Synthetic approaches based on the direct borylation of ferrocene by BBr(3), followed by boryl substituent modification, or on the lithiation of ferrocene derivatives and subsequent quenching with the electrophile FBMes(2), have given access to a range of ferrocene derivatized Lewis acids with which to conduct a systematic study of fluoride and cyanide binding. In particular, the effects of borane electrophilicity, net charge, and ancillary ligand electronics/cooperativity on the binding affinities for these anions have been probed by a combination of NMR, IR, mass spectrometric, electrochemical, crystallographic, and UV-vis titration measurements. In this respect, modifications made at the para position of the boron-bound aromatic substituents exert a relatively minor influence on the binding constants for both fluoride and cyanide, as do the electronic properties of peripheral substituents at the 1'- position (even for cationic groups). By contrast, the influence of a CH(2)NMe(3)(+) substituent in the 2- position is found to be much more pronounced (by >3 orders of magnitude), reflecting, at least in part, the possibility in solution for an additional binding component utilizing the hydrogen bond donor capabilities of the methylene CH(2) group. While none of the systems examined in the current study display any great differentiation between the binding of F(-) and CN(-) (and indeed some, such as FcBMes(2), bind both anions with equal affinity within experimental error), much weaker boronic ester Lewis acids will bind fluoride (but give a negative response for cyanide). Thus, by the incorporation of an irreversible redox-matched organic dye, a two-component [BMes(2)/B(OR)(2)] dosimeter system can be developed capable of colorimetrically signaling the presence of fluoride and cyanide in organic solution by Boolean AND/NOT logic.
A longitudinal study of the effect of time spent in lairage on salmonellas in the caecum and on the skin surface of 450 slaughter pigs from a single producer was conducted. Pigs were tested in 6 groups at 2 abattoirs, with one-third of a group being slaughtered after 18 h, one-third after 42 h and one-third after 66 h spent in lairage. The salmonella isolation rate from caeca and carcass surfaces increased significantly with increasing time spent in lairage. Salmonellas were isolated from the caeca of 18.5% of pigs held less than 24 h in lairage, 24.1% of pigs held a further 24 h and 47.7% of pigs held for 66 h in lairage before slaughter. The salmonella isolation rates from carcasses were 9.3%, 12.8% and 27.3% for the same groups. Thirteen salmonella serotypes were isolated from the caecal contents and carcasses over the 6 weeks of the trial. One abattoir had a higher salmonella isolation rate from pigs than the other and this was probably related to lairage management. It appeared that lairage is an important factor in the manipulation of the salmonella contamination of pig carcasses.
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