Sulfate Mineral Paragenesis in Pennsylvanian Rocks and The Occurrence of Slavikite in Nebraska

The acid weathering of pyrite-bearing Pennsylvanian clastic sedimentary rocks in southeastern Nebraska locally produces the secondary sulfate minerals alunogen, copiapite, epsomite, felsobanyaite/basaluminite, gypsum, halotrichite, jarosite, rozenite, and slavikite. Of these mineral occurrences, four are first-time discoveries in the state or the surrounding region. Slavikite (NaMg2Fe5 (S04)7 (OH) 6• 33H20), which has been reported only once before in North America and from a handful of sites in Europe and South America, was found in abundance at an outcrop at Brownville, NE. The pH values in 1:1 solutions of deionized water of the studied minerals, excluding epsomite, range from 1.94 to 4.82. Therefore, segregations of secondary minerals in themselves are significant microenvironmental reservoirs of acid that can be mobilized during precipitation events. Because of its role in liberating and concentrating ions such as Al3+, Fe2+, Fe3+, Mg3+, and SO42-, acid rock weathering should be considered in local to regional assessments of surface-water and groundwater chemistry. Observations also suggest that rock weathering by the growth of sulfate salts is a potential factor in local hillslope development, one that has not previously been considered in the study area.

Development of an Electrochemical Insulin Sensor Based on a High Affinity DNA Sequence Found in the Insulin-linked Polymorphic Region

The detection of pertinent biomarkers has the potential provide an early indication of disease progression before considerable damage has been incurred. A decrease in an individual’s sensitivity to insulin, which may be quantified as the ratio of insulin to glucose in the blood after a glucose pulse, has recently been reported as an early predictor of insulin-dependent diabetes mellitus. Routine measurement of insulin levels is therefore desirable in the care of diabetes-prone individuals. A rapid, simple, and reagentless method for insulin detection would allow for wide-spread screenings that provide earlier signs of diabetes onset. The aim of this thesis is to develop a folding-base electrochemical sensor for the detection of insulin. The sensor described herein consists of a DNA probe immobilized on a gold disc electrode via an alkanethiol linker and embedded in an alkanethiol self-assembled monolayer. The probe is labeled with a redox reporter, which readily transfers electrons to the gold electrode in the absence of insulin. In the presence of insulin, electron transfer is inhibited, presumably due to a binding-induced conformational or dynamic change in the DNA probe that significantly alters the electron-tunneling pathway. A 28-base segment of the insulin-linked polymorphic region that has been reported to bind insulin with high affinity serves as the capture element of the DNA probe. Three probe constructs that vary in their secondary structure and position of the redox label are evaluated for their utility as insulin-sensing elements on the electrochemical platform. The effects of probe modification on secondary structure are also evaluated using circular dichroism spectroscopy.