title: The effect of SDS and TEG on chain mobility and secondary structure of decolored bloodmeal

authors: Hicks, Talia

subjects: IR spectroscopy

abstract: The effect of sodium dodecyl sulfate (SDS) and triethylene glycol (TEG) on secondary structure of decolored bloodmeal (DBM) during heating was examined via synchrotron-based Fourier transform infra-red spectroscopy (FT-IR) and wide angle X-ray scattering (WAXS). Both additives homogenize secondary structure distribution; SDS increases α-helices and decreases β-sheets and β-turns, while SDS–TEG reduces α-helices and β-sheets and increase random coils. Short heat cycles only change the composition of SDS-TEG treated DBM, implying TEG is responsible for chain mobility. Prolonged heating slowly increases β-sheets and suddenly increases α-helices at 55–75 °C in SDS-TEG treated DBM and 100 °C in SDS-treated DBM. Finally, WAXS shows that structural change due to heating is reversible for SDS-TEG treated DBM

text: The effect of SDS and TEG on chain mobility and secondary structure of decolored bloodmeal The effect of sodium dodecyl sulfate (SDS) and triethylene glycol (TEG) on secondary structure of decolored bloodmeal (DBM) during heating was examined via synchrotron-based Fourier transform infra-red spectroscopy (FT-IR) and wide angle X-ray scattering (WAXS). Both additives homogenize secondary structure distribution; SDS increases α-helices and decreases β-sheets and β-turns, while SDS–TEG reduces α-helices and β-sheets and increase random coils. Short heat cycles only change the composition of SDS-TEG treated DBM, implying TEG is responsible for chain mobility. Prolonged heating slowly increases β-sheets and suddenly increases α-helices at 55–75 °C in SDS-TEG treated DBM and 100 °C in SDS-treated DBM. Finally, WAXS shows that structural change due to heating is reversible for SDS-TEG treated DBM

year: 2014-11

title: Synthesis and Characterisation of Cycloaurated Gold(III) Complexes with Bidentate (O,O), (N,S) and (S,S) Chelating Ligands

authors: Smith, Tiffany Sharee

subjects: Cycloaurated Gold(III) Complexes

abstract: The reaction of C,N-coordinated gold(III) dihalides; BpAuCl₂ (Bp = 2 benzylpyridyl), AnpAuCl₂ (Anp = 2 anilinopyridyl) and TypAuCl₂ (Typ = 2 tolylpyridyl) with catecholate ligands in hot methanol and trimethylamine produced metallacycles with structural isomers of the general formula (C,N)Au{O,O}. Similarly, BpAuCl₂ and AnpAuCl₂ were reacted with thiourea ligands to form complexes giving high yield and good purity with the general formula (C,N)Au{PhNCSNR₂}+, by means of the addition of BPh₄- for precipitation. X-ray crystal structures of the compounds [AnpAu{PhNCSNMe₂}]BPh₄ and [AnpAu{PhNCSNCy₂}]BPh₄ confirmed the coordination of the thiourea to the gold centre through the N and S atoms. In both cases the geometry around the gold atom is square-planar with complex [AnpAu{PhNCSNCy₂}]BPh₄ showing a slightly more puckered conformation than [AnpAu{PhNCSNMe₂}]BPh₄ due to the sterically bulky cyclohexyl groups attached. Some thiourea derivatives were tested against P388 murine leukaemia cells with complex [AnpAu{PhNCSNHPh}]BPh₄ showing promising anti-tumour activity.

When thiourea ligands were replaced by dithiophosphinate and dithiophosphate ligands the reaction proceeded at room temperature without the need for the presence of a base. Relatively low yields of impure metallacycles with the general formula (C,N)Au{S₂PR₂}+ were obtained on the addition of BPh₄- or BF₄-. Attempts to improve purity by varying batches of starting materials, anion and solvents used were unsuccessful. X-ray crystal data from a single crystal of [(C,N)Au{S₂PPh₂}]BPh₄ shows the reduction of gold(III) to gold(I) forming a known polymeric gold(I) dithiophosphinate complex. In order to extend this study the synthesis of complexes with the general formula R₂PS₂AuCl₂ was attempted, but no new compounds were characterised.

Where possible, all new compounds reported in this thesis were characterised by ES-MS, IR, NMR, melting point and micro-elemental analysis.

text: Synthesis and Characterisation of Cycloaurated Gold(III) Complexes with Bidentate (O,O), (N,S) and (S,S) Chelating Ligands The reaction of C,N-coordinated gold(III) dihalides; BpAuCl₂ (Bp = 2 benzylpyridyl), AnpAuCl₂ (Anp = 2 anilinopyridyl) and TypAuCl₂ (Typ = 2 tolylpyridyl) with catecholate ligands in hot methanol and trimethylamine produced metallacycles with structural isomers of the general formula (C,N)Au{O,O}. Similarly, BpAuCl₂ and AnpAuCl₂ were reacted with thiourea ligands to form complexes giving high yield and good purity with the general formula (C,N)Au{PhNCSNR₂}+, by means of the addition of BPh₄- for precipitation. X-ray crystal structures of the compounds [AnpAu{PhNCSNMe₂}]BPh₄ and [AnpAu{PhNCSNCy₂}]BPh₄ confirmed the coordination of the thiourea to the gold centre through the N and S atoms. In both cases the geometry around the gold atom is square-planar with complex [AnpAu{PhNCSNCy₂}]BPh₄ showing a slightly more puckered conformation than [AnpAu{PhNCSNMe₂}]BPh₄ due to the sterically bulky cyclohexyl groups attached. Some thiourea derivatives were tested against P388 murine leukaemia cells with complex [AnpAu{PhNCSNHPh}]BPh₄ showing promising anti-tumour activity.

When thiourea ligands were replaced by dithiophosphinate and dithiophosphate ligands the reaction proceeded at room temperature without the need for the presence of a base. Relatively low yields of impure metallacycles with the general formula (C,N)Au{S₂PR₂}+ were obtained on the addition of BPh₄- or BF₄-. Attempts to improve purity by varying batches of starting materials, anion and solvents used were unsuccessful. X-ray crystal data from a single crystal of [(C,N)Au{S₂PPh₂}]BPh₄ shows the reduction of gold(III) to gold(I) forming a known polymeric gold(I) dithiophosphinate complex. In order to extend this study the synthesis of complexes with the general formula R₂PS₂AuCl₂ was attempted, but no new compounds were characterised.

Where possible, all new compounds reported in this thesis were characterised by ES-MS, IR, NMR, melting point and micro-elemental analysis.

year: 2012

title: Frozen rights?: The right to develop Maori treaty and aboriginal rights

authors: Joseph, Robert

subjects: Maori

abstract: Bishop Manuhuia Bennett often asked the question: "What did Maori call New Zealand before the arrival of the Pakeha [Europeans]?" After a deliberate pause, he would then simply utter: "Ours".

text: Frozen rights?: The right to develop Maori treaty and aboriginal rights Bishop Manuhuia Bennett often asked the question: "What did Maori call New Zealand before the arrival of the Pakeha [Europeans]?" After a deliberate pause, he would then simply utter: "Ours".

year: 2011