Semiempirical Study of the Bergman Reaction: Towards a Computationally Efficient and Accurate Method for Modeling Enediyne Anticancer Antibiotics

Over the past 7 years, the enediyne anticancer antibiotics have been widely studied due to their DNA cleaving ability. The focus of these antibiotics, represented by kedarcidin chromophore, neocarzinostatin chromophore, calicheamicin, esperamicin A, and dynemicin A, is on the enediyne moiety contained within each of these antibiotics. In its inactive form, the moiety is benign to its environment. Upon suitable activation, the system undergoes a Bergman cycloaromatization proceeding through a 1,4-dehydrobenzene diradical intermediate. It is this diradical intermediate that is thought to cleave double-stranded dna through hydrogen atom abstraction. Semiempirical, semiempiricalci, Hartree–Fock ab initio, and mp2 electron correlation methods have been used to investigate the inactive hex-3-ene-1,5-diyne reactant, the 1,4-dehydrobenzene diradical, and a transition state structure of the Bergman reaction. Geometries calculated with different basis sets and by semiempirical methods have been used for single-point calculations using electron correlation methods. These results are compared with the best experimental and theoretical results reported in the literature. Implications of these results for computational studies of the enediyne anticancer antibiotics are discussed.

The Effect of Grade Point Average on Undergraduates' Understanding of Heat Transfer

Engineering students continue to develop and show misconceptions due to prior knowledge and experiences (Miller, Streveler, Olds, Chi, Nelson, & Geist, 2007). Misconceptions have been documented in students’ understanding of heat transfer(Krause, Decker, Niska, Alford, & Griffin, 2003) by concept inventories (e.g., Jacobi,Martin, Mitchell, & Newell, 2003; Nottis, Prince, Vigeant, Nelson, & Hartsock, 2009). Students’ conceptual understanding has also been shown to vary by grade point average (Nottis et al., 2009). Inquiry-based activities (Nottis, Prince, & Vigeant, 2010) haveshown some success over traditional instructional methods (Tasoglu & Bakac, 2010) in altering misconceptions. The purpose of the current study was to determine whether undergraduate engineering students’ understanding of heat transfer concepts significantly changed after instruction with eight inquiry-based activities (Prince & Felder, 2007) supplementing instruction and whether students’ self reported GPA and prior knowledge, as measured by completion of specific engineering courses, affected these changes. The Heat and Energy Concept Inventory (Prince, Vigeant, & Nottis, 2010) was used to assess conceptual understanding. It was found that conceptual understanding significantly increased from pre- to post-test. It was also found that GPA had an effect on conceptual understanding of heat transfer; significant differences were found in post-test scores onthe concept inventory between GPA groups. However, there were mixed results when courses previously taken were analyzed. Future research should strive to analyze how prior knowledge effects conceptual understanding and aim to reduce the limitations of the current study such as, sampling method and methods of measuring GPA and priorknowledge.