Molecular parallelism in signaling function across different sexually selected ornaments in a warbler.

Extravagant ornaments are thought to signal male quality to females choosing mates, but the evidence linking ornament size to male quality is controversial, particularly in cases in which females prefer different ornaments in different populations. Here, we use whole-genome sequencing and transcriptomics to determine the genetic basis of ornament size in two populations of a widespread warbler, the common yellowthroat (Geothlypis trichas). Within a single subspecies, females in a Wisconsin population prefer males with larger black masks as mates, while females in a New York population prefer males with larger yellow bibs. Despite being produced by different pigments in different patches on the body, the size of the ornament preferred by females in each population was linked to numerous genes that function in many of the same core aspects of male quality (e.g., immunity and oxidative balance). These relationships confirm recent hypotheses linking the signaling function of ornaments to male quality. Furthermore, the parallelism in signaling function provides the flexibility for different types of ornaments to be used as signals of similar aspects of male quality. This could facilitate switches in female preference for different ornaments, a potentially important step in the early stages of divergence among populations.

Evaluation and implementation of a Just-In-Time bed-assignment strategy to reduce wait times for surgical inpatients.

Early bed assignments of elective surgical patients can be a useful planning tool for hospital staff; they provide certainty in patient placement and allow nursing staff to prepare for patients' arrivals to the unit. However, given the variability in the surgical schedule, they can also result in timing mismatches-beds remain empty while their assigned patients are still in surgery, while other ready-to-move patients are waiting for their beds to become available. In this study, we used data from four surgical units in a large academic medical center to build a discrete-event simulation with which we show how a Just-In-Time (JIT) bed assignment, in which ready-to-move patients are assigned to ready-beds, would decrease bed idle time and increase access to general care beds for all surgical patients. Additionally, our simulation demonstrates the potential synergistic effects of combining the JIT assignment policy with a strategy that co-locates short-stay surgical patients out of inpatient beds, increasing the bed supply. The simulation results motivated hospital leadership to implement both strategies across these four surgical inpatient units in early 2017. In the several months post-implementation, the average patient wait time decreased 25.0% overall, driven by decreases of 32.9% for ED-to-floor transfers (from 3.66 to 2.45 hours on average) and 37.4% for PACU-to-floor transfers (from 2.36 to 1.48 hours), the two major sources of admissions to the surgical floors, without adding additional capacity.

High MHC diversity confers no advantage for phenotypic quality and reproductive performance in a wild bird.

Genes of the major histocompatibility complex (MHC) encode antigen-binding molecules and are an integral part of the acquired immune response of vertebrates. In general, high individual MHC diversity is expected to increase fitness by broadening the spectrum of pathogens recognized by the immune system, in accordance with the heterozygote advantage mechanism. On the other hand, the optimality hypothesis assumes that individuals with optimal (intermediate), rather than maximum, diversity of the MHC will achieve the highest fitness because of inherent costs associated with expressing diverse MHC alleles. Here, we tested for associations between individual diversity of the MHC class I and class II genes (binding antigens of intra- and extracellular pathogens respectively) and a range of fitness-related traits (condition, ornament expression and reproduction) in an urban population of the Eurasian coot Fulica atra. Contrary to our expectation, we found that high within-individual allelic diversity of MHC genes (both class I and II) was associated with poorer condition (lower blood haemoglobin concentrations), weaker expression of the putative ornament (smaller frontal shield), later onset of breeding and smaller clutches. An analysis of functional MHC allele clusters (supertypes) provided further support for negative associations of MHC diversity with phenotypic quality and reproductive performance, but most of these relationships could not be explained by the presence of specific maladaptive supertypes. Finally, we found little empirical support for the optimality hypothesis in the Eurasian coot. Our results suggest that the costs of high MHC diversity outweighed any benefits associated with broad MHC repertoire, which could be driven by depauperate pathogen diversity in an urban landscape. To the best of our knowledge, this is one of the first studies providing consistent evidence for negative associations of MHC diversity with a range of fitness-related traits in a natural avian population.

Hydrogen Atom Abstraction from an OsII(NH3)2 Complex Generates an OsIV(NH2)2 Complex: Experimental and Computational Analysis of the N-H Bond Dissociation Free Energies and Reactivity.

