Anion recognition and anion-mediated self-assembly with thiourea-functionalised fused [3]polynorbornyl frameworks

Three conformationally preorganised host molecules based on the [3]polynorbornyl framework and incorporating di-urea receptors were synthesised and their interaction with a series of anions investigated by 1H NMR spectroscopy. A high affinity of each host molecule for dihydrogenphosphate (H2PO4–) and dihydrogenpyrophosphate (H2P2O72–) was identified. In addition to binding to the urea receptors of the host molecules, evidence for an interaction involving the non-polar C–H groups within the binding cavity of the framework and guest anions was also discovered. Furthermore, an unusual 2 : 1 host-to-anion stoichiometry was indicated when binding H2P2O72–, and a model for the anion-mediated self-assembly of this complex species is proposed.

Weissenhof siedlung exhibition

UK sound-artist Scanner (whom we met on the program earlier this year) has been Artist-in-Residence for BBC Radio 4's 'Front Row' arts program where he's been experimenting with the medium of broadcasting. We heard one piece which explores the idea of social spaces in the city - associated with the visionary architectural ideas of Buckminster Fuller.

This morning we are staying with ideas of housing for the modern world.

Stuttgart, Germany, is our place of disembarkation - where in 1927 a modern housing estate - the Weissenhof Seidlung - was built to showcase the very latest work from the biggest names in modern architecture. 33 houses and apartments of all shapes and sizes - unified by their white, cubic streamlined forms.

The Estate is now a national monument and is a site of pilgrimage for architecture fans the world over.

Melbourne's Span Gallery is showing photographs of the Weissenhof Seidlung - and waiting in the wings to take us through it is historian Judith Trimble, joined by our own Rhiannon Brown, and - making a few guest appearances - the master of the modern movement, Le Corbusier, caught on tape here in the late 1950s.

Little con

Performed on the last Friday of every month (December and January excluded) 2005 – at a variety of venues in Melbourne, including the Cecil Street Studio and the Dancehouse. Founders and regular participants: Shaun McLeod, Paul Romano, Ann-maree Ellis, Dianne Reid, Grace Walpole and Joseph Lehrer. National and international guest artists include: Rosalind Crisp (Australia & France), Andrew Morrish (Australia and France), Tony Osborne (Sydney), Jane McKernan (Sydney) and many other Melbourne based performers.

Size matters—strong binding of the terephthalate dianion by thiourea functionalised fused [n]polynorbornane hosts

Remarkably strong binding of the new [5]polynorbornane based host 2b to the terephthalate dianion is based on size complementarity of the preorganised binding cleft with the rigid dicarboxylate guest.

The influence of failure severity and perceived employee effort on consumers' postcomplaint negative WOM intentions in a service guarantee context

This study employed a 2 x 2 full-factorial, between-subjects design experiment examining the influence of failure severity and perceived employee effort on hotel guests’ negative word-ofmouth (WOM) intentions following invocation of a service guarantee. The study involved a sample of 131 online panel members. Results suggest that negative WOM intentions reduced when a greater level of effort is exerted by staff in rectifying the guest’s problem and increased when a more severe failure is experienced. There is a stronger difference in guests’ negative WOM intentions between the high and low employee effort conditions when a minor versus a severe service failure is experienced by guests.

‘My history is a tile in a mosaic’ : an interview with Jim Cullen

JIM CULLEN was born in Queens, New York, and attended public schools on Long Island. He received his B.A. in English from Tufts University, and his A.M. and Ph.D. degrees in American Civilization from Brown University. He has taught at a number of colleges and universities, including Harvard and Brown. He is currently a teacher, and serves on the Board of the Trustees, at the Ethical Culture Fieldston School in New York City. Jim is married to historian Lyde Cullen Sizer and has four children.
CONTEXT: Dr Glenn Moore co-ordinates the subject 'Searching for the American Dream’ at The University of Melbourne. For the last nine years he has taken second and third year history students to Boston, New York and Washington, D.C to explore the philosophy of genius loci. Dr Moore gets students to work in food banks, visit homeless shelters, museums and organizes an array of guest speakers with experts such as Boston public defender, Denise Regan, Neera Tanden, Hillary Clinton’s campaign manager and Alec Ross, vice president of One Economy. As the leading expert on the American Dream, with the publication of so many books in American history such as: The American Dream: A Short History of an Idea that Shaped a Nation, Born in the U.S.A.: Bruce Springsteen and the American Tradition and Restless in the Promised Land: Catholics and the American Dream, Jim Cullen has spoken to the students for the last five years. I interviewed him prior to his recent discussion with the students in New York on 5 July 2006 at the Fashion Institute of Technology.

