Studies Directed toward the Synthesis of Asymmetric Loline Alkaloids

This thesis discusses the progress toward the synthesis of asymmetric loline alkaloids. Lolines are polycyclic pyrrolizidine alkaloids that contain four contiguous stereocenters and a strained ether bridge. Lolines are present in symbiotic relationships between grass species and fungal endophytes and act as a natural pesticide and feeding deterrent that protects the grass host from insects, yet are believed to possess low toxicity to mammals. Our Scheerer 2nd generation synthesis takes precedent from the 1st generation Scheerer synthesis, but with some key changes. The synthetic route has fewer steps, a different nitrogen protecting group, and usage of stereoselective tethered aminhydroxylation 3rd generation conditions. Other key reactions include Petasis borono-Mannich addition and ring closing metathesis using Hoveyda-Grubbs 2nd generation catalyst

Deep Chandra Observations of the Compact Starburst Galaxy Henize 2–10: X-Rays from the Massive Black Hole

We present follow-up X-ray observations of the candidate massive black hole (BH) in the nucleus of the low-mass, compact starburst galaxy Henize 2–10. Using new high-resolution observations from the Chandra X-ray Observatory totaling 200 ks in duration, as well as archival Chandraobservations from 2001, we demonstrate the presence of a previously unidentified X-ray point source that is spatially coincident with the known nuclear radio source in Henize 2–10 (i.e., the massive BH). We show that the hard X-ray emission previously identified in the 2001 observation is dominated by a source that is distinct from the nucleus, with the properties expected for a high-mass X-ray binary. The X-ray luminosity of the nuclear source suggests the massive BH is radiating significantly below its Eddington limit (∼10−6 LEdd), and the soft spectrum resembles other weakly accreting massive BHs including Sagittarius A*. Analysis of the X-ray light curve of the nucleus reveals the tentative detection of a ~9 hr periodicity, although additional observations are required to confirm this result. Our study highlights the need for sensitive high-resolution X-ray observations to probe low-level accretion, which is the dominant mode of BH activity throughout the universe

Relationship of Metabolizable Protein Balance, Purine Derivative Excretion, and 3-Methyl Histidine Excretion to Feed Efficiency in Individually Fed Finishing Heifers

Individually fed heifers were used to determine the relationship of 3-methyl histidine, purine derivatives, and metabolizableprotein balance to feed efficiency. Heifers were fed finishing dietsthat were either deficient or sufficient in metabolizable protein. Urine samples were collected and analyzed for early, late, and entire feeding period concentrations of 3-methyl histidine, purine derivatives, and creatinine. Results from this study indicated a negative relationship between feed efficiency and metabolizable protein balance, and no relationship between 3-methyl histidine excretion and feed efficiency, suggesting that protein turnover and microbial protein synthesis are not related to feed efficienc

Relationship of Metabolizable Protein Balance, Purine Derivative Excretion, and 3-Methyl Histidine Excretion to Feed Efficiency in Individually Fed Finishing Heifers

Individually fed heifers were used to determine the relationship of 3-methyl histidine, purine derivatives, and metabolizableprotein balance to feed efficiency. Heifers were fed finishing dietsthat were either deficient or sufficient in metabolizable protein. Urine samples were collected and analyzed for early, late, and entire feeding period concentrations of 3-methyl histidine, purine derivatives, and creatinine. Results from this study indicated a negative relationship between feed efficiency and metabolizable protein balance, and no relationship between 3-methyl histidine excretion and feed efficiency, suggesting that protein turnover and microbial protein synthesis are not related to feed efficienc

The role of dietary fatty acids in predicting myocardial structure in fat-fed rats

<p>Abstract</p> <p><it>Background</it></p> <p>Obesity increases the risk for development of cardiomyopathy in the absence of hypertension, diabetes or myocardial ischemia. Not all obese individuals, however, progress to heart failure. Indeed, obesity may provide protection from cardiovascular mortality in some populations. The fatty acid milieu, modulated by diet, may modify obesity-induced myocardial structure and function, lending partial explanation for the array of cardiomyopathic phenotypy in obese individuals.</p> <p><it>Methods</it></p> <p>Adult male Sprague-Dawley rats were fed 1 of the following 4 diets for 32 weeks: control (CON); 50% saturated fat (SAT); 40% saturated fat + 10% linoleic acid (SAT+LA); 40% saturated fat + 10% α-linolenic acid (SAT+ALA). Serum leptin, insulin, glucose, free fatty acids and triglycerides were quantitated. <it>In vivo </it>cardiovascular outcomes included blood pressure, heart rate and echocardiographic measurements of structure and function. The rats were sacrificed and myocardium was processed for fatty acid analysis (TLC-GC), and evaluation of potential modifiers of myocardial structure including collagen (Masson's trichrome, hydroxyproline quantitation), lipid (Oil Red O, triglyceride quantitation) and myocyte cross sectional area.</p> <p><it>Results</it></p> <p>Rats fed SAT+LA and SAT+ALA diets had greater cranial LV wall thickness compared to rats fed CON and SAT diets, in the absence of hypertension or apparent insulin resistance. Treatment was not associated with changes in myocardial function. Myocardial collagen and triglycerides were similar among treatment groups; however, rats fed the high-fat diets, regardless of composition, demonstrated increased myocyte cross sectional area.</p> <p><it>Conclusions</it></p> <p>Under conditions of high-fat feeding, replacement of 10% saturated fat with either LA or ALA is associated with thickening of the cranial LV wall, but without concomitant functional changes. Increased myocyte size appears to be a more likely contributor to early LV thickening in response to high-fat feeding. These findings suggest that myocyte hypertrophy may be an early change leading to gross LV hypertrophy in the hearts of "healthy" obese rats, in the absence of hypertension, diabetes and myocardial ischemia.</p

Minimizing radiation injury and neoplastic effects during pediatric fluoroscopy: what should we know?