Double hydrogen atom abstraction from (TMP)OsII(NH3)2 (TMP = tetramesitylporphyrin) with phenoxyl or nitroxyl radicals leads to (TMP)OsIV(NH2)2. This unusual bis(amide) complex is diamagnetic and displays an N-H resonance at 12.0 ppm in its 1H NMR spectrum. 1H-15N correlation experiments identified a 15N NMR spectroscopic resonance signal at -267 ppm. Experimental reactivity studies and density functional theory calculations support relatively weak N-H bonds of 73.3 kcal/mol for (TMP)OsII(NH3)2 and 74.2 kcal/mol for (TMP)OsIII(NH3)(NH2). Cyclic voltammetry experiments provide an estimate of the pKa of [(TMP)OsIII(NH3)2]+. In the presence of Barton's base, a current enhancement is observed at the Os(III/II) couple, consistent with an ECE event. Spectroscopic experiments confirmed (TMP)OsIV(NH2)2 as the product of bulk electrolysis. Double hydrogen atom abstraction is influenced by π donation from the amides of (TMP)OsIV(NH2)2 into the d orbitals of the Os center, favoring the formation of (TMP)OsIV(NH2)2 over N-N coupling. This π donation leads to a Jahn-Teller distortion that splits the energy levels of the dxz and dyz orbitals of Os, results in a low-spin electron configuration, and leads to minimal aminyl character on the N atoms, rendering (TMP)OsIV(NH2)2 unreactive toward amide-amide coupling.

Level-loading a health system by transferring emergency department patients to a community hospital: Prospective cohort study.

BACKGROUND: Emergency department boarding and crowding lead to worse patient outcomes and patient satisfaction. OBJECTIVE: We describe the implementation of a program to transfer patients requiring medical admission from an academic emergency department to a community hospital's medical floor and analyze its effects on patient outcomes. METHODS: A prospective cohort study was performed. Data was collected on patient flow through the transfer program. Patient characteristics, boarding time in the emergency department, and hospital-based outcome measures were compared between patients in the transfer program who were successfully transferred to the community hospital and patients who were admitted to the academic medical center. RESULTS: 79 patients were successfully transferred to the community hospital between November 23, 2020 and August 5, 2021, resulting in 279 bed days in the community hospital. Successfully transferred patients experienced a statistically shorter ED boarding time (5.7 vs. 10.9 h, p < 0.0001), ED length of stay (10.5 vs 16.1 h, p < 0.0001), and hospital length of stay (3.5 vs 5.7 days, p < 0.0001) compared to patients initially referred to the transfer program who were admitted to the academic medical center. There were no reported adverse events during transfer, upgrades to the ICU within 24 h of admission, or inpatient deaths for patients who were transferred. CONCLUSION: We implemented an academic emergency department to partner community hospital transfer program that safely level-loads medical patients in a healthcare system.

Polymorphism and varying selection within the MHC class I of four Anas species.

Ducks (Anatidae) are often vectors for the spread of pathogens because of their long-distance migrations. These migrations also expose ducks to a wide variety of pathogens in their wintering and breeding grounds, and, as a consequence, we might expect strong selection on their immune genes. Here, we studied exons 2 and 3 of the MHC class I in four species of Anas ducks (A. platyrhynchos, A. poecilorhyncha, A. formosa, and A. querquedula) using Illumina-sequencing. Both exons 2 and 3 code for the peptide-binding region of class I molecules; however, most previous studies of birds have only focused on exon 3. Here, we found stronger positive selection on exon 2 than exon 3, as indicated by more species with dN/dS > 1 and higher Wu-Kabat values. There was little evidence that divergence time influenced polymorphism, the numbers of identical alleles (partial α1 or α2 regions) among four Anas, or selection, suggesting that these widespread species might share similar levels of selection from pathogens. The high similarity of allele numbers, positively selected sites (PSS), conserved motifs, and variable protein sites (VPS) supported the persistence of trans-species polymorphism in Anas for at least 10 million years. Our study revealed exon 2 as a relatively unexplored source of variation in avian MHC class I, which should be considered in future studies.

Immunocompetent birds choose larger breeding colonies.

