Cleavage of Lipids and DNA by Metal Ions and Complexes

Metal ions and complexes utilized as cleavage agents have influenced many synthetic approaches of scientists to assist in the cleavage and transformation of biomolecules. These metal-based synthetic cleavage agents have potential applications in biotechnology or as molecular therapeutic agents. Herein, we have examined Ce(IV) metal ion and complexes as acidic hydrolytic agents in lipid hydrolysis reactions (Chapter 2 and 3), and a copper(II) complex that photo-oxidizes DNA upon exposure to ultraviolet light (Chapter 4). In Chapter 2 we examined the hydrolysis of sphingomyelin vesicles by Ce(NH4)2(NO3)6 (Ce(IV)) and compared the results to twelve d- and f-block metal salts, hydrolysis of mixed lipid vesicles and mixed micelles of sphingomyelin by Ce(IV), and hydrolysis of phosphatidylcholine vesicles by Ce(IV), using either MALDI-TOF mass spectrometry or colorimetric assays. In Chapter 3, we described the study of a Ce(IV) complex based on 1,3-bis[tris(hydroxymethyl)methylamino]propane as a potential acidic hydrolytic agent of phospholipids using colorimetric assays and NMR spectroscopy. The hydrolytic agent provided markedly enhance hydrolysis at lysosomal pH (~ 4.8), but suppress hydrolysis when pH was raised to near-neutral pH (~ 7.2). This was due to the pKa values of the donor atoms of the ligand, in which the metal’s electrophilicity was reduced to a greater extent at ~ pH 7.2 compared to ~ pH 4.8. Chapter 4 describes the synthesis and study of a Cu(II) complex based on a hexaazatriphenylene derivative for photo-assisted cleavage of double-helical DNA. Scavenger and chemical assays suggested the formation of DNA damaging reactive oxygen species, hydroxyl and superoxide radicals, and hydrogen peroxide, in the photocleavage reactions. Thermal denaturation and UV-vis absorption studies suggested that the Cu(II) complex binds in a non-intercalative fashion to duplex DNA

The Constitutional Validity of Declarations of Incompatibility in Australian Charters of Rights

New Australian human rights legislation has created novel ‘dialogues’ between different arms of government. In Victoria and the ACT courts have been empowered to make declarations of incompatibility to the Attorney-General regarding the human rights acts and other legislation. This article examines the Constitutional implications for a similar mechanism in a proposed Commonwealth Human Rights Ac

Metal-Assisted Hydrolysis Reactions Involving Lipids: A Review

This report covers major advances in the use of metal ions and complexes to hydrolyze ester and phosphate ester lipid bonds. These metal-based Lewis acids have been investigated as catalysts to isolate fatty acids from biological sources, as probes to study phospholipid bilayer properties, as tools to examine signal transduction pathways, and as lead compounds toward the discovery of therapeutic agents. Metal ions that accelerate phosphate ester hydrolysis under mild conditions of temperature and pH may have the potential to mimic phospholipase activity in biochemical applications

Increased canine pancreatic lipase immunoreactivity (cPLI) and 1,2-o-dilauryl-rac-glycero-3-glutaric acid-(6 '-methylresorufin) ester (DGGR) lipase in dogs with evidence of portal hypertension and normal pancreatic histology : a pilot study

The clinical presentations of both liver disease and pancreatitis are nonspecific and overlapping, which may cause difficulty in diagnosis. In our retrospective pilot study, we assessed whether dogs with evidence of portal hypertension and absence of pancreatitis on pancreatic histology have increases in canine pancreatic lipase immunoreactivity (cPLI) and 1,2-o-dilauryl-rac-glycero-3-glutaric acid-(6 '-methylresorufin) ester (DGGR) lipase. We included dogs that had been presented between 2008 and 2019 if they had normal pancreatic histology, histologically confirmed hepatopathy, and if canine pancreas-specific lipase (Spec cPL; Idexx) or DGGR lipase had been measured. Only dogs with portal hypertension were included. Six dogs fulfilled the inclusion criteria. Four of 6 and 2 of 6 dogs had Spec cPL and DGGR lipase exceeding the upper reference limit, respectively. From the 4 dogs with increased Spec cPL, 2 had concentrations of 200-400 mu g/L and 2 had concentrations >= 400 mu g/L. Our results suggest that canine portal hypertension might lead to increased Spec cPL and DGGR lipase values in the absence of pancreatitis on histology. Until more evidence in a larger number of dogs with portal hypertension is available, both tests should be interpreted cautiously in the presence of portal hypertension

