Cryptic post-transition state bifurcations that reduce the efficiency of lactone-forming Rh-carbenoid C-H insertions.

Byproducts of chemical reactions are generally thought to result from the competition between two reaction pathways, each with its own rate-determining transition state structure. We show here, however, that pathways with a single transition state structure followed by a post-transition state bifurcation may also be a source of undesired products, especially those whose appearance is unexpected. The viability of this scenario for intramolecular C-H insertion reactions affording β-lactones via Rh-carbenoid intermediates is assessed through quantum chemical calculations on potential energy surfaces and quasi-classical molecular dynamics simulations. It appears that, in these cases, the rhodium catalyst is to blame for the accessibility of a second, unintended, pathway following the transition state structure for β-lactone formation that leads to fragmentation to a ketene and carbonyl compound. If an unexpected product is formed via a post-transition state bifurcation, conventional strategies for suppressing its formation are unlikely to succeed. Guidelines for recognizing the presence of a post-transition state bifurcation are described here, along with hints at means for controlling product distributions

Conceptual design of thermal energy storage systems for near term electric utility applications. Volume 2: Appendices - screening of concepts

Volume 2 of this 2 volume report is represented. This volume contains three appendices: (1) bibliography and cross references; (2) taxonomy - proponents and sources; and (3) concept definitions

Conceptual design of thermal energy storage systems for near term electric utility applications. Volume 1: Screening of concepts

Over forty thermal energy storage (TES) concepts gathered from the literature and personal contacts were studied for their suitability for the electric utility application of storing energy off-peak discharge during peak hours. Twelve selections were derived from the concepts for screening; they used as storage media high temperature water (HTW), hot oil, molten salts, and packed beds of solids such as rock. HTW required pressure containment by prestressed cast-iron or concrete vessels, or lined underground cavities. Both steam generation from storage and feedwater heating from storage were studied. Four choices were made for further study during the project. Economic comparison by electric utility standard cost practices, and near-term availability (low technical risk) were principal criteria but suitability for utility use, conservation potential, and environmental hazards were considered

Cardiac Depression Scale: Mokken scaling in heart failure patients

Background: There is a high prevalence of depression in patients with heart failure (HF) that is associated with worsening prognosis. The value of using a reliable and valid instrument to measure depression in this population is therefore essential. We validated the Cardiac Depression Scale (CDS) in heart failure patients using a model of ordinal unidimensional measurement known as Mokken scaling. Findings: We administered in face-to-face interviews the CDS to 603 patients with HF. Data were analysed using Mokken scale analysis. Items of the CDS formed a statistically significant unidimensional Mokken scale of low strength (H<0.40) and high reliability (Rho>0.8). Conclusions: The CDS has a hierarchy of items which can be interpreted in terms of the increasingly serious effects of depression occurring as a result of HF. Identifying an appropriate instrument to measure depression in patients with HF allows for early identification and better medical management. Keywords: Cardiac Depression Scale, Heart failure, Depression, Mokken scalin

Choosing a calcium supplement for sheep fed cereal grains

Sheep fed cereal grains as an energy source over summer usually need added calcium because cereal grains are generally low in calcium (for example, 0.03 per cent calcium compared to 0.26 per cent phosphorus), and there may not be a natural source such as clover, weeds, leafy stubble or edible bush in the paddock. The safestt and most effective calcium supplement is finely ground limestone added to the feed, but some farmers have used other sources of calcium such as gypsum and superphosphate in this manner