Radiation-induced injuries from fluoroscopic procedures in pediatric patients have occurred, and young patients are at greatest risk of many radiation-induced neoplasms. Some fluoroscopists have been injured from their use of fluoroscopy, and they are known to be at risk of radiation-induced neoplasm when radiation is not well-controlled. This article reviews the circumstances that lead to radiation injury and delineates some procedural methods to avoid injury and limit radiation exposure to both the patient and the fluoroscopist

Comparison of conventional and Alltech beef PN finishing programs: performance and

The objective of this study was to compare the feedlot and carcass performance of the PN Beef Program in relation to a conventional feedlot diet when both diets are combined with or without exogenous growth promotants

Complications from Surgeries Related to Ovarian Cancer Screening

The aim of this study was to evaluate complications of surgical intervention for participants in the Kentucky Ovarian Cancer Screening Program and compare results to those of the Prostate, Lung, Colorectal and Ovarian Cancer Screening trial. A retrospective database review included 657 patients who underwent surgery for a positive screen in the Kentucky Ovarian Cancer Screening Program from 1988–2014. Data were abstracted from operative reports, discharge summaries, and office notes for 406 patients. Another 142 patients with incomplete records were interviewed by phone. Complete information was available for 548 patients. Complications were graded using the Clavien–Dindo (C–D) Classification of Surgical Complications and considered minor if assigned Grade I (any deviation from normal course, minor medications) or Grade II (other pharmacological treatment, blood transfusion). C–D Grade III complications (those requiring surgical, endoscopic, or radiologic intervention) and C–D Grade IV complications (those which are life threatening) were considered “major”. Statistical analysis was performed using SAS 9.4 software. Complications were documented in 54/548 (10%) subjects. For women with malignancy, 17/90 (19%) had complications compared to 37/458 (8%) with benign pathology (p \u3c 0.003). For non-cancer surgery, obesity was associated with increased complications (p = 0.0028). Fifty patients had minor complications classified as C–D Grade II or less. Three of 4 patients with Grade IV complications had malignancy (p \u3c 0.0004). In the Prostate, Lung, Colorectal and Ovarian Cancer Screening trial, 212 women had surgery for ovarian malignancy, and 95 had at least one complication (45%). Of the 1080 women with non-cancer surgery, 163 had at least one complication (15%). Compared to the Prostate, Lung, Colorectal and Ovarian Cancer Screening trial, the Kentucky Ovarian Cancer Screening Program had significantly fewer complications from both cancer and non-cancer surgery (p \u3c 0.0001 and p = 0.002, respectively). Complications resulting from surgery performed as a result of the Kentucky Ovarian Cancer Screening Program were infrequent and significantly fewer than reported in the Prostate, Lung, Colorectal and Ovarian Cancer Screening trial. Complications were mostly minor (93%) and were more common in cancer versus non-cancer surgery

California’s methane super-emitters

Methane is a powerful greenhouse gas and is targeted for emissions mitigation by the US state of California and other jurisdictions worldwide. Unique opportunities for mitigation are presented by point-source emitters—surface features or infrastructure components that are typically less than 10 metres in diameter and emit plumes of highly concentrated methane. However, data on point-source emissions are sparse and typically lack sufficient spatial and temporal resolution to guide their mitigation and to accurately assess their magnitude4. Here we survey more than 272,000 infrastructure elements in California using an airborne imaging spectrometer that can rapidly map methane plumes. We conduct five campaigns over several months from 2016 to 2018, spanning the oil and gas, manure-management and waste-management sectors, resulting in the detection, geolocation and quantification of emissions from 564 strong methane point sources. Our remote sensing approach enables the rapid and repeated assessment of large areas at high spatial resolution for a poorly characterized population of methane emitters that often appear intermittently and stochastically. We estimate net methane point-source emissions in California to be 0.618 teragrams per year (95 per cent confidence interval 0.523–0.725), equivalent to 34–46 per cent of the state’s methane inventory for 2016. Methane ‘super-emitter’ activity occurs in every sector surveyed, with 10 per cent of point sources contributing roughly 60 per cent of point-source emissions—consistent with a study of the US Four Corners region that had a different sectoral mix. The largest methane emitters in California are a subset of landfills, which exhibit persistent anomalous activity. Methane point-source emissions in California are dominated by landfills (41 per cent), followed by dairies (26 per cent) and the oil and gas sector (26 per cent). Our data have enabled the identification of the 0.2 per cent of California’s infrastructure that is responsible for these emissions. Sharing these data with collaborating infrastructure operators has led to the mitigation of anomalous methane-emission activity

Results from the Super Cryogenic Dark Matter Search (SuperCDMS) experiment at Soudan

We report the result of a blinded search for Weakly Interacting Massive Particles (WIMPs) using the majority of the SuperCDMS Soudan dataset. With an exposure of 1690 kg days, a single candidate event is observed, consistent with expected backgrounds. This analysis (combined with previous Ge results) sets an upper limit on the spin-independent WIMP--nucleon cross section of $1.4 \times 10^{-44}$ ($1.0 \times 10^{-44}$) cm$^2$ at 46 GeV/$c^2$. These results set the strongest limits for WIMP--germanium-nucleus interactions for masses $>$12 GeV/$c^2$