Anisotropy of spin relaxation of water protons in cartilage and tendon

Transverse spin relaxation rates of water protons in articular cartilage and tendon depend on the orientation of the tissue relative to the applied static magnetic field. This complicates the interpretation of magnetic resonance images of these tissues. At the same time, relaxation data can provide information about their organisation and microstructure. We present a theoretical analysis of the anisotropy of spin relaxation of water protons observed in fully hydrated cartilage. We demonstrate that the anisotropy of transverse relaxation is due almost entirely to intramolecular dipolar coupling modulated by a specific mode of slow molecular motion: the diffusion of water molecules in the hydration shell of a collagen fibre around the fibre, such that the molecular director remains perpendicular to the fibre. The theoretical anisotropy arising from this mechanism follows the “magic-angle” dependence observed in magnetic-resonance measurements of cartilage and tendon and is in good agreement with the available experimental results. We discuss the implications of the theoretical findings for MRI of ordered collagenous tissues.

Thermogravimetric analysis-mass spectrometry (TG-MS) of selected Chinese kaolinites

Thermogravimetric analysis-mass spectrometry, X-ray diffraction and scanning electron microscopy (SEM) were used to characterize eight kaolinite samples from China. The results show that the thermal decomposition occurs in three main steps (a) desorption of water below 100 °C, (b) dehydration at about 225 °C, (c) well defined dehydroxylation at around 450 °C. It is also found that decarbonization took place at 710 °C due to the decomposition of calcite impurity in kaolin. The temperature of dehydroxylation of kaolinite is found to be influenced by the degree of disorder of the kaolinite structure and the gases evolved in the decomposition process can be various because of the different amount and kinds of impurities. It is evident by the mass spectra that the interlayer carbonate from impurity of calcite and organic carbon is released as CO2 around 225, 350 and 710 °C in the kaolinite samples.

Investigation of 'off-line‘ relaxation phenomena in oil filled transformers

Power transformers are one of the most important and costly equipment in power generation, transmission and distribution systems. Current average age of transformers in Australia is around 25 years and there is a strong economical tendency to use them up to 50 years or more. As the transformers operate, they get degraded due to different loading and environmental operating stressed conditions. In today‘s competitive energy market with the penetration of distributed energy sources, the transformers are stressed more with minimum required maintenance. The modern asset management program tries to increase the usage life time of power transformers with prognostic techniques using condition indicators. In the case of oil filled transformers, condition monitoring methods based on dissolved gas analysis, polarization studies, partial discharge studies, frequency response analysis studies to check the mechanical integrity, IR heat monitoring and other vibration monitoring techniques are in use. In the current research program, studies have been initiated to identify the degradation of insulating materials by the electrical relaxation technique known as dielectrometry. Aging leads to main degradation products like moisture and other oxidized products due to fluctuating thermal and electrical loading. By applying repetitive low frequency high voltage sine wave perturbations in the range of 100 to 200 V peak across available terminals of power transformer, the conductive and polarization parameters of insulation aging are identified. An in-house novel digital instrument is developed to record the low leakage response of repetitive polarization currents in three terminals configuration. The technique is tested with known three transformers of rating 5 kVA or more. The effects of stressing polarization voltage level, polarizing wave shapes and various terminal configurations provide characteristic aging relaxation information. By using different analyses, sensitive parameters of aging are identified and it is presented in this thesis.

