http://hdl.handle.net/2440/4284 2013-06-20T00:17:24Z 2013-06-20T00:17:24Z Bloch, Witold Marek Babarao, Ravichandar Hill, Matthew Roland Doonan, Christian James Sumby, Christopher James http://hdl.handle.net/2440/78252 2013-06-13T05:30:17Z 2012-12-31T13:30:00Z

Title: Post-synthetic structural processing in a metal-organic framework material as a mechanism for exceptional CO₂/N₂ selectivity Author: Bloch, Witold Marek; Babarao, Ravichandar; Hill, Matthew Roland; Doonan, Christian James; Sumby, Christopher James Abstract: Here we report the synthesis and ceramic‐like processing of a new Metal‐organic Framework (MOF) material, [Cu(bcppm)H₂O], that shows exceptional selective separation for CO₂ over N₂ (ideal adsorbed solution theory, IAST S(ads) = 590). [Cu(bcppm)H₂O]·xS was synthesized in 82% yield by reaction of Cu(NO₃)₂∙2.5H₂O with the link bis(4‐(4‐ carboxyphenyl)‐1H‐pyrazolyl)methane (H₂bcppm) and shown to have a 2‐D 4⁴‐connected structure with an eclipsed arrangement of the layers. Activation of [Cu(bcppm)H₂O] generates a pore‐constricted version of the material through concomitant trellis‐type pore narrowing (b‐axis expansion and c‐axis contraction) and a 2‐D‐to‐3‐D transformation (a‐axis contraction) to give the adsorbing form, [Cu(bcppm)H₂O]‐ac. The pore contraction process and 2‐D‐to‐3‐D transformation were probed by single crystal and powder X‐ray diffraction experiments. The 3‐D network and shorter hydrogen bonding contacts do not allow [Cu(bcppm)H₂O]‐ac to expand under gas loading, across the pressure ranges examined, or following re‐solvation. This exceptional separation performance associates with a moderate adsorption enthalpy and therefore an expected low energy cost for regeneration.

2012-12-31T13:30:00Z Bruce, Michael Ian http://hdl.handle.net/2440/78149 2013-06-03T02:30:36Z 2012-12-31T13:30:00Z

Title: Reactions of polycyano-alkenes with alkynyl- and poly-ynyl-Group 8 metal complexes Author: Bruce, Michael Ian

2012-12-31T13:30:00Z Bell, Stephen Graham Zhou, Ruimin Yang, Wen Tan, Adrian B. H. Gentleman, Alexander Wong, Luet-Lok Zhou, Weihong http://hdl.handle.net/2440/76779 2013-04-10T02:30:48Z 2011-12-31T13:30:00Z

Title: Investigation of the substrate range of CYP199A4: modification of the partition between hydroxylation and desaturation activities by substrate and protein engineering Author: Bell, Stephen Graham; Zhou, Ruimin; Yang, Wen; Tan, Adrian B. H.; Gentleman, Alexander; Wong, Luet-Lok; Zhou, Weihong

2011-12-31T13:30:00Z Murphy, Rhys B. Pham, Duc-Truc Lincoln, Stephen Frederick Johnston, Martin Ross http://hdl.handle.net/2440/76743 2013-04-10T00:30:32Z 2012-12-31T13:30:00Z

Title: Molecular tweezers with freely rotating linker and porphyrin moieties Author: Murphy, Rhys B.; Pham, Duc-Truc; Lincoln, Stephen Frederick; Johnston, Martin Ross Abstract: Molecular tweezers were synthesised by using a microwave accelerated alkene plus cyclobutane epoxide reaction between norbornyl appended porphyrin moieties and a diepoxide functionalised phenyl diimide spacer. The tweezers contain several rotational degrees of freedom; about the porphyrin with respect to the norbornyl linker, and between the two norbornyl backbone sections. The ability of Zn(super)II metallated tweezer 1 to complex 1,4-diazabicyclo[2.2.2]octane (DABCO) was studied by UV/Vis and ¹H NMR spectroscopy and multivariate global spectral analysis. The system was found to form a strong 1:1 intramolecular complex (1:DABCO) with an association constant of K₁₁ = 8.1 × 10⁷ M⁻¹, transforming to a 1:2 open complex [1:(DABCO)₂] with K₁₂ = 2.7 × 10⁹ M⁻² at high concentrations of DABCO.

2012-12-31T13:30:00Z