Organotin-oxo clusters

This thesis reports on the development and expansion of reliable synthetic di-and multi-tin precursors for the assembly of oligomeric organotin-oxo compounds in which the shape, dimension and tin nuclearity can be controlled. The reaction of polymeric diorganotin oxides, (R2SnO)m (R = Me, Et, n-Bu, n-Oct, c-Hex, i-Pr, Ph), with saturated aqueous NH4X solutions (X = F, Cl, Br, I, OAc) in refluxing 1,4-dioxane afforded in high yields dimeric tetraorganodistannoxanes, [R2(X)SnOSn(X)R2]2, and in a few cases diorganotin dihalides or diacetates, R2SnX2. This method appears to be particularly good for the synthesis of halogenated tetraorganodistannoxanes but a less suitable method for the preparation of dicarboxylato tetraorganodistannoxanes. Identification of [R2(OH)SnOSn(X)R2]2 (R = n-Bu; X = Cl, Br) and [R2(OH)SnOSn(X)R2][R2(X)SnOSn(X)R2] suggest a serial substitution mechanism starting from [R2(OH)SnOSn(OH)R2]2. A series of α, ω -bis(triphenylstannyl)alkanes, [Ph3Sn]2(CH2)n (n = 3-8, 10, 12) and some of their derivatives were synthesised and characterised. These α, ω-bis(triphenylstannyl)alkanes, [Ph3Sn]2(CH2)n were converted to the corresponding halides [R(Cl)2Sn]2(CH2)n (R = CH2SiMe3) and subsequently to the polymeric oxides {[R(0)Sn]2(CH2)n}m. Reaction of {[R(O)Sn]2(CH2)n}m with [R(Cl)2Sn]2(CH2)n. (n = 3, n' = 4 and n = 4, n' = 3) in toluene at 100°C results in a mixture of symmetric and asymmetric double ladders, where different spacer chain lengths (n and n') provide the source of asymmetry. The coexistence at high temperature of separate 119Sn NMR signals belonging to symmetric and asymmetric double ladders suggests an equilibrium that is slow on the 119Sn NMR time scale and the position of which is temperature dependent. However, 119Sn NMR spectroscopic experiments of {[R(0)Sn]2(CH2)3}m with [R(Cl)2Sn]2(CH2)n for longer spacers (n - 5, 6, 8, 10, 12) reveal that molecular self-assembly of symmetric spacer-bridged di-tin precursors of equal chain length is preferred over asymmetric species. An ether-bridged di-tin tetrachloride [R(Cl)2Sn(CH2)3]2O (R = CH2SiMe3) and its corresponding polymeric oxide {[R(O)Sn(CH2)3]2O}m were synthesised and characterised. Reaction of [R(Cl)2Sn(CH2)3]2O with {[R(O)Sn(CH2)3]2O}m results in a unique functionalised double ladder {{[RSn(Cl)](CH2)3O(CH2)3[RSn(Cl)]}O}4 whose structure in the solid state was determined by X-ray analysis. Identification of tetrameric functionalised double ladder as well as dimeric and monomeric species suggest the existence of an equilibrium in solution. The feasibility of the functionalised double ladder to form host-guest complexes with a variety of metal cations is investigated using electrospray mass spectrometry (ESMS). Evidence for such complexes is found only for sodium cations. The reaction between {[R(O)Sn]2(CH2)n}m (n = 3, 4, 8, 10) and triflic acid is described. The initial formed products [RSn(CH2)nSnR](OTf)4 are easily hydrolysed. For n = 3, self-assembly leads to a discrete double ladder type structure, {{[RSn(OH)](CH2)3[RSn(H2O)]}O}44OTf, which is the first example of a cationic double ladder. For n ≥ 3, hydrolysis gives polymeric products, as demonstrated by the crystal structure of {[(H2O)(OH)RSn]2(CH2)4-2OTf2H2O}m. Two spacer-bridged terra-tin octachlorides [R(Cl)2Sn(CH2)3Sn(Cl)2]2(CH2)n (R = CH2SiMes; n = 1, 8) and their corresponding polymeric oxides {[R(O)Sn(CH2)3Sn(O)]2(CH2)n}m were successfully synthesised and characterised. Attempts were made to synthesise quadruple ladders from these precursors. Reactions of [R(Cl)2Sn(CH2)3Sn(Cl)2]2CH2 with {[R(O)Sn(CH2)3Sn(O)]2CH2}m or (Y-Bu2SnO)3 result in, mostly insoluble, amorphous solids. Reactions of [R(Cl)2Sn(CH2)3Sn(Cl)2]2(CH2)8 with {[R(O)Sn(CH2)3Sn(O)]2(CH2)8}m or (t-Bu2SnO)s result in new tin-containing species which are presumably oligomeric. The synthesis of a series of alkyl-bridged di-tin hexacarboxylates [(RCO2)3Sn]2(CH2)n (n = 3, 4; R = Ph, c-C6H11, CH3, C1CH2) is also reported. The hydrolysis of these compounds is facile and complex. There appears to be no correlation between spacer chain length and hydrolysis product. However, the conjugate acid strength of the carboxylate does appear to be important. In general only insoluble amorphous polymeric organotin-oxo compounds were obtained.

