Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks

Introduction of hydrogen bond functionality into metal-organic frameworks can enhance guest binding and activation, but a combination of linker flexibility and interligand hydrogen bonding often results in the generation of unwanted structures where the functionality is masked. Herein, we describe the self-assembly of three materials, where Cd2+, Ca2+, and Zn2+ are linked by N,Nʹ-bis(4-carboxyphenyl)urea, and examine the effect of the urea units on structure formation, the generation of unusual secondary building units, structural flexibility, and guest binding. The flexibility of the Zn MOF is probed through single-crystal to single-crystal transformations upon exchange of DMF guests for CS2, showing that the lability of the [Zn4O(RCO2)6] cluster towards solvation enables the urea linkers to adopt distorted conformations as the MOF breathes, even facilitating rotation from the trans/trans to the trans/cis conformation without compromising the overall topology. The results have significant implications in the mechanistic understanding of the hydrolytic stability of MOFs, and in preparing heterogeneous organocatalysts

The Lack of Recognition for the Film Choreographer in Hollywood

The following research directly addresses why the film choreographer has lacked adequate recognition within the Academy Awards, popularly known as the Oscars, presented by the Academy of Motion Picture Arts and Sciences. Additionally, this study aims to fill the research gap in relation to the minimal documentation that exists regarding the role and contributions of the film choreographer within the film industry. In order to move forward in assessing how the film choreographer can be recognized within the Oscars, one must address why they have not been sufficiently recognized within the history of the Academy Awards. By assessing the film choreographer’s value within the film industry through semi-structured interviews and data analysis methodologies, it was concluded their lack of recognition within the Oscars is due to the lack of dance’s presence in film, the undefined role of a film choreographer, and the general lack of awareness revolving around their contributions to film. All of which directly contribute to the film choreographer’s disproportionately perceived value within the film industry. Overall, this research intends to increase the dialogue revolving around the film choreographer as well as validate their value within the film industry. In conclusion, it is demonstrated there is an evident need for steps to advocate for film choreography to be recognized within the Oscars. It is time to give film choreographers recognition by the industry in which they work for, and this thesis hopes to serve as a catalyst for this change

MAO-A and the EEG Recognition Memory Signal in Left Parietal Cortex

A key part of episodic memory, or memory for the events of our lives, is recognition memory. Recognition memory is the ability to remember previously encountered stimuli. Studies have linked recognition memory to the old/new effect, an EEG indicator of stimulus familiarity. Monoamine oxidase A (MAO-A) is an enzyme that catalyzes monoamines, leading to the depletion of norepinephrine, epinephrine, serotonin, and dopamine. MAO-A is more efficiently transcribed in individuals with a 4 repeating sequence variation (4R) of the MAO-A gene leading to less monoamine availability. As many of these monoamines have been linked to episodic memory, we hypothesized that individuals homozygous for the 4R MAO-A polymorphism would show differences in mean EEG signal amplitudes during recognition memory. EEG data was recorded as participants viewed both new words and words that had been previously presented. Our results show that mean peak amplitudes over the left parietal cortex 500-800 ms post-stimulus presentation for hits were greater than those for correct rejections, indicating the old/new effect. Critically, our results revealed an interaction between mean hit and correct rejection amplitude over the left parietal cortex and MAO-A group. Individuals homozygous for the 4R variation (the High MAO-A group) do not show an old/new effect due to increased correct rejection amplitudes. These results suggest that less monoamine availability leads to new stimuli being identified as old by the left parietal cortex

Synthetic considerations in the self-assembly of coordination polymers of pyridine-functionalised hybrid Mn-Anderson polyoxometalates

The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilised, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups towards linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesise POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn2+ and Cu2+ link pyridine-appended Mn-Anderson clusters into two- and three-dimensional network solids with complex connectivities and topologies. Careful inspection of their solid-state structures has allowed us to identify common structure-directing features across these coordination polymers, including a square motif where two Zn2+ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, co-ligands and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials

Rearrangement of {α-P2W15} to {PW6} moieties during the assembly of transition-metal-linked polyoxometalate clusters

We report the formation of two polyoxotungstates of the general formula [M6(PW6O26)(α-P2W15O56)2(H2O)2]23− (M = CoII or MnII), which contain {PW6} fragments generated from the [P2W15O56]12− precursor, which demonstrates for the first time the transformation of a Dawson lacunae into a Keggin lacunary building block. Solution analysis of the clusters has been conducted via electrospray ionisation mass spectrometry

Uncovering the structural diversity of Y(III) naphthalene-2,6-dicarboxylate MOFs through coordination modulation

Metal-organic frameworks (MOFs) – network structures built from metal ions and clusters and connecting organic ligands – are typically synthesized by solvothermal self-assembly. For transition metal based MOFs, structural predictability is facilitated by control over coordination geometries and linker connectivity under the principles of isoreticular synthesis. For rare earth MOFs, coordination behaviour is dominated by steric and electronic factors, leading to unpredictable structures and poor control over self-assembly. Herein we show that coordination modulation – the addition of competing ligands into MOF syntheses – offers programmable access to six different Y(III) MOFs all connected by the same naphthalene-2,6-dicarboxylate ligand, despite controlled synthesis of multiple phases from the same metal-ligand combination often being challenging for rare earth MOFs. Four of the materials are isolable in bulk phase purity, three are amenable to rapid microwave synthesis, and the fluorescence sensing ability of one example towards metal cations is reported. The results show that a huge variety of structurally versatile MOFs can potentially be prepared from simple systems, and that coordination modulation is a powerful tool for systematic control of phase behaviour in rare earth MOFs

Enhancing Museum Narratives: Tales of Things and UCL’s Grant Museum

Emergent mobile technologies offer museum professionals new ways of engaging visitors with their collections. Museums are powerful learning environments and mobile technology can enable visitors to experience the narratives in museum objects and galleries and integrate them with their own personal reflections and interpretations. UCL‟s QRator project is exploring how handheld mobile devices and interactive digital labels can create new models for public engagement, personal meaning making and the construction of narrative opportunities inside museum spaces. The use of narrative in museums has long been recognised as a powerful communication technique to engage visitors and to explore the different kinds of learning and participation that result. Many museums make extensive use of narrative, or storytelling, as a learning, interpretive, and meaning making tool. This chapter discusses the potential for mobile technologies to connect museums to audiences through co-creation of narratives, taking the QRator project as a case study. The QRator project aims to stress the necessity of engaging visitors actively in the creation of their own interpretations of museum collections through the integration of QR codes, iPhone, iPad, and Android apps into UCL‟s Grant Museum of Zoology. Although this chapter will concentrate on mobile technology created for a natural history museum, issues of meaning making and narrative creation through mobile technology are applicable to any discipline. In the first instance, the concern is with the development of mobile media in museums followed by a discussion of the QRator project which stresses the opportunities and challenges in utilizing mobile technology to enhance visitor meaning making and narrative construction. Finally, this chapter discusses the extent to which mobile technologies might be used purposefully to transform institutional cultures, practices and relationships with visitors

A Framework for Building Technological Learning: Evidence from the New Zealand Dairy Industry

One aspect of the process of technology adoption is technological learning (TL), the way farmers gather information and turn it into knowledge. In a study of the New Zealand dairy industry, researchers examined the factors that affect TL. Findings suggest that the speed with which farmers engage in TL is influenced by the efficiency of the innovation system, the maturity of the farm system, and the individual characteristics of the farmer. The article presents a model demonstrating how these three sets of factors may affect TL that can be used by Extension agents to help them develop a strategy for engaging farmers in TL