Synthetic and computational investigations into reaction pathways towards complex heterocyclic ring systems

Tetrazocines are eight-membered rings possessing four nitrogen atoms. The development of new synthetic routes to novel heterocyclic systems has remained a critical branch of synthetic organic chemistry due to potential applications in biomimetics and pharmaceuticals, such as dyes and explosives. 1,2,3,5-tetrazocines were originally proposed as an intermediate in the formation of 1,3a,6,6atetrahydroimidazo[4,5-c]pyrazole (a promising anti-fungal agent) from the irradiation of 2,3a,4,6a-tetraphenyl-3,3a,4,5,6,6a hexahydropyrrolo-[2,3-d]-1,2,3-triazole. One of our main aims was to synthesise novel 1,2,3,5-tetrazocines that possessed three phenyl and one methyl group(s) attached to the eight-membered ring, as previously synthesised 1,2,3,5-tetrazocines are of the tetra-phenyl variety. Adopting the established synthetic route in the pursuit of novel 1,2,3,5-tetrazocines proved difficult however, as the asymmetric nature of the 1,2,3,5-tetrazocine precursors (dihydrazones) resulted in altered reactivity as compared with their symmetric equivalents, this finding was rationalised using distributed multipole analysis. Ab initio calculations (B3LYP/6-31G(d)) indicate that for an underivatised 1,2,3,5- tetrazocine, the planar (aromatic) structure is the most stable, though this is not observed experimentally, presumably due to steric repulsions between the large aromatic substituents often used to stabilise these molecules. Excluding the planar geometry, we found that there is a significant thermodynamic stabilisation of 1,2,3,5- tetrazocine over the 1,3a,6,6a-tetrahydroimidazo[4,5-c]pyrazole, providing a novel route to heterocyclic systems

A settlers' guide: Designing for resilience in the hinterlands

© 2017 by the authors. There has often been a mutually beneficial relationship between cities and their rural hinterlands. The Kapiti region outside the city of Wellington in New Zealand is a prime example: it once provided Wellington's food, water and cultural diversity for both Māori and European settlers. However, productivity-driven agriculture and extensive dormitory-suburbanization have affected significant parts of this once-abundant hinterland. Food production is becoming more mono-cultural, water quality is degrading, ecosystems' biodiversity is disappearing, provincial town centres are shrinking, emigrating youth are leaving unbalanced demographics, Māori are increasingly disassociating their culture from their traditional lands and natural disasters are causing more impact-all of which is making Kapiti less resilient, and severing the once-healthy city-hinterland relationship. Our work on future settlement opportunities in Kapiti proposes alternatives, using experimental design-led research methods to develop speculative architectural and landscape architectural schemes. The schemes are framed by some of the spatial attributes of resilience: diversity, complexity, redundancy, interconnectivity and adaptability. Collectively, the work reveals design strategies that have a potential to rebuild hinterlands' culture, town centres, housing, agriculture, community and ecosystems and to recalibrate the broader relationship between hinterlands and metropolitan systems

The changing face of English freemasonry, 1640-1740

EThOS - Electronic Theses Online ServiceGBUnited Kingdo

The Law Commission : anti-money laundering and counter-terrorism financing - reform of the suspicious activity reporting regimes

In July 2018 the Law Commission published a Consultation Paper on proposed reforms to the United Kingdom (UK) suspicious activity reporting ( SARs) regimes relating to Anti-Money Laundering ( AML) and Counter-Terrorism Financing ( CTF). This article argues that, notwithstanding the proposed retention of an "all-crimes" approach to AML, the SARs regime may still be streamlined by way of the proposed amendments to the scope of reporting. The proposals to elevate the thresholds for reporting suspicions of money laundering, whilst conceptually appealing, present operational challenges for those within the reporting sectors

Probability Based Screening Guidelines to Estimate Soil Venting Remediation Viability

Environmental Engineerin