Molecules to Burn: A Mechanistic Characterization of Cyanobacterial Aldehyde Deformylating Oxygenase.

The development of hydrocarbon based biofuels that can replace fossil fuels is essential to address the challenge of energy sustainability. However, there are few known biosynthetic pathways to produce these molecules and, generally, they are not well understood. The focus of this dissertation is to explore one of the very few biosynthetic routes to produce entirely unfunctionalized hydrocarbons through investigation of the highly unusual reaction catalyzed by cyanobacterial aldehyde deformylating oxygenase (cADO). To investigate the proton transfer step, solvent isotope effect (SIE) studies were undertaken. No appreciable difference in rate in D2O or H2O was observed, implying that proton transfer is not a kinetically significant step. However, when the ratio of protium to deuterium in the product alkane was measured as a function of the mole fraction of D2O, a D2OSIEobs of 2.19 ± 0.02 was observed. We interpret this SIE as most likely arising from a reactant state equilibrium isotope effect on a proton donor with an inverse fractionation factor, for which Φ = 0.45, consistent with an iron-bound water molecule being the proton donor to the alkane. Substrate analogs and binding channel mutations were used to investigate substrate binding or product release acting as a non-chemical rate limiting step. The kinetics of the mutants were investigated using octadecanal and, although no increase apparent rate was observed, two mutants displayed shifts in KM. These results suggest the hydrophobic pocket may be important in determining the binding affinity of long chain substrates. Protein film voltammetry experiments were used to explore the electrochemistry of cADO. The midpoint reduction potential was determined to be -73 ± 10 mV (vs SHE). Catalytic cyclic voltammetry with heptanal indicated a lower limit on alkane turnover of kobs > 0.63 per s, significantly faster than the rate of ~1 per min observed in solution. Interestingly, an alternative reaction was observed with enzyme and O2 indicating a futile cycle leading to H2O2 formation. These observations indicate that inefficient interactions with the reducing system or a partitioning effect between alkane and H2O2 turnover may be responsible for the sluggish activity of cADO.PHDChemical BiologyUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/113585/1/mwaugh_1.pd

Coming conflicts for liberty : a Thanksgiving sermon, preached November 30th, 1899, at a Union service in the First Baptist Church of Fall River, Mass.

The print copy of this sermon is held by Pitts Theology Library. The Pitts Theology Library's digital copy was produced as part of the ATLA/ATS Cooperative Digital Resources Initiative (CDRI), funded by the Luce Foundation. Reproduction note: Electronic reproduction. Atlanta, Georgia : Pitts Theology Library, Emory University, 2003. (Thanksgiving Day Sermons, ATLA Cooperative Digital Resources Initiative, CDRI). Joint CDRI project by: Andover-Harvard Library (Harvard Divinity School), Pitts Theology Library (Emory University), and Princeton Theological Seminary Libraries

A study exploring the relationship between employee happiness and financial performance within a South African financial institution

This research is an investigation of the relationship between employees 'happiness' and the financial performance of a financial services organisation in South Africa. As a component of the financial services industry the banking sector contributes greatly to the economic growth of the country. The South African Banking sector is concentrated and highly competitive. It is vital for banks to maintain competitiveness and ever increasing global competition adds further pressure on organisations to financially perform so as to meet the demands of their shareholders. The literature that has been reviewed and previous research suggest that employee 'happiness' is a vital variable influencing the performance and success of individuals. Organisational performance will be measured in terms of financial performance for the purposes of this research. The concept of financial performance and 'happiness' are discussed and a questionnaire based on the Satisfaction With Life Scale (Diener et al,1985) is used to determine the levels of 'happiness' at selected branches within the institution. The individual branches financial performance is determined via calculating selected ratios, namely cumulative leverage, cost to income ratio and net yield. An analysis of correlation was conducted to establish whether or not a relationship of statistical significance exists between employee 'happiness' and financial performance. It was concluded that there is no relationship of statistical significance between employee 'happiness' and the financial performance of branches within the organisation, it was suggested that other factors exert a much greater influence over financial performance. Some of these factors influencing financial performance are discussed and recommendations for further research are made