Biocatalysis in organic synthesis

The first chapter provides an overview of the use of biocatalysis for the synthesis of pharmaceutical intermediates and natural products. This review focuses, in particular, on the impact of recent developments in technologies which enable the increased use of biocatalysts. These developments include: • the immobilisation of biocatalysts to enhance stability and ease of use, and enabling use in combination with metal and organocatalysts leading to dynamic kinetic resolution, as well as in continuous flow. • discovery and development of novel enzymes using molecular biology for enzyme engineering and metagenomics. The second chapter describes the lipase-mediated kinetic resolution of 2-phenylalkanols by tuning the steric properties of the acyl group to control the efficiency and selectivity of the resolution. In contrast to literature reports, efficient resolution was achieved using short-chain acyl groups through careful process control and substrate modification. The effect of increased steric demand at the stereocentre was also explored. Chapter three describes proof of concept that a hydrolase-catalysed dynamic kinetic resolution of a lactol is possible. By taking advantage of the spontaneous racemisation of the unreacted starting material, the dynamic kinetic resolution was carried out without the need for a separate racemisation catalyst. While the kinetic resolution was effective in a model system, the biotransformation was inhibited by the introduction of a second, remote stereocentre. Chapter four describes a dynamic kinetic resolution of synthetically versatile nitroalcohols by combination of a lipase-mediated resolution and the reversible intramolecular nitroaldol (Henry) reaction. Significant challenges in effecting the combination of the base-mediated racemisation step and the lipase-mediated resolution step were encountered. Reaction engineering allowed design of a sequential one-pot reaction system which furnished the products with excellent enantioselectivity, and good diastereoselectivity. Chapter five describes the use of novel transaminases in the kinetic resolution of model amine substrates and pharmaceutical intermediates by oxidative deamination, including exploration of the substrate scope of these novel biocatalysts. While transaminase-mediated reductive amination is an attractive method for asymmetric synthesis of chiral amines, the reductive amination is generally thermodynamically disfavoured. Preliminary investigation of approaches to favour the reductive amination is described. The final chapter contains the full experimental details, including spectroscopic and analytical data of all the compounds synthesised in this project; details of chiral phase HPLC analysis are included in the appendix

The significance of interconnector counter-trading in a security constrained electricity market

AbstractThroughout the European Union there is an increasing amount of wind generation being dispatched-down due to the binding of power system operating constraints from high levels of wind generation. This paper examines the impact a system non-synchronous penetration limit has on the dispatch-down of wind and quantifies the significance of interconnector counter-trading to the priority dispatching of wind power. A fully coupled economic dispatch and security constrained unit commitment model of the Single Electricity Market of the Republic of Ireland and Northern Ireland and the British Electricity Trading and Transmission Arrangement was used in this study. The key finding was interconnector counter-trading reduces the impact the system non-synchronous penetration limit has on the dispatch-down of wind. The capability to counter-trade on the interconnectors and an increase in system non-synchronous penetration limit from 50% to 55% reduces the dispatch-down of wind by 311GWh and decreases total electricity payments to the consumer by €1.72/MWh. In terms of the European Union electricity market integration, the results show the importance of developing individual electricity markets that allow system operators to counter-trade on interconnectors to ensure the priority dispatch of the increasing levels of wind generation

Electric vehicle: infrastructure regulatory requirements

In 2009 the European Union (EU) Directive on Renewable Energy placed an obligation on each Member State to ensure that 10% of transport energy (excluding aviation and marine transport) come from renewable sources by 2020. The Irish Government intends to achieve part of this target by making sure that 10% of all vehicles in its transport fleet are powered by electricity by 2020. Stakeholder groups include but are not limited to policy makers, the public, regulatory bodies, participants in the electricity retail market, the transmission and distribution system grid operators, the automotive industry, private enterprise, civil engineers, electrical engineers, electricians, architects, builders, building owners, building developers, building managers, fleet managers and EV owners. Currently it appears both internationally and Nationally the automotive industry is focused on EV manufacture, governments and policy makers have highlighted the potential environmental and job creation opportunities while the electricity sector is preparing for an additional electrical load on the grid system. The focus of this paper is to produce an international EV roadmap. A review of current international best practice and guidelines under consideration or recommended is presented. An update on any EV infrastructure charging equipment standards is also provided. Finally the regulatory modifications to existing National legislation as well as additional infrastructure items which may need control via new regulations are identified

The impact of recent developments in technologies which enable the increased use of biocatalysts

While biocatalytic transformations are very powerful in enantioselective synthesis, frequently occurring under mild conditions, and proceed with extraordinary selectivity, there are practical challenges associated with the use of biocatalysis, such as limited substrate scope, stability, and reusability. Recent technological developments, for example immobilization, continuous flow, and molecular biology, all contribute towards enhancing the use of enzymes in synthesis

Review of Energy Transition Policies in Singapore, London, and California

The paper contains the online supplementary materials for "Data-Driven Prediction and Evaluation on Future Impact of Energy Transition Policies in Smart Regions". We review the renewable energy development and policies in the three metropolitan cities/regions over recent decades. Depending on the geographic variations in the types and quantities of renewable energy resources and the levels of policymakers' commitment to carbon neutrality, we classify Singapore, London, and California as case studies at the primary, intermediate, and advanced stages of the renewable energy transition, respectively