Ethnomusicological study of music makers in an Australian military band

This dissertation reports on a study of music making in a band of the Australian Army Band Corps. The thesis of the dissertation is how the world views of the soldier-musicians of the Australian Army Band, Kapooka, are constructed in the context of their work in military music performance. In arguing this thesis, the author provides a brief history of military music in Australia, and - demonstrates how rank and military discipline intersect with music making in the lived experience of the soldier-musicians; - explores how the dichotomy between music making as a craft and music making as art is resolved in a setting where the employer regards music making as a trade, while the soldier-musicians strive to meet artistic goals; - demonstrates how successful music making and successful soldiering are both forms of work which depend upon effective collective action; - demonstrates that while military bands play the widest repertoire of musical styles of any Western music ensemble, the styles converge toward a homogenous, eclectic, military band performance style: and - explores how military music, which may have limited intrinsic interest, in certain ceremonial settings may link with other visual and auditory symbol systems to generate profound meaning both for the soldier-musicians themselves and for their audiences. The study examines the processes by which the world views of soldier-musicians are shaped by the institutional context in which they work, as they participate in a music tradition which has been a powerful agent in the shaping of Australian patriotic traditions. The study uses a naturalistic participant observation methodology. The author worked as an honorary guest civilian member of the band’s trombone section to collect data in the form of fieldnotes and interviews. Data analysis and interpretation was made according to the tenets of grounded theory. Evidence in the form of first hand accounts from the perspective of the researcher and from the soldier-musicians themselves is employed to generate both emic and etic understandings. An understanding of a music culture from the participant's point of view is a central concern of the study.

The design and evaluation of two types of chemical sensor

During the course of this investigation it was discovered that functionalised Ruthenium tris(bipyridyl) complexes exhibit different chemical, spectroscopic and electrochemical properties to those of the parent compound. Furthermore, it was possible to develop 1,8-naphthalimide-based compounds that furnished strong 1:1 host:guest complexes with larger anions such as hydrogen pyrophosphate. This dissertation presents in investigation into the systhesis and analytical evaluation of two types of chemical sensors: chemiluminescent and fluorescent.

Norbornenes and [n]polynorbornanes as molecular scaffolds for anion recognition

In total, 18 novel norbornene and [n]polynorbornane based anion receptors were synthesised and evaluated. The host:guest complexes examined were influenced by the position and number of available recognition sites within each binding cleft. It was concluded that [n]polynorbornane scaffolds are ideal for studying the fundamental concepts of supramolecular chemistry.

Transparent uv-shielding films from organic small molecule-intercalated layered double hydroxide nanoplatelets/polymer composite

In this study, layered double hydroxide (LDH) with nitrate as the interlayer anion has been partially exfoliated in dimethyl sulfoxide (DMSO). Atomic force microscopy (AFM) images showed that both the lateral size and the thickness of the LDH nanoplatelets were decreased after DMSO treatment. Formation of transparent LDH suspension in DMSO was observed. Taking this advantage, we have prepared transparent LDH/ethylene-vinyl alcohol copolymer (EVOH) nanocomposite films using DMSO as the processing solvent. Organic small molecules, UV absorbers, were intercalated into the LDH interlayers to incorporate the UV-shielding property into the transparent composite films. The thermal stability of UV absorbers was considerably improved after intercalation, which was attributed to the electrostatic interaction between the guest UV absorbers and the host LDH layers. The prepared composite films were flexible and exhibited excellent UV-shielding capability, but had transmittance as high as 90% in the visible region. The effect of LDH filler on thermal and mechanical properties of the composite films was also examined.

Visible transparent, UV-blocking polymer nanocomposite films containing nano-sized organic-LDH (Layered Double Hydroxide) hybrid

A nano-sized Mg2Al layered double hydroxide (LDH) was used for encapsulating an organic UV absorber, 2-hydroxy-4- methoxybenzeophenone-5-sulfonic acid (HMBS), to produce HMBS@LDH hybrid nano-platelets. Upon dispersing this organic-inorganic hybrid LDH into ethylene-vinyl alcohol copolymer (EVOH) for film casting, a thin polymer
nanocomposite film that is UV opaque but highly transparent to visible light (higher than 90%) was formed. Thermogravimetry (TG) analysis confirmed that the intercalation of HMBS into LDH considerably increased the thermal stability of HMBS. Such an improvement was attributed to the strong guest-host interaction between the HMBS anions and the LDH layers. Also, the nanocomposite films were flexible and had good mechanical properties.