Properties of lignin and poly(hydroxybutyrate) blends

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of Seven published/submitted papers and one poster presentation, of which five have been published and the other two are under review. This project is financially supported by the QUTPRA Grant. The twenty-first century started with the resurrection of lignocellulosic biomass as a potential substitute for petrochemicals. Petrochemicals, which enjoyed the sustainable economic growth during the past century, have begun to reach or have reached their peak. The world energy situation is complicated by political uncertainty and by the environmental impact associated with petrochemical import and usage. In particular, greenhouse gasses and toxic emissions produced by petrochemicals have been implicated as a significant cause of climate changes. Lignocellulosic biomass (e.g. sugarcane biomass and bagasse), which potentially enjoys a more abundant, widely distributed, and cost-effective resource base, can play an indispensible role in the paradigm transition from fossil-based to carbohydrate-based economy. Poly(3-hydroxybutyrate), PHB has attracted much commercial interest as a plastic and biodegradable material because some its physical properties are similar to those of polypropylene (PP), even though the two polymers have quite different chemical structures. PHB exhibits a high degree of crystallinity, has a high melting point of approximately 180°C, and most importantly, unlike PP, PHB is rapidly biodegradable. Two major factors which currently inhibit the widespread use of PHB are its high cost and poor mechanical properties. The production costs of PHB are significantly higher than for plastics produced from petrochemical resources (e.g. PP costs $US1 kg-1, whereas PHB costs $US8 kg-1), and its stiff and brittle nature makes processing difficult and impedes its ability to handle high impact. Lignin, together with cellulose and hemicellulose, are the three main components of every lignocellulosic biomass. It is a natural polymer occurring in the plant cell wall. Lignin, after cellulose, is the most abundant polymer in nature. It is extracted mainly as a by-product in the pulp and paper industry. Although, traditionally lignin is burnt in industry for energy, it has a lot of value-add properties. Lignin, which to date has not been exploited, is an amorphous polymer with hydrophobic behaviour. These make it a good candidate for blending with PHB and technically, blending can be a viable solution for price and reduction and enhance production properties. Theoretically, lignin and PHB affect the physiochemical properties of each other when they become miscible in a composite. A comprehensive study on structural, thermal, rheological and environmental properties of lignin/PHB blends together with neat lignin and PHB is the targeted scope of this thesis. An introduction to this research, including a description of the research problem, a literature review and an account of the research progress linking the research papers is presented in Chapter 1. In this research, lignin was obtained from bagasse through extraction with sodium hydroxide. A novel two-step pH precipitation procedure was used to recover soda lignin with the purity of 96.3 wt% from the black liquor (i.e. the spent sodium hydroxide solution). The precipitation process is presented in Chapter 2. A sequential solvent extraction process was used to fractionate the soda lignin into three fractions. These fractions, together with the soda lignin, were characterised to determine elemental composition, purity, carbohydrate content, molecular weight, and functional group content. The thermal properties of the lignins were also determined. The results are presented and discussed in Chapter 2. On the basis of the type and quantity of functional groups, attempts were made to identify potential applications for each of the individual lignins. As an addendum to the general section on the development of composite materials of lignin, which includes Chapters 1 and 2, studies on the kinetics of bagasse thermal degradation are presented in Appendix 1. The work showed that distinct stages of mass losses depend on residual sucrose. As the development of value-added products from lignin will improve the economics of cellulosic ethanol, a review on lignin applications, which included lignin/PHB composites, is presented in Appendix 2. Chapters 3, 4 and 5 are dedicated to investigations of the properties of soda lignin/PHB composites. Chapter 3 reports on the thermal stability and miscibility of the blends. Although the addition of soda lignin shifts the onset of PHB decomposition to lower temperatures, the lignin/PHB blends are thermally more stable over a wider temperature range. The results from the thermal study also indicated that blends containing up to 40 wt% soda lignin were miscible. The Tg data for these blends fitted nicely to the Gordon-Taylor and Kwei models. Fourier transform infrared spectroscopy (FT-IR) evaluation showed that the miscibility of the blends was because of specific hydrogen bonding (and similar interactions) between reactive phenolic hydroxyl groups of lignin and the carbonyl group of PHB. The thermophysical and rheological properties of soda lignin/PHB blends are presented in Chapter 4. In this chapter, the kinetics of thermal degradation of the blends is studied using thermogravimetric analysis (TGA). This preliminary investigation is limited to the processing temperature of blend manufacturing. Of significance in the study, is the drop in the apparent energy of activation, Ea from 112 kJmol-1 for pure PHB to half that value for blends. This means that the addition of lignin to PHB reduces the thermal stability of PHB, and that the comparative reduced weight loss observed in the TGA data is associated with the slower rate of lignin degradation in the composite. The Tg of PHB, as well as its melting temperature, melting enthalpy, crystallinity and melting point decrease with increase in lignin content. Results from the rheological investigation showed that at low lignin content (.30 wt%), lignin acts as a plasticiser for PHB, while at high lignin content it acts as a filler. Chapter 5 is dedicated to the environmental study of soda lignin/PHB blends. The biodegradability of lignin/PHB blends is compared to that of PHB using the standard soil burial test. To obtain acceptable biodegradation data, samples were buried for 12 months under controlled conditions. Gravimetric analysis, TGA, optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, and X-ray photoelectron spectroscopy (XPS) were used in the study. The results clearly demonstrated that lignin retards the biodegradation of PHB, and that the miscible blends were more resistant to degradation compared to the immiscible blends. To obtain an understanding between the structure of lignin and the properties of the blends, a methanol-soluble lignin, which contains 3× less phenolic hydroxyl group that its parent soda lignin used in preparing blends for the work reported in Chapters 3 and 4, was blended with PHB and the properties of the blends investigated. The results are reported in Chapter 6. At up to 40 wt% methanolsoluble lignin, the experimental data fitted the Gordon-Taylor and Kwei models, similar to the results obtained soda lignin-based blends. However, the values obtained for the interactive parameters for the methanol-soluble lignin blends were slightly lower than the blends obtained with soda lignin indicating weaker association between methanol-soluble lignin and PHB. FT-IR data confirmed that hydrogen bonding is the main interactive force between the reactive functional groups of lignin and the carbonyl group of PHB. In summary, the structural differences existing between the two lignins did not manifest itself in the properties of their blends.

