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.

Parameters of Reform and Unification in Modern Japanese Buddhist Thought: Murakami Senshō and Critical Buddhism

Reform is a word that, one might easily say, characterizes more than any other the history and development of Buddhism. Yet, it must also be said that reform movements in East Asian Buddhism have often taken on another goal—harmony or unification; that is, a desire not only to reconstruct a more worthy form of Buddhism, but to simultaneously bring together all existing forms under a single banner, in theory if not in practice. This paper explores some of the tensions between the desire for reform and the quest for harmony in modern Japanese Buddhism thought, by comparing two developments: the late 19th century movement towards ‘New Buddhism’ (shin Bukkyō) as exemplified by Murakami Senshō 村上専精 (1851–1929), and the late 20th century movement known as ‘Critical Buddhism’ (hihan Bukkyō), as found in the works of Matsumoto Shirō 松本史朗 and Hakamaya Noriaki 袴谷憲昭. In all that has been written about Critical Buddhism, in both Japanese and English, very little attention has been paid to the place of the movement within the larger traditions of Japanese Buddhist reform. Here I reconsider Critical Buddhism in relation to the concerns of the previous, much larger trends towards Buddhist reform that emerged almost exactly 100 years previous—the so-called shin Bukkyō or New Buddhism of the late-Meiji era. Shin Bukkyō is a catch-all term that includes the various writings and activities of Inoue Enryō, Shaku Sōen, and Kiyozawa Manshi, as well as the so-called Daijō-hibussetsuron, a broad term used (often critically) to describe Buddhist writers who suggested that Mahāyāna Buddhism is not, in fact, the Buddhism taught by the ‘historical’ Buddha Śākyamuni. Of these, I will make a few general remarks about Daijō-hibusseturon, before turning attention more specifically to the work of Murakami Senshō, in order to flesh out some of the similarities and differences between his attempt to construct a ‘unified Buddhism’ and the work of his late-20th century avatars, the Critical Buddhists. Though a number of their aims and ideas overlap, I argue that there remain fundamental differences with respect to the ultimate purposes of Buddhist reform. This issue hinges on the implications of key terms such as ‘unity’ and ‘harmony’ as well as the way doctrinal history is categorized and understood, but it also relates to issues of ideology and the use and abuse of Buddhist doctrines in 20th-century politics.

Thought-Action Fusion and Neutralization Behavior

This study presents a new inventory to assess thought-action fusion (TAF). 160 college students ages 18 to 22 (M = 19.17, SD = 1.11) completed the new Modified Thought Action Scale (MTAFS). Results indicated high internal consistency in the MTAFS (Cronbach’s α = .95). A principal component analysis suggested a three factor solution of TAF-Moral (TAFM), TAFLikelihood (TAFL), and TAF-Harm avoidance-Positive (TAFHP) all with eigenvalues above 1, and factor loadings above .4. A second study examined the association between TAF, obsessivecompulsive and anxiety tendencies after the activation of TAF-like thought processes in a nonclinical sample (n=76). Subjects were randomly assigned to one of three treatment groups intended to provoke TAFL-self, TAFL-other, and TAF moral thought processes. Stepwise regression analyses revealed: 1) the Obsessive-Compulsive Inventory subscales Neutralizing and Ordering significantly predicted instructed neutralization behavior (INB) in non-clinical participants; 2) TAF-Likelihood contributed significant unique variance in INB. These findings suggest that the provocation of neutralization behavior may be mediated by specific subsets of TAF and obsessive-compulsive tendencies.