Optimal size of social groups may vary between individuals, depending on their phenotypic traits, such as dominance status, age or personality. Larger social groups often enhance transmission rates of pathogens and should be avoided by individuals with poor immune defences. In contrast, more immunocompetent individuals are expected to take advantage of larger group sizes (e.g. better protection, information transfer) with smaller extra costs from pathogen or parasite pressure. Here, we hypothesized that immunocompetence may be a key determinant of group size choice and tested this hypothesis in a colonial waterbird, the common tern Sterna hirundo. We used a unique experimental framework, where formation of breeding colonies of different sizes was induced under uniform environmental conditions. For this purpose, different-size patches of attractive nesting substrate (artificial floating rafts) were provided at a single site with limited availability of natural nesting habitat. Colony size was identified as the only significant predictor of both innate (natural antibody-mediated complement activation) and adaptive (immunoglobulin concentrations) immunological traits in the common terns, as more immunocompetent birds settled in larger experimental colonies. In contrast, we found no significant associations between colony size and genetic diversity of key pathogen-recognition receptors, toll-like receptors (TLRs) and the Major Histocompatibility Complex (MHC) or genome-wide heterozygosity. We conclude that settlement decisions may be flexible within individuals and, thus, are likely to be primarily determined by the current immunological status, rather than fixed immunogenetic traits. Our study sheds new light on the complex interface between immunity and sociality in animals.

Diversion of Catalytic C-N Bond Formation to Catalytic Oxidation of NH3 through Modification of the Hydrogen Atom Abstractor.

We report that (TMP)Ru(NH3)2 (TMP = tetramesitylporphryin) is a molecular catalyst for oxidation of ammonia to dinitrogen. An aryloxy radical, tri-tert-butylphenoxyl (ArO·), abstracts H atoms from a bound ammonia ligand of (TMP)Ru(NH3)2, leading to the discovery of a new catalytic C-N coupling to the para position of ArO· to form 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to 2,6-di-tert-butyl-4-tritylphenoxyl radical, which contains a trityl group at the para position, prevents C-N coupling and diverts the reaction to catalytic oxidation of NH3 to give N2. We achieved 125 ± 5 turnovers at 22 °C for oxidation of NH3, the highest turnover number (TON) reported to date for a molecular catalyst.

Oxidation of Ammonia with Molecular Complexes.

Oxidation of ammonia by molecular complexes is a burgeoning area of research, with critical scientific challenges that must be addressed. A fundamental understanding of individual reaction steps is needed, particularly for cleavage of N-H bonds and formation of N-N bonds. This Perspective evaluates the challenges of designing molecular catalysts for oxidation of ammonia and highlights recent key contributions to realizing the goals of viable energy storage and retrieval based on the N-H bonds of ammonia in a carbon-free energy cycle.

Avian major histocompatibility complex copy number variation is associated with helminth richness.

Genes of the major histocompatibility complex (MHC) play a key role in the adaptive immunity of vertebrates, as they encode receptors responsible for antigen recognition. Evolutionary history of the MHC proceeded through numerous gene duplications, which increase the spectrum of pathogens recognized by individuals. Although pathogen-mediated selection is believed to be a primary driver of MHC expansion over evolutionary times, empirical evidence for this association is virtually lacking. Here, we used an extensive dataset on MHC class II copy number variation in non-passerine birds to test for an evolutionary correlation with helminth parasite richness. As expected, our phylogenetically-informed modelling revealed a positive association between MHC copy number and total helminth richness, even after controlling for a broad spectrum of ecological and life-history traits. Thus, total helminth richness appears to be the most important correlate of MHC copy number, supporting a leading role of pathogen-mediated selection in the evolution of MHC in birds. Our results provide some of the first, although correlative, evidence linking parasitism to interspecific variation in MHC copy number among birds.

Synthesis and Characterization of Tantalum-Based Early-Late Heterobimetallic Complexes Supported by 2-(diphenylphosphino)pyrrolide Ligands.

