Magister Pharmaceuticae - MPharm / Leonotis leonurus (L. leonurus) and Artemisia afra (A. afra) are two of the most commonly used medicinal plants in South Africa traditionally advocated for use in asthma. However, proper scientific studies to validate these claimed uses are lacking and little is known about the mechanisms for this effect. These plants contain flavonoids, which are reported to have smooth muscle relaxant activity and may be responsible for the activity of these two plants. The objectives of this study were to: (1) determine and compare the flavonoid profiles and levels in A. afra and L. leonurus, (2) compare the respiratory smooth muscle relaxant effects of freeze-dried aqueous extracts of A. afra and L. leonurus and (3) investigate whether K⁺ - channel activation (i.e. KATP channel) is one possible mechanism of action that can explain the effect obtained in traditional use of these two plants. It was hypothesized that: (1) the flavonoid levels and profile of A. afra would be greater than the flavonoid levels and profile of L. leonurus, (2) A. afra would have a more potent respiratory muscle relaxant effect than L. leonurus and (3) A. afra and L. leonurus will inhibit K⁺ - induced contractions in a superior manner than carbachol and histamine - induced contractions. To realize these objectives, freeze-dried aqueous extracts (FDAE) of the dried leaves of the two plants were prepared. A validated HPLC assay was developed and used to identify and determine the levels of luteolin in the plant preparations. Solutions of the plant extracts were studied in the isolated guinea-pig trachea tissue preparation in the presence of carbachol, histamine and KCL. The possible mechanism of action of the two plants was determined by cumulative log dose-response curves (LDRC) for carbachol, histamine and KCL in the absence and presence of 1, 30 and 100 mg/ml solutions of the plant extracts. The flavonoid profile of un-hydrolyzed and hydrolyzed L. leonurus was greater than that of un-hydrolyzed and hydrolyzed A. afra. The levels of free and total luteolin in A. afra FDAE (8.977 ± 0.73 μg/ml and 16.394 ± 0.884 μg/ml, respectively) were significantly (p < 0.001) higher than that in L. leonurus FDAE (0.929 ± 0.066 μg/ml and 3.093 ± 0.531 μg/ml, respectively). L. leonurus and A. afra relaxed tracheal smooth muscles contracted with histamine, KCL and carbachol in a dose dependent manner. The degree of relaxant activity of L. leonurus versus the three inducers of contraction (agonists) could be classified as KCL > carbachol > histamine, with EC₅₀ values of 9.87, 29.34 and 94.76 mg/ml, respectively. The A. afra tracheal smooth muscle relaxant activity was categorized as carbachol > histamine > KCL, with EC₅₀ values of 13.93, 15.47 and 19.88 mg/ml, respectively. Overall, A. afra which contained the higher levels of luteolin, was more potent at relaxing the guinea pig tracheal smooth muscle than L. leonurus. Collectively, the results confirm that aqueous solutions of A. afra and L. leonurus as used in local traditional practice have potent but different degrees of bronchodilator activities that could be useful in the treatment of asthma, and that these actions may be related to each plant's luteolin (or flavonoid) levels. Moreover it is very unlikely that KATP channels are primarily responsible for the actions of A. afra and L. leonurus, but rather that more than one mechanism of action is involved in the tracheal smooth muscle relaxant effects of these two plants. / National Research Foundation

Stearate anions were successfully intercalated into the layered double hydroxide Mg4Al2(OH)12CO3.3H2O (LDH-CO3) by several methods to form LDH-SA. The intercalation method which involved the acid-base reaction between emulsified stearic acid (SA) and the carbonate anions in aqueous media was studied for the first time. This method led to the formation of more LDH-SA than well known methods such as melting the carboxylic acid in the presence of the LDH, allowing the interlayer region to swell in the presence of glycerol and reconstructing the calcined LDH in the presence of aqueous sodium stearate. Other literature methods involve ion-exchange of Cl- in LDH-Cl with stearate in aqueous sodium stearate, usually under N2 atmosphere. The methods developed in this study are more industrially viable because the more easily produced LDH-CO3 is used and no N2 atmosphere is necessary. The LDH-SA was successfully used to intercalate sodium polyvinyl sulphonate by an ion exchange with the intercalated stearate, without the need for a N2 atmosphere. This method of production could be useful for the production of nanocomposites in general, for example anionic polymer chains (such as DNA) and anionic clays. The same intercalation reaction was allowed to take place in situ during the formation of dextrin-alginate-glycerol film solutions in water-ethanol media. The stearate intercalated as a bilayer in the interlayer region of the LDH. The SA to LDH ratio was varied from 100% SA to 100% LDH. Around the middle of the series a minimum water vapour permeability (WVP) was obtained, which corresponded to an 80% reduction in WVP in comparison to the reference (blank) film. Around the middle of the series a maximum increase in Young’s modulus, corresponding to a 213% increase in comparison to the blank film, was obtained. Around the middle of the series a reduction in the intensity of the basal reflection and interlayer distance showed that some exfoliation (delamination) took place. / Thesis (PhD (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

