Keystone individuals - linking predator traits to community ecology.

Individual behavioral plasticity enables animals to adjust to different scenarios. Yet, personality traits limit this flexibility, leading to consistent interindividual differences in behavior. These individual behavioral traits have the potential to govern community interactions, although testing this is difficult in complex natural systems.

Direct determination of oligomeric organization of integral membrane proteins and lipids from intact customizable bilayer.

Hierarchical organization of integral membrane proteins (IMP) and lipids at the membrane is essential for regulating myriad downstream signaling. A quantitative understanding of these processes requires both detections of oligomeric organization of IMPs and lipids directly from intact membranes and determination of key membrane components and properties that regulate them. Addressing this, we have developed a platform that enables native mass spectrometry (nMS) analysis of IMP-lipid complexes directly from intact and customizable lipid membranes.

Bridges and Vertices in Heteroboranes.

A number of (hetero)boranes are known in which a main group atom 'bridges' a B-B connectivity in the open face, and in such species has previously been described as simply a bridge or, alternatively, as a vertex in a larger cluster. In this study we describe an approach to distinguish between these options based on identifying the best fit of the experimental {B} cluster fragment with alternate exemplar {B} fragments derived from DFT-optimized [BH] models. In most of the examples studied atom is found to be better regarded as a vertex, having 'a 'verticity' of ca.

Integration of mark-recapture and acoustic detections for unbiased population estimation in animal communities.

Abundance estimation methods that combine several types of data are becoming increasingly common because they yield more accurate and precise parameter estimates and predictions than are possible from a single data source. These beneficial effects result from increasing sample size (through data pooling) and complementarity between different data types. Here, we test whether integrating mark-recapture data with passive acoustic detections into a joint likelihood improves estimates of population size in a multi-guild community.

,'-Ru to ,'-Ru isomerisation in bis(phosphine)Ru complexes of [1,1'-bis(-carborane)].

We report herein the first example of the controlled isomerisation of a ,'-bound (to metal) bis(-carborane) ligand to ,'-bound with no other change in the molecule. Since the C and B vertices of carboranes have different electron-donating properties this transformation allows the reactivity of the metal centre to be fine-tuned.

Integrating Sequence Capture and Restriction Site-Associated DNA Sequencing to Resolve Recent Radiations of Pelagic Seabirds.

The diversification of modern birds has been shaped by a number of radiations. Rapid diversification events make reconstructing the evolutionary relationships among taxa challenging due to the convoluted effects of incomplete lineage sorting (ILS) and introgression. Phylogenomic data sets have the potential to detect patterns of phylogenetic incongruence, and to address their causes.

The quandary of registered nurses untrained in adult intellectual disability nursing when caring for this diverse patient group in acute care settings: An integrated literature review.

Aims And Objectives: To critically appraise relevant literature on the lived experiences of registered nurses caring for adults with intellectual disability in the acute care setting in Australia to determine current knowledge and gaps in the literature.

Background: People with intellectual disability have the right to the highest attainable health care the same as everyone else. However, inequities still exist in the delivery of health care across the globe, including Australia that result in poorer health outcomes for this population group.

Bitter fruits of hard labour: diet metabarcoding and telemetry reveal that urban songbirds travel further for lower-quality food.

Rapidly increasing urbanisation requires mitigation against associated losses of biodiversity and species abundance. In urban-breeding birds, altered food availability for nestlings is thought to reduce reproductive success compared to forest populations. To compensate for shortages of preferred foods, urban parents could increase their search effort for optimal diets or provision other foods.

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO Reduction in Aqueous Electrolytes.

We report the light-induced modification of catalytic selectivity for photoelectrochemical CO reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO reduction on the Cu surface, while charge separation is accomplished by hot-hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts increased selectivity for CO reduction over hydrogen evolution in aqueous electrolytes.

Exopolyhedral Ligand Orientation Controls Diastereoisomer in Mixed-Metal Bis(carboranes).

Heterobimetallic derivatives of a bis(carborane), [μ-(1',3'-3'-Cl-3'-PPh--3',1',2'-RhCBH)-2-(-cymene)--2,1,8-RuCBH] () and [μ-(1',3'-3'-Cl-3'-PPh--3',1',2'-RhCBH)-2-Cp--2,1,8-CoCBH] () have been synthesised and characterised, including crystallographic studies. A minor co-product during the synthesis of compound is the new species [8-{8'-2'-H-2',2'-(PPh)--2',1',8'-RhCBH}-2-Cp--2,1,8-CoCBH] (), isolated as a mixture of diastereoisomers. Although, in principle, compounds and could also exist as two diastereoisomers, only one (the same in both cases) is formed.

