Despite strong twisting of the conjugated system, the tetrathiafulvalene homologue 1 reacts with the electron acceptor tetracyanoquinonodimethane to give the dication 12⊕. The anthracene moiety is embedded in the 12⊕ [(TCNQ)4]2⊖, and the dithiol rings are twisted 86° with respect to the anthracene plane: The 1:4 stoichiometry of the highly conductive salt (σ300K = 60S cm−1) is very unusual for TCNQ complexes.

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The combination of molecular recognition [1] and selfassembly processes [2] offers a powerful route to the development of nanoscale systems that have technological applications as sensors, devices, and switches. [3] Macrocyclic ligands continue to attract widespread attention, [4] especially when complexation of a neutral or ionic guest at one site in the molecule induces a change in the optical [5] or redox properties [6] of the system.The recent incorporation of the electroactive tetrathiafulvalene (TTF) unit into metal-binding macrocyclic structures has demonstrated that they can function as metal-cation sensors in organic media. [7] The presence of a metal cation imposes an inductive effect on the polarizable TTF system, resulting in an anodic shift of the first oxidation potential as indicated by cyclic voltammetry experiments (e.g., for compound 1, a maximum shift of DE 1,1/2 = 80 mV for Na + complexation has been observed); [7] the second oxidation potential is essentially unchanged, consistent with the expulsion of the metal cation after the first oxidation. There is current interest in electrochemically active self-assembled monolayers (SAMs), [8] and the recent observation of stable redox chemistry of TTF derivatives 2 in self-assembled monolayers [8b] prompted us to investigate thin-film electrochemical sensors based on the cation-sensitive redox-active molecules 6 and 9 immobilized on a metal surface. SAMs represent an attractive method for device fabrication, having the advantages of straightforward preparation and being generally very robust (stable to solvents, acids, and bases). The key starting reagent in our syntheses of compounds 6 and 9 (Scheme 1) is compound 3, [9] the hydrolysis of which under basic conditions (1 M sodium hydroxide in dioxane) yielded, after acidic work-up, the acid derivative 4 (75 % yield). Treatment of acid 4 with either 12-bromo-1-dodecanol or 6-bromo-1-hexanol in the presence of dicyclohexylcarbodiimide (DCC) and N,N-dimethylaminopyridine (DMAP) afforded ester derivatives 5a and 5b, respectively (75 and 85 % yield, respectively) with subsequent conversion of the bromide into a thiol being achieved by treatment with thiourea followed by basic hydrolysis of the intermediate isothiouronium salt to afford the target derivatives 6a and 6b (42 and 33 % yield, respectively). In both cases, this last step gave a complex reaction mixture; consequently, the purified yields for compounds 6a and 6b were reduced as a result of repeated chromatography. The byproducts could not be obtained pure and their structures are unknown. Reduction of compound 3 to afford the methanol derivative 7 occurred in dichloromethane at ±78 C using diisobutylaluminum hydride (DIBAL-H) [10] (85 % yield). Using a modification [11] of the Mitsunobu reaction [12] we successfully converted alcohol 7 into sulfanylmethyl derivative 9:[13] a mixture of compound 7 and thioacetic acid in tetrahydrofuran was added to a stirred mixture of diisopropyl azodicarboxylate (DIAD) and triphenylphosphine in tetrahydrofur...

It has been suggested that Perthes' disease is more prevalent in urban areas, and that the risk increases with deprivation. We present the findings of a preliminary analysis of Perthes' disease in Northern Ireland, which is shown to have one of the highest national annual rates of incidence in the world (11.6 per 100 000). Of the 313 children diagnosed over a seven-year period, 311 were allocated to the enumeration districts of the 1991 census, thus allowing the incidence to be calculated using both spatial and non-spatial aggregation. The cases were grouped according to the size of the settlement from highly urbanised to open countryside and by level of area deprivation. While the incidence of Perthes' disease was found to be associated with indicators of the level of deprivation for areas, there was no evidence to suggest that there was an increased risk in urban areas; the highest rate was found in the most deprived rural category.

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This analysis combining data from two health systems shows that area deprivation is an independent risk factor for cognitive dysfunction in older adults. Adults living in areas of greatest socioeconomic deprivation may benefit from targeted strategies aimed at improving modifiable risk factors for dementia. Further cross-national analysis investigating the impact of area- level deprivation is needed to address socioeconomic disparities and shape future policy to improve health outcomes in older adults.© 2018 American Geriatrics Society and Wiley Periodicals, Inc.