Chemiluminescence detection of piperazine designer drugs and related compounds using tris(2,2'-bipyridine)ruthenium(III).

We present an exploration of the chemiluminescence from reactions of benzylpiperazines and phenylpiperazines with tris(2,2'-bipyridine)ruthenium(III). The selectivity of the reagent towards these compounds was found to be highly dependent upon the pH of the solution, and the relative emission intensity was strongly influenced by electron donating or withdrawing substituents on the phenyl or benzyl ring. In spite of previous investigations showing poor responses for aromatic-substituted amines (compared to their aliphatic amine counterparts), intense emissions were observed with phenylpiperazines under acidic conditions, particularly those with halogen or trifluoromethyl substituents on the aromatic ring. Buffered alkaline conditions provided much broader selectivity for the detection of both phenylpiperazine and benzylpiperazine compounds, which we have applied to a rapid HPLC procedure for the determination of piperazines of forensic interest in 'party pill' samples.

Chemiluminescence detection of amino acids and related compounds using acidic potassium permanganate, manganese(IV) or tris(2,2'-bipyridine)ruthenium(III).

We have explored the chemiluminescence response of amino acids and related compounds (including the tripeptide glutathione, and disulfides: cystine, homocystine and glutathione disulfide) with several new adaptations of the permanganate and tris(2,2'-bipyridine)ruthenium(III) ([Ru(bipy)(3)](3+)) reagents and a recently developed colloidal manganese(IV) system. The selectivity of the permanganate reagent can be directed towards tyrosine or thiol compounds like cysteine, homocysteine and glutathione by manipulating reaction conditions (providing limits of detection of 4 nM tyrosine and 5 nM glutathione). Colloidal Mn(IV) produced measureable responses with all analytes, but was most suitable for tryptophan, tyrosine, thiols and disulfides, including α-lipoic acid and dihydrolipoic acid, for which the limits of detection were 30 nM and 20 nM, respectively. A stabilised form of [Ru(bipy)(3)](3+), prepared by oxidising [Ru(bipy)(3)](ClO(4))(2) in acetonitrile, exhibited similar selectivity to that of the conventional aqueous reagent. The [Ru(bipy)(3)](3+) reagent was effective for the detection of secondary amino acids such as proline and hydroxyproline, as well as the disulfide, homocystine.

Captive husbandry and socialization of the red-billed chough (Pyrrhocorax pyrrhocorax).

Since the 1970s, Paradise Park Wildlife Sanctuary in Cornwall, United Kingdom, has built up a captive flock of red-billed choughs Pyrrhocorax pyrrhocorax and over 30 years has developed successful methods of keeping, breeding, and appropriately socializing them in captivity. A total of 77 nests reached the egg stage with 27 nests producing at least one young and 48 young fledging in total. Several components are important in achieving successful breeding and socialization. Provision of live food, especially ant's eggs and small mealworms and crickets, in the first days after hatching is essential, improving the condition of adults and survival of nestlings. Situating aviaries in quiet areas, away from public view, is important. Socialization in family groups during the winter months and allowing choughs to choose partners induces better compatibility. Introduction of nest cameras greatly improved young survival through early identification of health problems enabling treatment of young between hatching and 10-days old, when mortality is otherwise highest, and enabling precautionary medication shortly after hatching. We show that clutch size increases significantly with female age and that direct intervention such as artificial egg incubation and hand rearing can be successful and worthwhile, but its requirement is reduced by closer monitoring. Red-billed choughs provide a good model species to further develop captive management and release techniques that can then be applied to critically endangered species that show similar social and long-learning behaviors. Captive breeding programs can play an important role in such work through provision of suitable birds and supporting avicultural expertise.