Cyclophospholipids Increase Protocellular Stability to Metal Ions

Model protocells have long been constructed with fatty acids, because these lipids are prebiotically plausible and can, at least theoretically, support a protocell life cycle. However, fatty acid protocells are stable only within a narrow range of pH and metal ion concentration. This instability is particularly problematic as the early Earth would have had a range of conditions, and life as we know it is completely reliant on metal ions for catalysis and the folding and activity of biological polymers. Here we show that prebiotically plausible monoacyl cyclophospholipids form robust vesicles that survive a broad range of pH and high concentrations of Mg2+, Ca2+, and Na+. Importantly, stability to Mg2+ and Ca2+ is improved by the presence of environmental concentrations of Na+. These results suggest that cyclophospholipids, or lipids with similar characteristics, may have played a central role during the emergence of Darwinian evolution.</p

Development of Oxidation Reactions Based on Vanadium Pentoxide, Dimethylsulfoxide, and Synthetic Iron-Rich Clays

In this dissertation we offer a discussion on the development of three novel oxidation methods. Chapter 1 presents the dehydroaromatization of N-heterocycles using vanadium pentoxide. Tetrahydrocarbazole is readily aromatized to carbazole by vanadium pentoxide in refluxing acetic acid under both stoichiometric and catalytic conditions. Eight other substrates are similarly aromatized in good yields. An extended application of this methodology is the efficient one-pot Fischer indole synthesis and dehydrogenation to form carbazoles. Chapter 2 describes a unique process for 1,2-dibromination of olefins using aqueous HBr and dimethyl sulfoxide. This novel methodology offers a simple, inexpensive, and mild alternative to the use of Br2 or other bromine carrying reagents. The substrate scope includes 21 olefins brominated in good to excellent yields. Three of six styrene derivatives yielded bromohydrins in good yields under the reaction conditions. Chapter 3 discloses the discovery of a synthetic iron-rich nontronite clay and its use as a dehydrogenating reagent. N-heterocycles such as 1,2,3,4-tetrahydrocarbazole, indoline, N-phenylbenzylamine are effectively aromatized by this unique new reagent in refluxing toluene. Extensive reaction optimization, investigation of substrate scope, characterization of the novel heterogeneous reagent is presented.Thesis (Ph.D., Chemistry) -- University of Idaho, 201

Nitrogenous Derivatives of Phosphorus and the Origins of Life: Plausible Prebiotic Phosphorylating Agents in Water

Phosphorylation under plausible prebiotic conditions continues to be one of the defining issues for the role of phosphorus in the origins of life processes. In this review, we cover the reactions of alternative forms of phosphate, specifically the nitrogenous versions of phosphate (and other forms of reduced phosphorus species) from a prebiotic, synthetic organic and biochemistry perspective. The ease with which such amidophosphates or phosphoramidate derivatives phosphorylate a wide variety of substrates suggests that alternative forms of phosphate could have played a role in overcoming the “phosphorylation in water problem”. We submit that serious consideration should be given to the search for primordial sources of nitrogenous versions of phosphate and other versions of phosphorus

Feasibility of school-based health education intervention to improve the compliance to mass drug administration for lymphatic Filariasis in Lalitpur district, Nepal: A mixed methods among students, teachers and health program manager.

BACKGROUND:Ensuring reduction in transmission of lymphatic Filariasis (LF) and addressing the compliance of people to mass drug administration (MDA) has led to renewed efforts in the field. School-based health education (SBHE) intervention, considered a cost-effective strategy with potential to reach the wider public through young people, was adopted as a strategy for social mobilization. This study assessed SBHE perceptions, implementation barriers, and factors in the supporting environment as well as its efficiency to successfully change LF MDA-related knowledge and practice. METHODS:This mixed methods study was conducted in four sites of Lalitpur district, Nepal. Classroom-based interactive health education sessions were used as the main intervention strategy in the study. In total, 572 students were assigned to intervention and control groups. Questionnaires were distributed before and after the intervention. Mann-Whitney and McNemar tests were used for analysis. Focus-group discussions with teachers and students and in-depth interviews with the district LF program manager as well as Education Office and school management authorities were conducted. Qualitative thematic analysis approach was adopted. RESULTS:Intervention curriculum played a significant role in increasing children's knowledge and practice (p<0.001). Barriers for school-based interventions were budget constraints, human resource deficiencies, lack of opportunities to conduct practical classes under the curriculum, and lack of collaboration with parents. Supportive factors were training provision, monitoring and evaluation practice, adequate facilities and equipment, positive parental attitudes, presence of interested teachers and students, and prioritization by program implementers. CONCLUSION:Effective program planning practices such as proper fiscal management, human resource management, training mechanisms, and efforts to promote practical classes and coordination with parents are required to develop and institutionalize the intervention. Effective learning and a supportive school environment appear to be important components to support implementation. The SBHE intervention is a feasible and promising intervention for accelerating compliance towards MDA to eliminate LF

Oxidation of Aliphatic Aldehydes Using Synthetic Iron Rich Clay

The oxidation of aliphatic aldehydes is an important tool in modern synthesis. However, current methods utilize harsh conditions, or expensive transition metal reagents. In this work, we present a novel method for the oxidation of aliphatic aldehydes using a synthetic, high iron clay. This clay, Fe-Non, is environmentally benign, and cheap to produce. Additionally, Fe-Non is easily recoverable by filtration, simplifying the purification process. These qualities make Fe-Non an ideal reagent for aldehyde oxidation in the production of drug like scaffolds

Cyclophospholipids Increase Protocellular Stability to Metal Ions

Model protocells have long been constructed with fatty acids, because these lipids are prebiotically plausible and can, at least theoretically, support a protocell life cycle. However, fatty acid protocells are stable only within a narrow range of pH and metal ion concentration. This instability is particularly problematic as the early Earth would have had a range of conditions, and life as we know it is completely reliant on metal ions for catalysis and the folding and activity of biological polymers. Here we show that prebiotically plausible monoacyl cyclophospholipids form robust vesicles that survive a broad range of pH and high concentrations of Mg2+, Ca2+, and Na+. Importantly, stability to Mg2+ and Ca2+ is improved by the presence of environmental concentrations of Na+. These results suggest that cyclophospholipids, or lipids with similar characteristics, may have played a central role during the emergence of Darwinian evolution.</p

Cyclophospholipids Increase Protocellular Stability to Metal Ions

Model protocells have long been constructed with fatty acids, because these lipids are prebiotically plausible and can, at least theoretically, support a protocell life cycle. However, fatty acid protocells are stable only within a narrow range of pH and metal ion concentration. This instability is particularly problematic as the early Earth would have had a range of conditions, and life as we know it is completely reliant on metal ions for catalysis and the folding and activity of biological polymers. Here we show that prebiotically plausible monoacyl cyclophospholipids form robust vesicles that survive a broad range of pH and high concentrations of Mg2+, Ca2+, and Na+. Importantly, stability to Mg2+ and Ca2+ is improved by the presence of environmental concentrations of Na+. These results suggest that cyclophospholipids, or lipids with similar characteristics, may have played a central role during the emergence of Darwinian evolution.</p