Reactions of singlet oxygen and singlet oxygen mimics with dicyclopropylethylenes: Comparison of reactivity and mechanisms

An extensive study of the reaction pathways of 1,1-dicyclopropyl ethylene, cis- and trans- 1,2-dicyclopropylethylenes has been undertaken with different electrophiles 4-methyl-1,2,4-triazoline-3,5-dione (MTAD), tetracyanoethylene (TCNE), and singlet oxygen $\rm(\sp1O\sb2).$ Comparison of reactivity and reaction mechanisms among the electrophiles is investigated. Singlet oxygen exhibits significantly lower reactivity compared to the other electrophiles. MTAD and TCNE react with dicyclopropylethylenes to produce predominantly $\sp{\prime\prime}2+2\sp{\prime\prime}$ adducts and a small amount of the "ene" adducts. The $\sp{\prime\prime}2+2\sp{\prime\prime}$ is the major product presumably because of the high activation energy leading to the highly strained "ene" products. Solvent trapping studies provide strong evidence of a "stepwise" mechanism, involving a zwitterionic or aziridinium imide as an intermediate from the study of the reactions products of dicyclopropylethylenes and MTAD. ^

Community Development Districts: The entrepreneurial side of government

In an effort to reduce the cost and size of government public service delivery has become more decentralized, flexible and responsive. Public entrepreneurship entailed, among other things, the establishment of special-purpose governments to finance public services and carry out development projects. Community Development Districts (CDDs) are a type of special-purpose governments whose purpose is to manage and finance infrastructure improvements in the State of Florida. They have important implications for the way both growth management and service delivery occur in the United States. This study examined the role of CDDs for growth management policy and service delivery by analyzing the CDD profile and activity, the contribution of CDDs to the growth management and infrastructure development as well as the way CDD perceived pluses and minuses impact service delivery. The study used a mixed methods research approach, drawing on secondary data pertaining to CDD features and activity, semi-structured interviews with CDD representatives and public officials as well as on a survey of public officials within the counties and cities that have established CDDs. Findings indicated that the CDD institutional model is both a policy and a service delivery tool for infrastructure provision that can be adopted by states across the United States. Results showed that CDDs inhibit rather than foster growth management through their location choices, type and pattern of development. CDDs contributed to the infrastructure development in Florida by providing basic infrastructure services for the development they supported and by building and dedicating facilities to general-purpose governments. Districts were found to be both funding mechanisms and management tools for infrastructure services. The study also pointed to the fact that specialized governance is more responsive and more flexible but less effective than general-purpose governance when delivering services. CDDs were perceived as being favorable for developers and residents and not as favorable for general-purpose governments. Overall results indicated that the CDD is a flexible institutional mechanism for infrastructure delivery which has both advantages and disadvantages. Decision-makers should balance districts’ institutional flexibility with their unintended consequences for growth management when considering urban public policies.

Postmortem Demonstration of the Source of Pulmonary Thromboembolism: The Importance of the Autopsy

Periprostatic or paravaginal venous thromboses are rarely considered clinically as sites of clot origin in patients with pulmonary thromboembolism. The majority of emboli have been demonstrated to originate in the veins of the legs. This report raises awareness of pelvic vein thrombosis as a potential source of pulmonary embolism that is rarely considered or detected clinically, and which usually requires postmortem examination for recognition. It also reviews the possible routes emboli may take to reach the lungs.

Digital Initiatives Newsletter, Issue 2

Digital Initiatives is the newsletter of FIU Libraries’ Digital Collections and Institutional Repository (IR). This biannual newsletter serves as a resource for FIU students and faculty to keep up-to-date with the latest projects, collections, and services available from the FIU Libraries.

Reactions of singlet oxygen and singlet oxygen mimics with dicyclopropylethylenes: comparison of reactivity and mechanisms

An extensive study of the reaction pathways of 1,1- dicyclopropyl ethylene, cis- and trans- 1,2-dicyclopropylethylenes has been undertaken with different electrophiles 4-methyl-1,2,4- triazoline-3,5-dione (MTAD), tetracyanoethylene (TCNE), and singlet oxygen (102). Comparison of reactivity and reaction mechanisms among the electrophiles is investigated. Singlet oxygen exhibits significantly lower reactivity compared to the other electrophiles. MTAD and TCNE react with dicyclopropylethylenes to produce predominantly "2+2" adducts and a small amount of the "ene" adducts. The "2+2" is the major product presumably because of the high activation energy leading to the highly strained "ene" products. Solvent trapping studies provide strong evidence of a "stepwise" mechanism, involving a zwitterionic or aziridinium imide as an intermediate from the study of the reactions products of dicyclopropylethylenes and MTAD.