Bis(phosphine)hydridorhodacarborane Derivatives of 1,1'-Bis(-carborane) and Their Catalysis of Alkene Isomerization and the Hydrosilylation of Acetophenone.

Deprotonation of [7-(1'--1',2'-CBH)--7,8-CBH] and reaction with [Rh(PPh)Cl] results in isomerization of the metalated cage and the formation of [8-(1'--1',2'-CBH)-2-H-2,2-(PPh)--2,1,8-RhCBH] (). Similarly, deprotonation/metalation of [8'-(7--7,8-CBH)-2'-(-cymene)--2',1',8'-RuCBH] and [8'-(7--7,8-CBH)-2'-Cp*--2',1',8'-CoCBH] affords [8-{8'-2'-(-cymene)--2',1',8'-RuCBH}-2-H-2,2-(PPh)--2,1,8-RhCBH] () and [8-(8'-2'-Cp*--2',1',8'-CoCBH)-2-H-2,2-(PPh)--2,1,8-RhCBH] (), respectively, as diastereoisomeric mixtures. The performances of compounds - as catalysts in the isomerization of 1-hexene and in the hydrosilylation of acetophenone are compared with those of the known single-cage species [3-H-3,3-(PPh)--3,1,2-RhCBH] () and [2-H-2,2-(PPh)--2,1,12-RhCBH] (), the last two compounds also being the subjects of Rh NMR spectroscopic studies, the first such investigations of rhodacarboranes.

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au Dicarboranyl Chemistry.

The reaction of 1,1'-Li [(2,2'-C B H ) ] with the cyclometallated gold(III) complex (C^N)AuCl afforded the first examples of gold(III) dicarboranyl complexes. The reactivity of these complexes is subject to the trans-influence exerted by the dicarboranyl ligand, which is substantially weaker than that of non-carboranyl anionic C-ligands. In line with this, displacement of coordinated pyridine by chloride is only possible under forcing conditions.

On the Basicity of Carboranylphosphines.

Three new carboranylphosphines, [1-(1'--1',7'-CBH)-7-PPh--1,7-CBH], [1-(1'-7'-PPh--1',7'-CBH)-7-PPh--1,7-CBH], and [1-{PPh-(1'--1',2'-CBH)}--1,2-CBH], have been prepared, and from a combination of these and literature compounds, eight new carboranylphosphine selenides were subsequently synthesized. The relative basicities of the carboranylphosphines were established by (i) measurement of the NMR coupling constant of the selenide and (ii) calculation of the proton affinity of the phosphine, in an attempt to establish which of several factors are the most important in controlling the basicity. It is found that the basicity of the carboranylphosphines is significantly influenced by the nature of other substituents on the P atom, the nature of the carborane cage vertex (C or B) to which the P atom is attached, and the charge on the carboranylphosphine.

Arene-Ruthenium Complexes of 1,1'-Bis(-carborane): Synthesis, Characterization, and Catalysis.

Deprotonation of 1,1'-bis(-carborane) with BuLi in THF followed by reaction with [RuCl(-cymene)] affords, in addition to the known compound [Ru(κ-2,2',3'-{1-(1'--1',2'-CBH)--1,2-CBH)}(-cymene)] (), a small amount of a new species, [Ru(κ-2,2',11'-{1-(7'--7',8'-CBH)--1,2-CBH)}(-cymene)] (), with two -agostic B-H⇀Ru bonds, making the bis(carborane) unit a --X()L ligand, a previously unreported bonding mode. Similar species were also formed with arene = benzene (), mesitylene (), and hexamethylbenzene (), although in the last two cases the metallacarborane-carborane species [1-(1'--1',2'-CBH)-3-(arene)--3,1,2-RuCBH)], and , were also isolated. With the bis(-carborane) transfer reagent [Mg(κ-2,2'-{1-(1'--1',2'-CBH)--1,2-CBH)}(DME)], the target compounds [Ru(κ-2,2',3'-{1-(1'--1',2'-CBH)--1,2-CBH)}(arene)], and , were prepared in reasonable-to-good yields, although for arene = benzene and mesitylene small amounts of the unique paramagnetic species [{Ru(arene)}(μ-Cl)(μ-κ-2,2',3,3'-{1-(1'--1',2'-CBH)--1,2-CBH})], and , were also formed.

