Intensifying the Grid: A Typology for Medium Density Housing to Accommodate the Changing Demography of Wellington Suburbs

The combination of an increasing population, changing demographics and an ageing housing stock is driving the need for new and more varied housing types. Attempts to address these concerns have been less than satisfactory, leading to urban sprawl and the destruction of neighbourhood character. Residential intensification is a way of providing new housing while preserving both Wellington's compact urban form and open space. This thesis explores a process to increase housing density in the inner suburbs without a loss of urban form and character. Developed through design led research, the study first identifies those neighbourhoods most suited for intensification as Wellington's historic gridded suburbs. A representative street is then selected, and a strategy for integrating medium-density housing is developed. It then applies the principles in two multi-unit developments to address modern concerns with enhanced liveability and improved connection with private outdoor space. By manipulating the buildings in plan and section, complex internal configurations are possible, resulting in different sizes and types of dwellings, which accommodates varied demographic groups and household sizes. Through the elevation, the designs are then integrated into the local character of the site by reinterpreting the street's context in a contemporary manner. The design resolution was reached through a cyclical process, developing and being tested incrementally. The general principles of the design can be extrapolated and applied to other Wellington gridded neighbourhoods. They can also be applied to other locations with similar urban morphology in other New Zealand and Australian cities

Photocycloaddition of Arenes and Allenes

In this work, we report on a new intramolecular <i>para</i> cycloaddition of arenes with allenes, yielding attractive rigid scaffolds bearing several reactive functionalities to build in further diversity. Bicyclo[2.2.2]­octadiene-type products and benzoxepine acetals are formed in this reaction, in ratios and yields depending on the substitution pattern on the aromatic ring, the nature of the chromophore, and the tether. This unprecedented reaction has remarkable features that distinguish it from many other photochemical transformations: it is particularly robust with respect to substituents, it can be scaled up without a notable loss of efficiency, and it can lead to structures with a high degree of complexity in low to good yields. All photochemical precursors could be synthesized readily in three steps. We confirmed the compatibility of the nitrogen atom in the photocycloaddition step, which gives access to a bicyclo[2.2.2]­octadiene scaffold with two points that allow further diversification. This reaction was scaled up to multigram quantities without erosion of the typically high yields in photocycloadducts. Sequential deprotection of the N- or C-terminus of bicyclic amino acids gave access to two conformationally constrained unnatural amino acids with different dispositions of the two anchor points

Influence of Chlorinating Agents on the Formation of Stable Biomarkers in Hair for the Retrospective Verification of Exposure

Chlorine, as a dual-use chemical, is an essential industrial chemical which has been used as a chemical weapon in the past due to its toxicity and availability. The retrospective verification of chlorine intoxication is often especially challenging, and unambiguous markers are still missing. In this study, the effects of different chlorinating and oxidizing agents on human hair were investigated. Samples were exposed to a variety of chlorinating chemicals for a short time and then completely hydrolyzed by a HBr solution to break down their keratin proteins into individual amino acids. After derivatization and targeted liquid chromatography-mass spectrometry analysis, 3-chlorotyrosine and 3,5-dichlorotyrosine were unambiguously identified from human hair exposed to chlorine, hypochlorite, and sulfuryl chloride. Our results show long-term stability of these markers in the biological matrix, as the chlorotyrosines can still be found 10 months post-exposure at the same levels. Finally, an untargeted analysis was able to discriminate between some of the different intoxicants

Cytotoxic flavonoids and other constituents from the stem bark of <i>Ochna schweinfurthiana</i>

<div><p>Seven flavonoids, hemerocallone (<b>1</b>), 6,7-dimethoxy-3′,4′-dimethoxyisoflavone (<b>2</b>), amentoflavone (<b>4</b>), agathisflavone (<b>6</b>), cupressuflavone (<b>8</b>), robustaflavone (<b>9</b>) and epicatechin (<b>10</b>), together with three other compounds, lithospermoside (<b>3</b>), β-D-fructofuranosyl-α-D-glucopyranoside (<b>5</b>) and 3β-<i>O</i>-D-glucopyranosyl-β-stigmasterol (<b>7</b>), were isolated from the ethyl acetate extract of the stem bark of <i>Ochna schweinfurthiana</i> F. Hoffm. All the compounds were characterised by spectroscopic and mass spectrometric methods, and by comparison with literature data. Cytotoxicity of the extracts and compounds against cervical adenocarcinoma (HeLa) cells was evaluated by MTT assay. Compounds <b>4</b> and <b>6</b> exhibited good cytotoxic activity, with IC₅₀ values of 20.7 and 10.0 μM, respectively.</p></div

Secondary metabolites from <i>Triclisia gilletii</i> (De Wild) Staner (Menispermaceae) with antimycobacterial activity against <i>Mycobacterium tuberculosis</i>

<p>Triclisinone (<b>2</b>), a new ochnaflavone derivative, was isolated from the aerial parts of <i>Triclisia gilletii</i>, along with known drypemolundein B (<b>1</b>) and eight other known compounds. The chemical shifts of drypemolundein B (<b>1</b>) have been partially revised based on reinterpretation of NMR spectroscopic data. The eight other secondary metabolites are composed of: (+)-nonacosan-10-ol (<b>3</b>); stigmasterol (<b>4</b>), 3-<i>O</i>-β-D-glucopyranosylsitosterol (<b>5</b>), 3-<i>O</i>-β-D-glucopyranosylstigmasterol (<b>6</b>); oleanic acid (<b>7</b>); myricetin (<b>8</b>), quercetin (<b>9</b>) and 3-methoxyquercetin (<b>10</b>). Their structures were elucidated using IR, MS, NMR 1D and 2D, ¹H and ¹³C and comparison with literature data. Furthermore, compounds <b>1</b>, <b>2</b>, <b>5, 6, 8, 9</b> and the crude extract were tested against <i>Mycobacterium tuberculosis</i>. Compounds <b>1, 2, 8</b> and <b>9</b> displayed moderate to very good activity against resistant strain (codified AC 45) of <i>M. tuberculosis</i> with minimum inhibitory concentrations MICs ranging from 3.90 to 62.5 μg/mL<i>.</i></p