Organochlorine and trace metal residues in adult southern bent-wing bat (Miniopterus schreibersii bassanii) in Southeastern Australia

In recent times, the apparent population decline of the southern bent-wing bat (Miniopterus schreibersii bassanii) at Bat Cave, Naracoorte has been ascribed to pesticide use in the region, following the finding of organochlorine and orgaonophosphate insecticide residues in bat guano. Adult southern bent-wing bats were collected from Bat Cave and Starlight Cave in 2003. Organochlorine contaminants were detected in all carcass samples: p,p′-DDE was by far the most dominant contaminant with concentrations ranging from 11 000 to 59 000 ng g⁻¹, followed by p,p′-DDT (110–1600 ng g⁻¹), p,p′-DDD (35–620 ng g⁻¹), ∑PCBs (33–490 ng g⁻¹), ∑chlordane and related compounds (7.9–270 ng g⁻¹), HCB (1.6–120 ng g⁻¹), HP epox. (3.1–230 ng g⁻¹), TCPMOH (3.8–38 ng g⁻¹), ∑HCHs (1.4–9.6 ng g⁻¹), and TCPMe (0.1–4.2 ng g⁻¹) (all values on lipid-weight basis). No significant difference in DDE, DDD, DDT, ∑DDT, ∑PCB, trans-chlordane, heptachlor epoxide, trans-nonachlor, α-HCH, β-HCH, γ-HCH, TCPMOH or TCPMe concentrations were observed either between sexes within sites, or between sites (p > 0.05). However, there were significant differences in HCB and oxychlordane concentrations between sexes and between sites (p < 0.05), between site differences in cis-nonachlor concentrations in male bats (p < 0.05), and cis-chlordane concentrations between sexes at Starlight Cave, and between males of each site (p < 0.05). There were also significant differences in the liver concentrations of some metals between sexes within sites (Ag, Cd, Co, Cu, Pb, Se, Zn), and between sites (Ag, Cd, Co, Cu, Hg, Pb, Se, V, Zn). Clustering or grouping of sites was observed when the OC data was expressed on a lipid-weight basis. These inter-site differences in OC concentrations reflect local exposure over a period of time, and do not unambiguously support any suggestion that we are witnessing incipient speciation. However, for conservation purposes, it may be prudent to assume that there are two sub-populations of M. s. bassani feeding in different locations in this region of southern Australia, rather than the single homogeneous population suggested by genetic studies.

Electrochemiluminescent monomers for solid support syntheses of Ru(II)-PNA bioconjugates : multimodal biosensing tools with enhanced duplex stability

The feasibility of devising a solid support mediated approach to multimodal Ru(II)-peptide nucleic acid (PNA) oligomers is explored. Three Ru(II)-PNA-like monomers, [Ru(bpy)2(Cpp-L-PNA-OH)]2+ (M1), [Ru(phen)2(Cpp-L-PNA-OH)]2+ (M2), and [Ru(dppz)2(Cpp-L-PNA-OH)]2+ (M3) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, Cpp-L-PNA-OH = [2-(N-9-fluorenylmethoxycarbonyl)aminoethyl]-N-[6-(2-(pyridin-2yl)pyrimidine-4-carboxamido)hexanoyl]-glycine), have been synthesized as building blocks for Ru(II)-PNA oligomers and characterized by IR and 1H NMR spectroscopy, mass spectrometry, electrochemistry and elemental analysis. As a proof of principle, M1 was incorporated on the solid phase within the PNA sequences H-g-c-a-a-t-a-a-a-a-Lys-NH2 (PNA1) and H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-lys-NH2 (PNA4) to give PNA2 (H-g-c-a-a-t-a-a-a-a-M1-lys-NH2) and PNA3 (H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-M1-lys-NH2), respectively. The two Ru(II)-PNA oligomers, PNA2 and PNA3, displayed a metal to ligand charge transfer (MLCT) transition band centered around 445 nm and an emission maximum at about 680 nm following 450 nm excitation in aqueous solutions (10 mM PBS, pH 7.4). The absorption and emission response of the duplexes formed with the cDNA strand (DNA: 5′-T-T-T-T-T-T-T-A-T-T-G-C-T-T-T-3′) showed no major variations, suggesting that the electronic properties of the Ru(II) complexes are largely unaffected by hybridization. The thermal stability of the PNA·DNA duplexes, as evaluated from UV melting experiments, is enhanced compared to the corresponding nonmetalated duplexes. The melting temperature (Tm) was almost 8 °C higher for PNA2·DNA duplex, and 4 °C for PNA3·DNA duplex, with the stabilization attributed to the electrostatic interaction between the cationic residues (Ru(II) unit and positively charged lysine/arginine) and the polyanionic DNA backbone. In presence of tripropylamine (TPA) as co-reactant, PNA2, PNA3, PNA2·DNA and PNA3·DNA displayed strong electrochemiluminescence (ECL) signals even at submicromolar concentrations. Importantly, the combination of spectrochemical, thermal and ECL properties possessed by the Ru(II)-PNA sequences offer an elegant approach for the design of highly sensitive multimodal biosensing tools.