Enhancing Sensitivity In Natural Product Nmr: Exploring Optimal Non-Uniform Sampling

Recent optimizations of NMR spectroscopy have focused their attention on innovations in new hardware, such as novel probes and higher field strengths. Only recently has the potential to enhance the sensitivity of NMR through data acquisition strategies been investigated. This thesis has focused on the practice of enhancing the signal-to-noise ratio (SNR) of NMR using non-uniform sampling (NUS). After first establishing the concept and exact theory of compounding sensitivity enhancements in multiple non-uniformly sampled indirect dimensions, a new result was derived that NUS enhances both SNR and resolution at any given signal evolution time. In contrast, uniform sampling alternately optimizes SNR (t < 1.26T2) or resolution (t~3T2), each at the expense of the other. Experiments were designed and conducted on a plant natural product to explore this behavior of NUS in which the SNR and resolution continue to improve as acquisition time increases. Possible absolute sensitivity improvements of 1.5 and 1.9 are possible in each indirect dimension for matched and 2x biased exponentially decaying sampling densities, respectively, at an acquisition time of ¿T2. Recommendations for breaking into the linear regime of maximum entropy (MaxEnt) are proposed. Furthermore, examination into a novel sinusoidal sampling density resulted in improved line shapes in MaxEnt reconstructions of NUS data and comparable enhancement to a matched exponential sampling density. The Absolute Sample Sensitivity derived and demonstrated here for NUS holds great promise in expanding the adoption of non-uniform sampling.

Performance Tuning Non-Uniform Sampling for Sensitivity Enhancement of Signal-Limited Biological NMR

Non-uniform sampling (NUS) has been established as a route to obtaining true sensitivity enhancements when recording indirect dimensions of decaying signals in the same total experimental time as traditional uniform incrementation of the indirect evolution period. Theory and experiments have shown that NUS can yield up to two-fold improvements in the intrinsic signal-to-noise ratio (SNR) of each dimension, while even conservative protocols can yield 20-40 % improvements in the intrinsic SNR of NMR data. Applications of biological NMR that can benefit from these improvements are emerging, and in this work we develop some practical aspects of applying NUS nD-NMR to studies that approach the traditional detection limit of nD-NMR spectroscopy. Conditions for obtaining high NUS sensitivity enhancements are considered here in the context of enabling H-1,N-15-HSQC experiments on natural abundance protein samples and H-1,C-13-HMBC experiments on a challenging natural product. Through systematic studies we arrive at more precise guidelines to contrast sensitivity enhancements with reduced line shape constraints, and report an alternative sampling density based on a quarter-wave sinusoidal distribution that returns the highest fidelity we have seen to date in line shapes obtained by maximum entropy processing of non-uniformly sampled data.

Geophysical Analysis of Seasonal Montandon Gravel Ridge Water Table Fluctuation and Moisture Gradient Variation due to Storm Events

The purpose of this research project is to continue exploring the Montandon Long-Term Hydrologic Research Site(LTHR) by using multiple geophysical methods to obtain more accurate and precise information regarding subsurface hydrologic properties of a local gravel ridge,which are important to both the health of surrounding ecosystems and local agriculture. Through using non-invasive geophysical methods such as seismic refraction, Direct Current resistivity and ground penetrating radar (GPR) instead of invasive methods such as boreholedrilling which displace sediment and may alter water flow, data collection is less likely to bias the data itself. In addition to imaging the gravel ridge subsurface, another important researchpurpose is to observe how both water table elevation and the moisture gradient (moisture content of the unsaturated zone) change over a seasonal time period and directly after storm events. The combination of three types of data collection allows the strengths of each method combine together and provide a relatively strongly supported conclusions compared to previous research. Precipitation and geophysical data suggest that an overall increase in precipitation during the summer months causes a sharp decrease in subsurface resistivity within the unsaturated zone. GPR velocity data indicate significant immediate increase in moisture content within the shallow vadose zone (< 1m), suggesting that rain water was infiltrating into the shallow subsurface. Furthermore, the combination of resistivity and GPR results suggest that the decreased resistivity within the shallow layers is due to increased ion content within groundwater. This is unexpected as rainwater is assumed to have a DC resistivity value of 3.33*105 ohm-m. These results may suggest that ions within the sediment must beincorporated into the infiltrating water.

Attitudes and Social Factors as Predictors of Male Perpetration of Sexual Assault

Previous research has demonstrated a significant association between sexual assault perpetration and hooking up, male peer support for woman abuse, alcohol consumption, and rape myth acceptance (Burt, 1980; Flack, Daubman, Caron, Asadorian, D’Aureli, Gigliotti & Stine, 2007; Schwartz & DeKeseredy, 1997). In the present study, we tested these relationships on the collegiate level by asking male students to indicate levels of male peer support for woman abuse (MPS), acceptance of rape myths (RMA), alcohol consumption, and history of hooking up and sexual assault perpetration during their undergraduate experience. Participants in this study were 200 male Bucknell students (sophomores - seniors) who completed an online survey concerning these issues. The overall prevalence rate for some type of sexual assault perpetration was 10.5%. Specific prevalence rates for non-invasive contact, completed rape, and attempted rape were 5.5%, 2.0%, and 5.0%, respectively. Sexual assault perpetration was positively correlated with MPS and alcohol consumption but not with RMA. Sexual assault was perpetrated most frequently during acquaintance hook ups. These findings demonstrate direct, significant relationships between sexual assault perpetration, alcohol abuse, different types of hooking up, and rape-supportive attitudes, and an association between perpetration and MPS that requires further elaboration.

