10 research outputs found

    Using Isoelectronic Reasoning to Examine the Constancy of Bond Dissociation Enthalpy Ratios [abstract]

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    Abstract only availableFaculty Mentor: Dr. Carol Deakyne, ChemistryIt has been shown both computationally and experimentally that the bond dissociation enthalpy ratio , where X= O, S, Se (group 16) and Y= C, Si, Ge (group 14) is nearly constant at 0.8. Computations also show that the corresponding ratios when Y= N+, P+, As+ (group 15) or Y= B-, Al-, Ga- (group 13) are nearly constant at 0.7 and 0.9 respectively. We have extended these calculations to the isoelectronic systems HXYXH, where X= N, P, As (group 15) and Y=C, Si, Ge (group 14) or Y= N+, P+, As+ (group 15) to determine whether our earlier observations or the constancy and relative magnitudes of the bond dissociation enthalpy of the ratios still hold. The dependency of the ratios on the geometries of the HXYXH and HXY molecules is also being examined. It would be particularly advantageous if our isoelectronic reasoning is valid because many of the systems that we are now examining computationally are difficult to study in the laboratory.Missouri Academ

    Structural factors that determine the ability of adenosine and related compounds to activate the cardiac ryanodine receptor

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    1. The effects of adenosine and adenine on the gating of native sheep cardiac ryanodine receptor (RyR) channels were investigated. By examining the mechanisms underlying channel activation and by using comparative molecular field analysis (CoMFA) we have investigated the structural features of adenine-based ligands involved in channel activation. 2. In the presence of 10 ΌM cytosolic Ca(2+), adenosine and adenine both activate the channel but only to a level approximately 10 and 20% respectively of that of ATP indicating that both are partial agonists of low efficacy. 3. Adenosine was able to antagonize the ATP-induced increase in open probability (Po) as expected for a partial agonist of low efficacy at the ATP sites on the cardiac RyR. 4. GTP (100 ΌM–10 mM) had no effect on channel gating indicating that the adenine ring structure is important for agonist activity at the ATP-sites on RyR. 5. CoMFA revealed an extremely strong correlation between the structural features of the five ATP analogues and the ability to increase (Po). Our model indicates that the high efficacy of ATP results primarily from the large electrostatic field established by the ionized phosphate groups. Reducing the number of phosphate groups lowers the strength of this field, leading to ligands with lower efficacy. In addition, steric interactions between the α-phosphate and ribose moieties and the RyR are correlated with low Po

    THE GENESIS OF CERTAIN PALEOZOIC INTERBEDDED IRON ORE DEPOSITS

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    Evolution of the freshwater ecosystem: The fossil record

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