHROMIUM OXIDE CATHODE MATERIALS TO ENHANCE ELECTROCHEMICAL PERFORMANCE FOR SODIUM-ION BATTERIES
- Creator
- wang, ziyong
- Date
- 2019
- Description
-
In this project, we investigated the effects of doping several types of metals to NaCrO2 on its electrochemical performance. The doping method...
Show moreIn this project, we investigated the effects of doping several types of metals to NaCrO2 on its electrochemical performance. The doping method is aiming to stabilize the O3-type structure by partial substituting some of Cr with other metals during intercalation/deintercalation by suppressing Cr6+ migration to alkaline slab, and thus facilitate long-term cycle performance and reversible capacity. All doped NaCrO2 powders were hereby denoted to NaMe0.1Cr0.9O2 (Me=Al, Co, Ni, Mn). To achieve metal-doped NaCrO2 powders, sodium, chromium and dopant sources were mixed with various metal oxides and then subjected to 6-hour high energy ball milling, followed by heating in flow-Ar tube at 900℃ for 1 hour. Pristine NaCrO2 powder synthesized in the same process was to make comparisons with doped ones. To understand the mechanism of doping, field emission scanning microscopy (FESM) and energy Disperse Spectroscopy (EDS), as well as X-ray diffractometer (XRD), were employed to analyze the morphology and composition of final products. Benefiting from Ni doping, NaNi0.1Cr0.9O2 cell exhibited a high reversible capacity of 132 mAh g-1 at the initial cycle in a potential region between 2.0 and 3.6 V vs. Na/Na+, and 78 % of capacity retention over 70 cycles. For NaMn0.1Cr0.9O2, reversible capacity at first discharge is about 30 mAh g-1, lower than that of Ni-doped and pristine NaCrO2, while the cycle retention stays at nearly 100% after 100 cycles. The opposite charge/discharge behaviors from Ni- and Mn-doped NaCrO2 provide us a potential method for the optimization of cathode materials with the best electrochemical performance in the future.
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