An often overlooked connection between karst groundwater systems and surface water is spring flow reversal, the flow of river water into karst springs caused by changes in hydraulic gradient. Karst aquifers are subject to the intrusion of river water when the hydraulic head of a base level river is higher than the hydraulic head of a base level spring. When this occurs, the flow out of the spring reverses, allowing river water to enter base level conduits. River water thus becomes a source of recharge into karst basins, transporting both valuable nutrients and harmful contaminants into karst aquifers. The rapid recharge of meteoric water, brief groundwater residence times, and the interconnection of surface and subsurface waters through a variety of karst features necessitates studying groundwater and surface water in karst landscapes as a unified system. This study examines the influence of spring flow reversal on cave dissolution in a telogenetic karst aquifer in Mammoth Cave, Kentucky. Spring flow reversals in Mammoth Cave National Park (MCNP) were first recorded nearly one-hundred years ago, but a high-resolution study measuring the effects of spring flow reversals on dissolution in MCNP, or any other telogenetic karst system, had not been conducted until recently. In this study, high-resolution data were collected for pH, SpC, temperature, and stage, as well as weekly samples for major ion concentrations, alkalinity, and carbon isotopes, from June 2018 to December 2018. Surface water and groundwater data were used to quantify the complex hydrologic processes associated with the spring flow reversals, including seasonal changes in karst geochemistry and dissolution taking place between the Green River, River Styx Spring, and Echo River Spring. Data show distinct changes in geochemical parameters as flow reversals occur, with temperature being the principal indicator of flow direction change. During this study, all ten stable reverse flows coincided with increased discharge from the Green River Dam. The predominant drivers of dissolution in the River Styx and Echo River karst basins are storm events and seasonal changes in the hydrologic regime, rather than seasonal CO2 production, normal baseflow conditions, or stable reverse flow events. Estimated dissolution rates generally show that stable reverse flows contribute no more to dissolution than normal baseflow conditions – the highest amount of dissolution during a single stable reverse flow was only 0.003 mm. This is contrary to flow reversal studies in an eogenetic karst system in Florida, which estimated 3.4 mm of wall retreat during a single spring flow reversal. These contrasting results are likely due to significant differences in pH of river water, matrix porosity of the bedrock, basin morphology, and flow conditions.

Metal-organic frameworks (MOFs) are porous crystalline materials built by metal clusters coordinated to organic ligands. Synthesis of MOFs has attracted considerable attention in recent decades, owing to its potential for a wide range of applications such as gas separation, dye adsorption, and catalysis, etc. The development of MOF membranes further enhances the potential of this type of material in industrial applications. Membrane fabrication methods, including in-situ growth, seeded secondary growth, interfacial growth, and vapor-phase deposition, have been widely studied. However, most of these methods either require a complicated synthesis procedure or are timeconsuming. Recently, the electrochemical synthesis has emerged as a highly promising approach to fabricate MOF membranes in a scalable manner, because it allows shorter synthesis time, milder synthesis condition, continuous reaction, and crystal self-healing. In this thesis, for the first time, an aqueously cathodic deposition (ACD) approach was developed to fabricate ZIF-8 type of MOF membranes without the addition of any supporting electrolyte or modulator. The fabrication process used 100% water as the sole solvent, and a low-defect density membrane was obtained in only 60 min under room temperature without any pre-synthesis treatment. The membrane exhibited superior performance in C3H6/C3H8 separation with C3H6 permeance of 182 GPU and selectivity of 142, making it sit at the upper bound of permeance versus selectivity graph, outperforming the majority of the published data up to 2019. Notably, this approach used an extremely low current density (0.13 mA cm-2) operated under a facile apparatus setup, enabling an attractive method for environmentally friendly, energy-efficient, and scalable MOF membrane fabrications. This work demonstrates the enormous potential of aqueously electrochemical deposition of the MOF membrane in future research.

