Palladium Nanoparticles in Suzuki Cross‐Couplings: Tapping into the Potential of Tris‐Imidazolium Salts for Nanoparticle Stabilization

Inspired by the proclivity of various palladium sources to form nanoparticles in imidazolium‐based ionic liquids, we now report that tris‐imidazolium salts bearing hexadecyl chains and a bridging mesitylene moiety are potent stabilizers of palladium nanoparticles efficiently prepared via a Chaudret‐type hydrogenation of the bis(dibenzylideneacetone)palladium(0). The palladium nanoparticles have been isolated in pure form and characterized by ¹H nuclear magnetic resonance, transmission electron microscopy, electron diffraction and dynamic light scattering. The new materials proved effective in Suzuki cross‐coupling at a loading of 0.2% palladium. Thus, using a tris‐imidazolium iodide‐palladium material, a series of biaryl products has been prepared starting from aryl bromides and some activated chlorides. The possibility that this catalytic activity might be due to the formation of palladium N‐heterocyclic carbenes has been addressed through solid state ¹³C NMR and the synthesis of an imidazolium analogue in which the acidic 2‐H was replaced with a methyl group.     

Brilliant Cresyl Blue stain selects largest oocytes with highest mitochondrial activity, maturation-promoting factor activity and embryo developmental competence in prepubertal sheep

The aim of this study was to test the Brilliant Cresyl Blue (BCB) stain to select prepubertal sheep oocytes for in vitro blastocyst production. Oocyte diameter, mitochondrial activity, maturation-promoting factor (MPF) activity and mRNA relative expression (RE) of genes related to metabolism (ATPase Na(+)/K(+) transporting α 1 (ATP1A1) and cytochrome c oxidase subunit 1 (COX1)) and constitutive function of the cell (cytoplasmic polyadenylation-element-binding protein (CPEB) and S100A10) were assessed. Immature oocytes were exposed to different BCB concentrations (13, 26, 39 and 52 μM) and classified according to their cytoplasm colouration as grown BCB+ (blue cytoplasm) and growing BCB- (colourless cytoplasm). Staining oocytes with 13 μM BCB during 60 min allows selection of (BCB+) the largest (123.66 μm) and most competent oocytes to develop to the blastocyst stage (21%) with a higher number of cells (69.71 ± 6.19 s.e.m.) compared with non-stained BCB- oocytes (106.82 μm, 9% and 45.91 ± 3.35 s.e.m. respectively). Mitochondrial activity, assessed by MitoTracker Orange CMTMRos probe, was significantly higher in BCB+ than in BCB- oocytes after in vitro maturation (3369 and 1565 AU respectively). MPF activity was assessed by CDC2 kinase activity assay showing significantly higher activity at metaphase II stage in BCB+ than in BCB- oocytes (1.479 ± 0.09 and 1.184 ± 0.05 optical density respectively). The genes analysed in this work, ATP1A1, COX1, CPEB and S100A 10, did not show significant effect in mRNA RE between BCB selected oocytes. In conclusion, BCB stains larger and more competent oocytes to develop to the blastocyst stage with more active mitochondria and MPF activity and higher blastocyst cell number.     

Assessing the health implications of turbidity and suspended particles in protected catchments.

The supply of unfiltered disinfected drinking water from Melbourne's fully protected catchments means that the water-quality managers must ensure that the source water poses no public health risk. High turbidity is currently used as a surrogate of pathogens, and harvesting of water is based on its measurement. The work presented here summarises suspended particle and associated pathogen, microbial indicator and faecal biomarker concentrations collected to (a) quantify turbidity in an Australian water supply system and (b) assess the possibility of increasing water harvesting from selected tributaries. Pathogens and microbial indicators were present in low numbers in these source waters; increased turbidity during storm events was not associated with an increase in pathogen concentration. The results confirmed that protected catchments, along with good management, were effective barriers to pathogen contamination. Aesthetic issues still need to be addressed, but no measurable increase in microbiological risk was associated with storm-generated particles.     

Hydrogen sulphide production tests and the detection of groundwater faecal contamination by septic seepage.

The 'H2S test' is being advanced for microbiological water quality testing where conventional coliform based methods are impractical or too expensive. It involves ambient temperature incubation of water samples with nutrient formulated to generate hydrogen sulphide when 'faecal' bacteria are present. Recently a WHO review identified several concerns including the limited number of comparative studies, formulation variability, and false positives and negatives. In response we have compared the H2S test's ability to detect and quantify faecal contamination in an aquifer impacted by septic tank leachfields with measurements obtained concurrently using conventional bacterial indicators, coliphages, faecal sterol biomarkers, Cryptosporidium and Giardia. Like these other analytes, H2S testing detected a contamination gradient ranging from high (septic liquid) to moderate (exfiltration zones), to background (e.g. domestic bores), corresponding to indicator removal + dilution by factors > 10(6). Presence/absence tests could not distinguish between heavily and slightly contaminated waters, whereas multi-tube testing (e.g. 10 x 10 mL arrays) did. It was concluded that while the WHO review concerns are justified, the H2S test performance shows promise in sanitary survey work, can be improved by employing an mpn approach and has potential to aid in the protection of source water and identifying contaminated groundwater.     