Monitoring Stormwater Redistribution Into Low Resistivity Soils Using Noninvasive Geophysical Techniques

Water held in the unsaturated zone is important for agriculture and construction and is replenished by infiltrating rainwater. Monitoring the soil water content of clay soils using ground-penetrating radar (GPR) has not been researched, as clay soils cause attenuation of GPR signal. In this study, GPR common-midpoint soundings (CMPs) are used in the clayey soils of the Miller Run floodplain to monitor changes in the soil water content (SWC) before and after rainfall events. GPR accomplishes this task because increases in water content will increase the dielectric constant of the subsurface material, and decrease the velocity of the GPR wave. Using an empirical relationship between dielectric constant and SWC, the Topp relation, we are able to calculate a SWC from these velocity measurements. Non-invasive electromagnetics, resistivity, and seismic were performed, and from these surveys, the layering at the field site was delineated. EM characterized the horizontal variation of the soil, allowing us to target the most clay rich area. At the CMP location, resistivity indicates the vertical structure of the subsurface consists of a 40 cm thick layer with a resistivity of 100 ohm*m. Between 40 cm and 1.5 m is a layer with a resistivity of 40 ohm*m. The thickness estimates were confirmed with invasive auger and trenching methods away from the CMP location. GPR CMPs were collected relative to a July 2013 and September 2013 storm. The velocity observations from the CMPs had a precision of +/- 0.001 m/ns as assessed by repeat analysis. In the case of both storms, the GPR data showed the expected relationship between the rainstorms and calculated SWC, with the SWC increasing sharply after the rainstorm and decreasing as time passed. We compared these data to auger core samples collected at the same time as the CMPs were taken, and the volumetric analysis of the cores confirmed the trend seen in the GPR, with SWC values between 3 and 5 percent lower than the GPR estimates. Our data shows that we can, with good precision, monitor changes in the SWC of conductive soils in response to rainfall events, despite the attenuation induced by the clay.

Using Micro-Gravity Techniques to Map Alluvium Thickness and Pleistocene Location of the West Branch of the Susquehanna River Near Muncy, Pennsylvania

Laurentide glaciation during the early Pleistocene (~970 ka) dammed the southeast-flowing West Branch of the Susquehanna River (WBSR), scouring bedrock and creating 100-km-long glacial Lake Lesley near the Great Bend at Muncy, Pennsylvania (Ramage et al., 1998). Local drill logs and well data indicate that subsequent paleo-outwash floods and modern fluvial processes have deposited as much as 30 meters of alluvium in this area, but little is known about the valley fill architecture and the bedrock-alluvium interface. By gaining a greater understanding of the bedrock-alluvium interface the project will not only supplement existing depth to bedrock information, but also provide information pertinent to the evolution of the Muncy Valley landscape. This project determined if variations in the thickness of the valley fill were detectable using micro-gravity techniques to map the bedrock-alluvium interface. The gravity method was deemed appropriate due to scale of the study area (~30 km2), ease of operation by a single person, and the available geophysical equipment. A LaCoste and Romberg Gravitron unit was used to collect gravitational field readings at 49 locations over 5 transects across the Muncy Creek and Susquehanna River valleys (approximately 30 km2), with at least two gravity base stations per transect. Precise latitude, longitude and ground surface elevation at each location were measured using an OPUS corrected Trimble RTK-GPS unit. Base stations were chosen based on ease of access due to the necessity of repeat measurements. Gravity measurement locations were selected and marked to provide easy access and repeat measurements. The gravimeter was returned to a base station within every two hours and a looping procedure was used to determine drift and maximize confidence in the gravity measurements. A two-minute calibration reading at each station was used to minimize any tares in the data. The Gravitron digitally recorded finite impulse response filtered gravity measurements every 20 seconds at each station. A measurement period of 15 minutes was used for each base station occupation and a minimum of 5 minutes at all other locations. Longer or multiple measurements were utilized at some sites if drift or other externalities (i.e. train or truck traffic) were effecting readings. Average, median, standard deviation and 95% confidence interval were calculated for each station. Tidal, drift, latitude, free-air, Bouguer and terrain corrections were then applied. The results show that the gravitational field decreases as alluvium thickness increases across the axes of the Susquehanna River and Muncy Creek valleys. However, the location of the gravity low does not correspond with the present-day location of the West Branch of the Susquehanna River (WBSR), suggesting that the WBSR may have been constrained along Bald Eagle Mountain by a glacial lobe originating from the Muncy Creek Valley to the northeast. Using a 3-D inversion model, the topography of the bedrock-alluvium interface was determined over the extent of the study area using a density contrast of -0.8 g/cm3. Our results are consistent with the bedrock geometry of the area, and provide a low-cost, non-invasive and efficient method for exploring the subsurface and for supplementing existing well data.