Corrosion characteristics of seven varieties of metals—zinc, brass C260, stainless steel 302, stainless steel 316, stainless steel 420, stainless steel 430, and stainless steel 440—in three aqueous media—Atlantic Ocean, Charles River, and deionized waters—were assessed via mass loss methods over 32 weeks, with supplemental data in the form of photomicrographic records. Concurrently, tests were conducted to determine the degree of measurement error resulting from the analytical scale used during corrosion assessment. This was accomplished by using reference samples of each type of metal and a glass vial as the container that held the metal and water samples. These error tests indicated that while the mass error associated with the metal samples was low, the error in mass associated with the vial displayed error margins two orders of magnitude larger than the error margins for the smaller metal samples. Further, control tests and statistical analysis indicated that this variation was the result of some quality inherent to the vial. The metal samples involved in the corrosion assessment experiment generally displayed corrosion characteristics in agreement with trends reported in the literature. Zinc produced the greatest quantity of corrosion residues out of all the metals studied. Brass C260 also developed visible corrosion. For example, brass C260 developed dark green/brown adherent residue and whitish blue-tinted nonadherent residue in Atlantic Ocean water, faint greenish tarnishing and some dark green spots and dots over time in Charles River water, and only faint greenish tarnish in deionized water. In contrast with zinc and brass C260, the stainless steels did not exhibit signs of significant corrosion rates excepting stainless steel 420 (SS420), which displayed pitted features surrounded by multi-colored rings on all of its Atlantic Ocean immersion samples and 25% of its Charles River immersion samples. Atlantic Ocean water generally caused the greatest degree of corrosion for all metals, followed by Charles River water, then deionized water, except in the case of zinc. Residues found on zinc samples immersed in the three different water types were similar to each other in coloration. SS420 samples immersed in different waters also displayed similar-colored residues. Comparisons between the corrosion features of SS420 and the single stainless steel 430 and 440 samples that did show visible corrosion in Atlantic Ocean water suggested that minor compositional variations between stainless steels have little effect on the visual characteristics of the corrosion residues they form. Corrosion rates were calculated using linear regressions of the mass loss data for all metal sample sets. While some of these corrosion rates approached literature-reported values for the metal in question, the distributions of the mass loss data sets indicated that any mass changes that resulted from corrosion were likely too small for the electronic scale to detect. Consequently, it is recommended that future corrosion studies using the mass loss method utilize metal samples similar in size to objects typically found at crime scenes.

Calcium stable isotope ratios are a relatively new tool that biogeochemists can use to investigate the biogeochemical cycle of calcium in terrestrial ecosystems, having seen widespread application only in the past 15 years. To advance the application of calcium isotopes in biogeoscience research, I conducted three investigations focused on interpreting calcium isotope ratios in streamwater and in the cation exchange pool of forest soils. In the first study, we observe a shift toward lower 44Ca/40Ca ratios in streamwater draining a New Hampshire watershed after an experimental clearcutting event. Isotope ratio measurements of ecosystem calcium pools indicate that enhanced leaching of the soil exchangeable pool produced the observed shift in 44Ca/40Ca ratios. A trend towards decreased 44Ca/40Ca ratios in soils in the years following the harvesting indicates that calcium leached from the soil exchangeable reservoir was likely replaced by calcium released by the decay of belowground biomass, maintaining pre-harvest levels of exchangeable calcium even in the face of a significant ecosystem disturbance. In a second study, we observed significant differences in the 44Ca/40Ca of the soil exchange pool between two neighboring tropical watersheds, although 44Ca/40Ca of calcium inputs (bedrock and atmospheric deposition) at the two sites were indistinguishable. Further, both sites had higher 44Ca/40Ca ratios compared with external inputs, a relatively rare observation globally. We propose that hurricane disturbance best explains the high 44Ca/40Ca at each site, and that the difference in 44Ca/40Ca between the two sites can be accounted for by the magnitude of disturbance at each site. Finally, a synthesis of our new data with previously published results shows that globally, soil exchangeable 44Ca/40Ca ratios can be higher, lower or equal to external inputs. Modeling work indicates that in addition to isotopic fractionation, the balance in fluxes between vegetation and soil is critical in determining how soil exchangeable 44Ca/40Ca ratios vary relative to external inputs. When plant uptake and return to the soil are equal, soil and external inputs 44Ca/40Ca are equal, while high soil 44Ca/40Ca ratios develop when uptake exceeds return. Soil develops low 44Ca/40Ca when biomass obtains calcium from sources other than the exchangeable reservoir.