Abstract Congruence Criteria for Weak Bisimilarity

We introduce three general compositionality criteria over operational semantics and prove that, when all three are satisfied together, they guarantee weak bisimulation being a congruence. Our work is founded upon Turi and Plotkin's mathematical operational semantics and the coalgebraic approach to weak bisimulation by Brengos. We demonstrate each criterion with various examples of success and failure and establish a formal connection with the simply WB cool rule format of Bloom and van Glabbeek. In addition, we show that the three criteria induce lax models in the sense of Bonchi et al

AN ECOLOGICAL EXPLORATION OF COACHES' PERCEPTIONS ON SEX EDUCATION

Sex education is a broad term used to describe education about sexual reproduction, human sexual anatomy, sexual intercourse, and other aspects of human sexual behavior. Yet is absent from curriculum in Kindergarten through Grade 12 schools. The purpose of this study was to examine the experience of one Black female coach of a girls’ youth sports team with a specific focus on how Black feminist thought archetypes frame informal conversation as it relates to sex education, youth, and sports, as well as the sexual script framework. If those frameworks are present, this study aimed to discern what contributes to them, according to the coach. To address the purpose and research questions, a qualitative case study explored a girls’ basketball team, coached by a woman, in which the majority of players were Black. An individual interview with the coach was conducted. This woman was a self-identified Black female. Additional data accrued through observations, field notes, and demographic information. Findings revealed five major themes. The participant and players (player’s family dynamics) aligned with Black feminist-thought archetypes and the sexual-script framework. In conclusion, study findings suggested future research on the intersectionality of sex education, sports, and youth would enhance knowledge of sex education in schools

Variation in Plasma Corticosterone in Migratory Songbirds: A Test of the Migration-Modulation Hypothesis

Physiological mechanisms underlying migration remain poorly understood, but recent attention has focused on the role of the glucocorticoid hormone corticosterone (CORT) as a key endocrine regulator of migration. The migration-modulation hypothesis (MMH) proposes that baseline plasma CORT levels are elevated in migratory birds to facilitate hyperphagia and lipogenesis and that further elevation of CORT in response to acute stress is suppressed. Consequently, CORT may be a poor indicator of individual condition or environmental variation in migratory birds. We tested the MMH by measuring baseline and stress-induced CORT in common yellowthroats (Geothlypis trichas) during fall migration over 2 consecutive years in the Revelstoke Reach drawdown zone, a migratory stopover site affected by local hydroelectric operations. Birds had low baseline CORT at initial capture (/mL) and then showed a robust stress response, with CORT increasing to ca. 50 ng/mL within 10-20 min. Our data therefore do not support the MMH. Baseline CORT did not vary with body mass, time of capture, Julian day, or year, suggesting that variable flooding regimes did not affect baseline CORT. Individual variation in the rate of increase in CORT was correlated with Julian day, being higher later in the migration period. Our data suggest that plasma CORT can be a useful metric in migration studies

Variation in plasma corticosterone in migratory songbirds: A test of the migration-modulation hypothesis

Physiological mechanisms underlying migration remain poorly understood, but recent attention has focused on the role of the glucocorticoid hormone corticosterone (CORT) as a key endocrine regulator of migration. The migrationmodulation hypothesis (MMH) proposes that baseline plasma CORT levels are elevated in migratory birds to facilitate hyperphagia and lipogenesis and that further elevation of CORT in response to acute stress is suppressed. Consequently, CORT may be a poor indicator of individual condition or environmental variation in migratory birds. We tested the MMH by measuring baseline and stress-induced CORT in common yellowthroats (Geothlypis trichas) during fall migration over 2 consecutive years in the Revelstoke Reach drawdown zone, a migratory stopover site affected by local hydroelectric operations. Birds had low baseline CORT at initial capture (!5 ng/mL) and then showed a robust stress response, with CORT increasing to ca. 50 ng/ mL within 10-20 min. Our data therefore do not support the MMH. Baseline CORT did not vary with body mass, time of capture, Julian day, or year, suggesting that variable flooding regimes did not affect baseline CORT. Individual variation in the rate of increase in CORT was correlated with Julian day, being higher later in the migration period. Our data suggest that plasma CORT can be a useful metric in migration studies