Crystal structure of 1-hepta-fluoro-tolyl--1,2-dicarbadodeca-borane.

The mol-ecular structure of the title compound 1-(2',3',5',6'-tetra-fluoro-4'-trifluoro-methyl-phen-yl)--1,2-dicarbadodeca-borane, CHBF, features an intra-molecular -F⋯H2 hydrogen bond [2.11 (2) Å], which is responsible for an orientation of the hepta-fluoro-tolyl substituent in which the plane of the aryl ring nearly eclipses the C1-C2 cage connectivity.

Exploiting the Electronic Tuneability of Carboranes as Supports for Frustrated Lewis Pairs.

The first example of a carborane with a catecholborolyl substituent, [1-Bcat-2-Ph--1,2-C₂BH] (), has been prepared and characterized and shown to act as the Lewis acid component of an intermolecular frustrated Lewis pair in catalyzing a Michael addition. In combination with B(C₆F₅)₃ the -carboranylphosphine [1-PPh₂--1,2-C₂BH] () is found to be comparable with PPh₂(C₆F₅) in its ability to catalyze hydrosilylation, whilst the more strongly basic -carboranylphosphine [9-PPh₂--1,7-C₂BH] () is less effective and the very weakly basic species [μ-2,2'-PPh-{1-(1'-1',2'--C₂BH)-1,2--C₂BH}] () is completely ineffective. Base strengths are rank-ordered via measurement of the ¹ P-Se coupling constants of the phosphineselenides [1-SePPh₂--1,2-C₂BH] (), [9-SePPh₂--1,7-C₂BH] (), and [SePPh₂(C₆F₅)] ().

Carotenoid-based skin ornaments reflect foraging propensity in a seabird, .

Carotenoid-based ornaments are common signalling features in animals. It has long been proposed that such ornaments communicate information about foraging abilities to potential mates. However, evidence linking foraging with ornamentation is largely missing from unmanipulated, free-ranging populations.

Quantifying the role of surface plasmon excitation and hot carrier transport in plasmonic devices.

Harnessing photoexcited "hot" carriers in metallic nanostructures could define a new phase of non-equilibrium optoelectronics for photodetection and photocatalysis. Surface plasmons are considered pivotal for enabling efficient operation of hot carrier devices. Clarifying the fundamental role of plasmon excitation is therefore critical for exploiting their full potential.

Molecular systematics of swifts of the genus Chaetura (Aves: Apodiformes: Apodidae).

Phylogenetic relationships among swifts of the morphologically conservative genus Chaetura were studied using mitochondrial and nuclear DNA sequences. Taxon sampling included all species and 21 of 30 taxa (species and subspecies) within Chaetura. Our results indicate that Chaetura is monophyletic and support the division of the genus into the two subgenera previously identified using plumage characters.

Heterometalation of 1,1'-Bis( ortho-carborane).

Deboronation of [8-(1'- closo-1',2'-CBH)- closo-2,1,8-MCBH] affords diastereoisomeric mixtures of [8-(7'- nido-7',8'-CBH)- closo-2,1,8-MCBH] anions (1, M = Ru( p-cymene); 2, M = CoCp) isolated as [HNMe] salts. Deprotonation of 1 and reaction with CoCl/NaCp followed by oxidation yields [8-(1'-3'-Cp -closo-3',1',2'-CoCBH)-2-( p-cymene)- closo-2,1,8-RuCBH] isolated as two separable diastereoisomers, namely, 3α and 3β, the first examples of heterometalated derivatives of 1,1'-bis( ortho-carborane). Deprotonation of [7-(1'- closo-1',2'-CBH)- nido-7,8-CBH], metalation with CoCl/NaCp* and oxidation affords the isomers [1-(1'- closo-1',2'-CBH)-3-Cp*- closo-3,1,2-CoCBH] (4) and [8-(1'- closo-1',2'-CBH)-2-Cp*- closo-2,1,8-CoCBH] (5) as well as a trace amount of the 13-vertex/12-vertex species [12-(1'- closo-1',2'-CBH)-4,5-Cp*- closo-4,5,1,12-CoCBH] (6).