Organoclays modelling the Athabasca oil sands were prepared in heptane and toluene showing indole loading occurring exclusively on the external surface of the clay, via a multilayer adsorption mechanism. Solvent adsorption was minimal. Vermicular microstructures, similar to natural kaolinite were formed. Isotherms were constructed and fitted to the BET equation, giving monolayer quantities (9.28mg) that matched well to the theoretical amount calculated from surface area measurements (8.87mg). Dispersing the organoclays in isopropanol and in toluene left a monolayer equivalent. Using cellulose as a competitive desorption agent in asphaltene based organoclay dispersions achieved complete disaggregation of the dispersed organoclay stacks.13 C CP - MAS NMR, showed up to a 25% increase in desorption for aliphatic and up to 40% increase in desorption for aromatic functionalities of the loaded organic matter. Investigation of other saccharides and modified celluloses as competitive agents is recommended for future work.

Two major hurdles face the production of recombinant spider silk protein (rSSp) based materials. First, the production of sufficient quantities of rSSp has proven difficult due to their highly repetitive nature and protein size (>250kDa). Secondly, rSSp and native silks are practically insoluble in water based solutions, necessitating the use of harsh organic solvents that can remain in the material after production. While others are working on solving production problems, this dissertation demonstrates a novel aqueous solubilization method that is rapid (<1 minute) and results in near 100% solubilization of the rSSp. From this new solubilization method films, foams, gels (hydrogels and lyogels), adhesives, coatings and fibers have been produced as well as the previously unreported sponge. All of these novel materials were derived from entirely aqueous solutions with and without minor additives to influence the final physical state of the rSSp.

Spider silks are incredible natural materials that possess desirable combinations of strength, elasticity, weight, and robustness. Other properties such as biocompatibility and biodegradability further increase the worth of these materials. The possibility of farming spiders is impractical due to spiders’ natural behaviors. Modern biotechnologies have allowed for recombinant spider silk proteins (rSSps) to be produced without the use of spiders. However, the features responsible for spider silks impressive properties can cause difficulties with producing silk materials. A recently developed water-based and biomimetic solvation method has provided a solution to such difficulties and has also led to novel silk biomaterials. Most notable among these materials are; coatings, fibers, adhesives, films, foams, hydrogels, aerogels, capsules, and sponges. Many of these material possess specific properties that may be suitable for many commercial, industrial, and biomedical uses. This study has developed numerous spider silk biomaterials, identified their essential properties and features, provided preliminary evidence for various applications, and identified directions for future studies and uses.

The need for renewable energy is increasing as a result of global warming and other environmental challenges. Renewable energy systems are intermittent in nature and require energy storage solutions. Lithium-ion batteries are the first choice for storing electrical energy due to their high energy density, long cycle life, and small size. However, their widespread use in grid-scale applications is limited by high cost, low lithium resources, and security issues. Among the various options, the rechargeable zinc ion water battery has the advantages of high economic efficiency, high safety, and environmental friendliness, and there are great expectations for energy storage on a network scale. Inspired by these benefits, people have put a lot of effort into developing and manufacturing zinc-based energy storage devices. As the main component of zinc ion battery, the cathode material plays an important role in the storage / release of zinc ions during insertion and extraction. Vanadium-based materials are attracting attention due to their various oxidation states, diverse structures, and abundant natural resources. However, the details of suitable cathode materials and Zn2+ storage mechanism for rechargeable zinc ion battery are not yet fully understood. In this thesis, firstly, the prepared zinc pyrovanadate delivers good zinc ion storage properties owing to its open-framework crystal structure and multiple oxidation states. Mechanistic details of the Zn-storage mechanism in zinc pyrovanadate were also elucidated. Then, a calcium vanadium oxide bronze with expanding cavity size, smaller molecular weight, and higher electrical conductivity are proposed to deeply understand the impact of the crystal structure on battery performance. To improve the stability of the cathode in rechargeable zinc ion battery, an artificial solid electrolyte interphase strategy has been proposed by inducing an ultrathin HfO2 layer via the Atomic layer deposition method, which effectively alleviates the dissolution of active material. Finally, a nitrogen-doped 3D laser scribed graphene with a large surface area and uniform distribution of nucleation sites has been used as the interlayer to control Zn nucleation behavior and suppress Zn dendrite growth, which brings new possibilities for the practical rechargeable zinc ion battery.