More-than-care: People with intellectual disability and emerging vulnerability during pandemic lockdown.

This paper offers more-than-care as a framework for analysing how vulnerability emerges in the lives of people with intellectual disability beyond relations of care. More-than-care detaches vulnerability from the identity category of disability. It provides a framework for conceptualising vulnerability in an unequal, neoliberalising, and ableist world and sheds new light on the ever-evolving constitution of vulnerability and disability. This intervention breaks with conceptions of vulnerability centred on care needs that leave other circumstances that inform vulnerabilities unexamined. Importantly, the framework shifts responsibility for managing vulnerabilities away from carers alone. The more-than-care framework is grounded in socio-material conceptualisations of disability and advances a tripartite framing of vulnerability. First, it grounds studies of vulnerability in histories of spatially uneven investment in infrastructure and resources that shape how care and other practices can assemble to produce, challenge, and manage vulnerability. Second, it recalibrates dominant conceptions of the temporality of vulnerability to ensure sensitivity to the unpredictability of emergent vulnerabilities. Third, in following a socio-material conceptualisation of intellectual disability, more-than-care expands discussions about agency in the context of vulnerability. These concepts are empirically examined through an analysis of how vulnerability emerges in the lives of four self-advocates with intellectual disability during Melbourne's first and second COVID-19 lockdowns. The analysis shows that vulnerability was highly dynamic and unpredictable as it emerged in complex socio-material assemblages that included care arrangements, embodied experiences and agencies, and past instances of neglect and exploitation.

Syntheses and structural characterizations of inorganic ansa-metallocene analogues: ansa-ferratricarbadecaboranes.

New linked cyclopentadienyl-tricarbadecaboranyl and bis-tricarbadecaboranyl dianions have been used to form the first examples of ansa-metallatricarbadecaboranyl complexes. The hybrid cyclopentadienyl-tricarbadecaboranyl dianion, Li2(+)[6-C5H4-(CH2)2-nido-5,6,9-C3B7H9](2-) (1), was produced by an initial carbon-insertion reaction of a nitrile-substituted cyclopentadiene with the arachno-4,6-C2B7H12(-) anion, followed by deprotonation to the dianion with LiH. The linked-cage bis-tricarbadecaboranyl dianion, Li2(+)[6,6'-(CH2)2-nido-(5,6,9-C3B7H9)2](2-) (2), was produced by a similar carbon-insertion route involving the reaction of two equivalents of arachno-4,6-C2B7H12(-) with succinonitrile. The reaction of 1 with an equivalent of FeCl2 produced the hybrid complex, ansa-(2-(CH2)2)-(1-η(5)-C5H4-closo-1,2,3,4-C3B7H9)Fe (3), with a crystallographic determination confirming the formation of a sandwich structure where the ring and cage are linked by the ansa -CH2CH2- group with attachment to the cage at the C2 carbon. The reaction of 2 with FeCl2 produced three isomeric ansa-(CH2)2-ferrabistricarbadecaboranyl sandwich complexes, ansa-(CH2)2-(closo-C3B7H9)2Fe (4, 5 and 6). Crystallographic determinations showed that in 4, the two tricarbadecaboranyl ligands are linked by the ansa-CH2CH2- group at the C2 and C2' cage carbons, whereas in 5 and 6 they are linked at their C2 and C4' carbons, with the structures of 5 and 6 differing in the relative positions of the C4' carbons in the two cages of each complex. The structural determinations also showed that, depending upon the linking position of the ansa-tether, constraints in cage-orientation, such as observed in 4, produce unfavorable intercage steric interactions. However, the cage fragments in these complexes can readily undergo a cage-carbon migration that moves one -carbon and its tether linkage to the more favorable 4-position. This isomerization reduces the cage steric interactions and produces configurations, such as those found for 5 and 6, where the iron cage bonding is enhanced as a result of the binding effect of the tether.

Novel benzyl-substituted N-heterocyclic carbene-silver acetate complexes: synthesis, cytotoxicity and antibacterial studies.

From the reaction of 1-methylimidazole (1a), 4,5-dichloro-1H-imidazole (1b(I)) and 1-methylbenzimidazole (1c) with p-cyanobenzyl bromide (2a), non-symmetrically substituted N-heterocyclic carbene (NHC) [(3a-c)] precursors, 5,6-dimethyl-1H-benzimidazole (1d) and 4,5-diphenyl-1H-imidazole (1e) with p-cyanobenzyl bromide (2a) and benzyl bromide (2b), symmetrically substituted N-heterocyclic carbene (NHC) [(3d-f)] precursors were synthesised. These NHC-precursors were then reacted with silver(i) acetate to yield the NHC-silver complexes (1-methyl-3-(4-cyanobenzyl)imidazole-2-ylidene)silver(i)acetate (4a), (4,5-dichloro-1-(4-cyanobenzyl)-3-methyl)imidazole-2-ylidene)silver(i)acetate (4b), (1-methyl-3-(4-cyanobenzyl)benzimidazole-2-ylidene)silver(i)acetate (4c), (1,3-bis(4-cyanobenzyl)5,6-dimethylbenzimidazole-2-ylidene) silver(i) acetate (4d), (1,3-dibenzyl-5,6-dimethylbenzimidazole-2-ylidene) silver(i) acetate (4e) and (1,3-dibenzyl-4,5-diphenylimidazol-2-ylidene) silver(i) acetate (4f) respectively. Three NHC-precursors 3c-e and four NHC-silver complexes 4b and 4d-f were characterised by single crystal X-ray diffraction. Preliminary in vitro antibacterial activity of the NHC-precursors and NHC-silver complexes was investigated against Gram-positive bacteria Staphylococcus aureus, and Gram-negative bacteria Escherichia coli using the qualitative Kirby-Bauer disk-diffusion method. NHC-silver complexes have shown very high antibacterial activity compared to the NHC-precursors. All six NHC-silver complexes were tested for their cytotoxicity through MTT based in vitro tests on the human renal-cancer cell line Caki-1 in order to determine their IC50 values. NHC-silver complexes 4a-f were found to have IC50 values of 6.2 (±1.0), 7.7 (±1.6), 1.2 (±0.6), 10.8 (±1.9), 24.2 (±1.8) and 13.6 (±1.0) µM, respectively. These values represent improved cytotoxicity against Caki-1, most notably for 4c, which is a three times more cytotoxic than cisplatin (IC50 value = 3.3 µM) itself.

Pseudo-halide derivatives of titanocene: synthesis and cytotoxicity studies.

The well-known anticancer drug candidate bis-[(p-methoxybenzyl)cyclopentadienyl] titanium(IV) dichloride (Titanocene ) was reacted with sodium azide or potassium cyanate, thiocyanate or selenocyanate in order to give pseudo-halide analogues of Titanocene . and were characterised by single crystal X-ray diffraction, which confirmed the expected nitrogen binding of the cyanate and thiocyanate to the titanium centre. All four titanocenes had their cytotoxicity investigated through preliminary in vitro testing on the LLC-PK (pig kidney epithelial) cell line in an MTT based assay in order to determine their IC50 values. Titanocenes were found to have IC50 values of 24 (± 8) µM, 101 (± 14) µM, 54 (± 21) µM and 27 (± 4) µM respectively. All four titanocene derivatives show significant cytotoxicity improvement when compared to unsubstituted titanocene dichloride and and showed similiar cytotoxic behaviour to Titanocene in vitro.