Age-related loss of brain volume and T2 relaxation time in youth with type 1 diabetes

OBJECTIVE: Childhood-onset type 1 diabetes is associated with neurocognitive deficits, but there is limited evidence to date regarding associated neuroanatomical brain changes and their relationship to illness variables such as age at disease onset. This report examines age-related changes in volume and T2 relaxation time (a fundamental parameter of magnetic resonance imaging that reflects tissue health) across the whole brain. RESEARCH DESIGN AND METHODS: Type 1 diabetes, N = 79 (mean age 20.32 ± 4.24 years), and healthy control participants, N = 50 (mean age 20.53 ± 3.60 years). There were no substantial group differences on socioeconomic status, sex ratio, or intelligence quotient. RESULTS: Regression analyses revealed a negative correlation between age and brain changes, with decreasing gray matter volume and T2 relaxation time with age in multiple brain regions in the type 1 diabetes group. In comparison, the age-related decline in the control group was small. Examination of the interaction of group and age confirmed a group difference (type 1 diabetes vs. control) in the relationship between age and brain volume/T2 relaxation time. CONCLUSIONS: We demonstrated an interaction between age and group in predicting brain volumes and T2 relaxation time such that there was a decline in these outcomes in type 1 diabetic participants that was much less evident in control subjects. Findings suggest the neurodevelopmental pathways of youth with type 1 diabetes have diverged from those of their healthy peers by late adolescence and early adulthood but the explanation for this phenomenon remains to be clarified.

133Cs relaxation times in rat tissues

133Cs relaxation-time studies of tissues from rats into which cesium has been incorporated by dietary loading have been carried out in vivo and in vitro. Whereas tissue T1 values are on the order of seconds, T2 values are as low as a few tens of milliseconds, 133Cs tissue relaxation times are analogous to those of 39K in the same tissues, but are more readily measured because of the greater sensitivity of 133Cs compared with 39K, T1 and T2 data of excised tissue at two resonance frequencies (65.60 and 39.37 MHz) and temperatures (302 and 278 K) have been analyzed in terms of a general description of spin- relaxation. The results are consistent with most of the cesium ions being in a free state, undergoing fast exchange with bound ions having long correlation times located in one or more intracellular compartments,

NMR measurement of 39K detectability and relaxation constants in rat tissue

Differences in the NMR detectability of 39K in various excised rat tissues (liver, brain, kidney, muscle, and testes) have been observed. The lowest NMR detectability occurs for liver (61 ± 3% of potassium as measured by flame photometry) and highest for erythrocytes (100 ± 7%). These differences in detectability correlate with differences in the measured 39K NMR relaxation constants in the same tissues. 39K detectabilities were also found to correlate inversely with the mitochondrial content of the tissues. Mitochondria prepared from liver showed greatly reduced 39K NMR detectability when compared with the tissue from which it was derived, 31.6 ± 9% of potassium measured by flame photometry compared to 61 ± 3%. The detectability of potassium in mitochondria was too low to enable the measurement of relaxation constants. This study indicates that differences in tissue structure, particularly mitochondrial content are important in determining 39K detectability and measured relaxation rates.

NMR relaxation behavior and quadrupole coupling constants of 39K and 23Na ions in glycerol. Comparisons with 39K tissue data

The quadrupole coupling constants (qcc) for39K and23Na ions in glycerol have been calculated from linewidths measured as a function of temperature (which in turn results in changes in solution viscosity). The qcc of39K in glycerol is found to be 1.7 MHz, and that of23Na is 1.6 MHz. The relaxation behavior of39K and23Na ions in glycerol shows magnetic field and temperature dependence consistent with the equations for transverse relaxation more commonly used to describe the reorientation of nuclei in a molecular framework with intramolecular field gradients. It is shown, however, that τc is not simply proportional to the ratio of viscosity/temperature (ηT). The 39K qcc in glycerol and the value of 1.3 MHz estimated for this nucleus in aqueous solution are much greater than values of 0.075 to 0.12 MHz calculated from T2 measurements of39K in freshly excised rat tissues. This indicates that, in biological samples, processes such as exchange of potassium between intracellular compartments or diffusion of ions through locally ordered regions play a significant role in determining the effective quadrupole coupling constant and correlation time governing39K relaxation. T1 and T2 measurements of rat muscle at two magnetic fields also indicate that a more complex correlation function may be required to describe the relaxation of39K in tissue. Similar results and conclusions are found for23Na.