We describe a simple 1H NMR analysis that permits the stereochemistry of beta-hydroxy ketones to be assigned by visual inspection of the ABX patterns for the alpha-methylene unit of the beta-hydroxy ketone in the 1H NMR spectra. This method has been verified by application to a wide range of beta-hydroxy ketones deriving from aldol reactions of chiral aldehydes with a variety of chiral and achiral methyl ketone enolates (see Tables 1 and 2). The stereochemistry of 54 of these compounds have been assigned by rigorous chemical methods.

Publication informationEnergy, 35 (12): 4514-4521 Publisher ElsevierItem record/more information http://hdl.handle.net/10197/4906Publisher's statement This is the author's version of a work that was accepted for publication in Energy. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document.Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Energy (35, 12, (2010) it is found that electrification yields substantial and immediate reductions in greenhouse gas emissions for urban-type driving cycles. For inter-city travel, however, the percentage reduction attainable is much smaller, and the technical difficulty of achieving this capability is much greater. Unless that challenge can be overcome, it is shown, 50%-75% of CO 2 emissions from private cars will remain beyond the reach of electrification.

Abstract:Between 1990 and 2006, the primary energy requirement of the Irish transport sector increased by 166%. Associated greenhouse gas (GHG) emissions have followed a corresponding trajectory, and are responsible -at least in part -for Ireland's probable failure to meet its Kyoto targets. As in most countries, Ireland's transport sector is almost totally reliant on oil -a commodity for which Ireland is totally dependent on imports -and therefore vulnerable to supply and price shocks. Conversely, the efficiency and Carbon intensity of the Irish electricity supply system have both improved dramatically over the same period, with significant further improvements projected over the coming decade. This paper analyses the prospects for leveraging these changes by increasing the electrification of the Irish transport sector. Specifically, the potential benefits of plug-in hybrid-electric vehicles (PHEV) are assessed, in terms of reducing Primary Energy Requirement (PER) and CO 2 emissions. It is shown that, on a per-km basis, PHEV offer the potential for reductions of 50% or more in passenger car PER and CO 2 intensity. However, the time required to turn over the existing fleet means that a decade or more will be required to significantly impact PER and emissions of the PC fleet. (649.6 kt CO 2eq ), and sectoral share increasing to almost 21% of the national total (EPA 2008c). This continued growth in transport sector emissions means that, despite a trend towards reduced GHG emissions from the energy (primarily electricity generation) sector in particular, it is unlikely that Ireland will meet its Kyoto targets without purchasing carbon credits (EPA 2008c). Page | 3As in most countries, Ireland's transport sector is almost totally reliant on oil; in 2006 this reliance exceeded 99% . Having no indigenous oil resource, Ireland is totally dependent on imports, and therefore vulnerable to supply and price shocks. Indeed, Ireland's import dependence for all forms of energy exceeded 90% in 2007, making her the third most dependent amongst EU-27 member states, behind Cyprus (102.9%) and Luxembourg (98.9%) (European Commission DG TREN, 2008). This contrasts with the situation in 1990, when import dependence was approximately 68% , and with the average import dependency for energy of the EU27 at 53.8% (European Commission DG TREN, 2008). The increased import dependence is due in part to the decline in indigenous natural gas production from Kinsale since 1995, and decreasing peat production ; however, the strong increase in oil imports required to satisfy transport sector growth has also been a major factor.It is evident, therefore, that the continued oil-dependence of the Irish transport sector has significant negative implications in terms of TPER, GHG emissions, and import dependence.On the other hand, personal transport is central to individual freedom, to economic development, and as noted by then Irish Minister for Communications, Marine and Natural Resources in 2005 "…central to family life. Central to careers. Cen...

The effect of a three-way catalytic converter on particulate matter from a gasoline direct-injection engine during cold-start. AbstractThis work investigates the effect of a three-way catalytic converter and sampling dilution ratio on nano-scale exhaust particulate matter emissions from a gasoline direct-injection engine during cold-start and warm-up transients. Experimental results are presented from a four cylinder in-line, four stroke, wall-guided direct-injection, turbo-charged and inter-cooled 1.6 l gasoline engine. A fast-response particulate spectrometer for exhaust nano-particle measurement up to 1000 nm was utilised. It was observed that the three-way catalytic converter had a significant effect on particle number density, reducing the total particle number by up to 65 % over the duration of the cold-start test. The greatest change in particle number density occurred for particles less than 23 nm diameter, with reductions of up to 95 % being observed, whilst the number density for particles above 50 nm diameter exhibited a significant increase. The exhaust temperature plays a significant role on the influence of the catalytic converter on the nano-scale particulate matter. It is evident that the dilution ratio of the exhaust sample has a distinct effect on the particulate matter number and size distribution, influencing the engine-out PM more significantly than the tailpipe-out PM during cold-start engine operation. The catalytic converter also has a considerable effect on the estimated total particle mass.