Rhodium Nanoflowers Stabilized by a Nitrogen‐Rich PEG‐Tagged Substrate as Recyclable Catalyst for the Stereoselective Hydrosilylation of Internal Alkynes

Morphology and size controllable rhodium nanoparticles stabilized by a nitrogen‐rich polyoxyethylenated derivative have been prepared by reduction of RhCl₃ with NaBH₄ in water at room temperature and fully characterized. The flower‐like Rh NPs are effective and recyclable catalysts for the stereoselective hydrosilylation of challenging internal alkynes and diynes, affording the (E)‐vinylsilanes in quantitative yields for a wide range of substrates. The insolubility of the nanocatalyst in diethyl ether allows its easy separation and recycling.

     

Hydrosilylation of Internal Alkynes Catalyzed by Tris‐ Imidazolium Salt‐Stabilized Palladium Nanoparticles

Palladium nanoparticles stabilized with tris‐imidazolium tetrafluoroborates catalyze the stereoselective hydrosilylation of internal alkynes in a dry inert atmosphere to give (E)‐vinylsilanes in excellent yields. In the presence of controlled amounts of water a transfer hydrogenation reaction takes place with the formation of (Z) ‐ alkenes or the corresponding alkanes.

     

Consumption of Dietary n-3 Fatty Acids Decreases Fat Deposition and Adipocyte Size, but Increases Oxidative Susceptibility in Broiler Chickens

The aim of this study was to determine the effects of an omega-3 (n-3) polyunsaturated fatty acid (PUFA)-enriched diet on animal fat depots and lipid oxidation in the blood and meat of broiler chickens. Abdominal fat pad (AFP), sartorius muscle and liver histology were used to assess the effect of the dietary fat on animal lipid depots. A total of 60 female broilers (14 days old) was randomly divided into two groups which received a diet containing 10 % of tallow (S diet), rich in saturated fatty acids or 10 % of a blend of fish oil and linseed oil (N3 diet), rich in n-3 PUFA from 14 to 50 days of life. Both absolute and relative weights of AFP in N3 animals were lower than in the S group (P < 0.05). These results paralleled with a lower adipocyte mean area (P < 0.001) obtained in N3-fed animals, leading to a higher number of fat cells per unit of surface measured (383.4 adipocytes/mm² vs. 273.7 adipocytes/mm²). Similarly, fat content and the intramuscular fat-occupied area of muscle were lower in N3 (P < 0.0001) than in the S-fed birds. Neither macroscopic nor microscopic differences were observed in the liver. The inclusion of dietary n-3 PUFA increased meat and erythrocyte oxidation susceptibility; however, the erythrocytes from the S group were less resistant to osmotic changes. Results indicate that feeding an n-3 PUFA diet influences fat distribution and the oxidative status of broiler chickens.     

Solar radiation disinfection of drinking water at temperate latitudes: Inactivation rates for an optimised reactor configuration

Solar radiation-driven inactivation of bacteria, virus and protozoan pathogen models was quantified in simulated drinking water at a temperate latitude (34°S). The water was seeded with Enterococcus faecalis, Clostridium sporogenes spores, and P22 bacteriophage, each at ca 1 × 10⁵ m L⁻¹, and exposed to natural sunlight in 30-L reaction vessels. Water temperature ranged from 17 to 39 °C during the experiments lasting up to 6 h. Dark controls showed little inactivation and so it was concluded that the inactivation observed was primarily driven by non-thermal processes. The optimised reactor design achieved S₉₀ values (cumulative exposure required for 90% reduction) for the test microorganisms in the range 0.63-1.82 MJ m⁻² of Global Solar Exposure (GSX) without the need for TiO₂ as a catalyst. High turbidity (840-920 NTU) only reduced the S₉₀ value by <40%. Further, when all S₉₀ means were compared this decrease was not statistically significant (prob. > 0.05). However, inactivation was significantly reduced for E. faecalis and P22 when the transmittance of UV wavelengths was attenuated by water with high colour (140 PtCo units) or a suboptimally transparent reactor lid (prob. < 0.05). S₉₀ values were consistent with those measured by other researchers (ca 1-10 MJ m⁻²) for a range of waters and microorganisms. Although temperatures required for SODIS type pasteurization were not produced, non-thermal inactivation alone appeared to offer a viable means for reliably disinfecting low colour source waters by greater than 4 orders of magnitude on sunny days at 34°S latitude.