The synthesis of the metalloligand Ta(κ2-NP)3Cl2 (NP = 2-diphenylphosphinopyrrolide) and its coordination chemistry with group 9 and 10 metals is reported. Treatment of Ta(κ2-NP)3Cl2 with group 9 and 10 metals resulted in clean formation of the heterobimetallic complexes Cl2Ta(µ2-NP)3M (M = Ni (2), Pd (3)) or Cl2Ta(µ2-NP)3MCl (M = Rh (4), Ir (5)). Each pair of complexes is isostructural and contains three phosphinopyrrolide ligands that bridge the metal centers. The d10 or d8 complexes are all diamagnetic and X-ray crystallographic analysis reveals similarly short metal-metal distances, ranging from 2.2979(5) Å to 2.4366(2) Å. Despite the similar bonding metrics in 2-5, treatment with an L type donor (2,6-dimethylphenylisocyanide (CNXylyl)) reveals 3 different coordination geometries in TaNi(CNXylyl) (6), TaPd(CNXylyl) (7), and TaIr(CNXylyl) (8). While complexes 6, 7, and 8 all bind the isocyanide at the late metal, ligand rearrangements are observed in the first row complex 6. Complex 7 binds the isocyanide in the axial position while equatorial binding is observed in 8. All isocyanide adducts maintain close metal-metal contacts in the solid state.

A range-wide domino effect and resetting of the annual cycle in a migratory songbird.

Latitudinal differences in timing of breeding are well documented but how such differences carry over to influence timing of events in the annual cycle of migratory birds is not well understood. We examined geographical variation in timing of events throughout the year using light-level geolocator tracking data from 133 migratory tree swallows ( Tachycineta bicolor) originating from 12 North American breeding populations. A swallow's breeding latitude influenced timing of breeding, which then carried over to affect breeding ground departure. This resulted in subsequent effects on the arrival and departure schedules at autumn stopover locations and timing of arrival at non-breeding locations. This 'domino effect' between timing events was no longer apparent by the time individuals departed for spring migration. Our range-wide analysis demonstrates the lasting impact breeding latitude can have on migration schedules but also highlights how such timing relationships can reset when individuals reside at non-breeding sites for extended periods of time.

The 4-Electron Cleavage of a N═N Double Bond by a Trimetallic TiNi2 Complex.

The synthesis and reactivity of a new trimetallic complex Ti(NP)4Ni2 (NP = 2-diphenylphosphinopyrrolide) (3) is reported. Single-crystal X-ray diffraction and X-ray absorption studies point to a unique bonding motif: a d10-d10, Ni0-Ni0 bond stabilized by a proximal d0 TiIV metal center. The coordination chemistry of 3 with a variety of L (L = isocyanide and alkyne) donors has also been explored. In the case of isocyanide coordination, the Ni-Ni bond is broken, while diphenylacetylene binding results in a symmetric butterfly µ2-κ2-alkyne bridge across the Ni-Ni moiety. Finally, complex 3 is capable of the 4-electron cleavage of the N═N double bond in benzo[c]cinnoline, the first example of N═N bond cleavage by Ni. The resulting product, 7, has been characterized structurally and spectroscopically, and the mechanistic implications are discussed in the context of metal-metal cooperativity.

Extensive shared polymorphism at non-MHC immune genes in recently diverged North American prairie grouse.

Gene polymorphisms shared between recently diverged species are thought to be widespread and most commonly reflect introgression from hybridization or retention of ancestral polymorphism through incomplete lineage sorting. Shared genetic diversity resulting from incomplete lineage sorting is usually maintained for a relatively short period of time, but under strong balancing selection it may persist for millions of years beyond species divergence (balanced trans-species polymorphism), as in the case of the major histocompatibility complex (MHC) genes. However, balancing selection is much less likely to act on non-MHC immune genes. The aim of this study was to investigate the patterns of shared polymorphism and selection at non-MHC immune genes in five grouse species from Centrocercus and Tympanuchus genera. For this purpose, we genotyped five non-MHC immune genes that do not interact directly with pathogens, but are involved in signaling and regulate immune cell growth. In contrast to previous studies with MHC, we found no evidence for balancing selection or balanced trans-species polymorphism among the non-MHC immune genes. No haplotypes were shared between genera and in most cases more similar allelic variants sorted by genus. Between species within genera, however, we found extensive shared polymorphism, which was most likely attributable to introgression or incomplete lineage sorting following recent divergence and large ancestral effective population size (i.e., weak genetic drift). Our study suggests that North American prairie grouse may have attained relatively low degree of reciprocal monophyly at nuclear loci and reinforces the rarity of balancing selection in non-MHC immune genes.

Major histocompatibility complex variation and blood parasites in resident and migratory populations of the common yellowthroat.

Genes of the major histocompatibility complex (MHC) are a critical part of the adaptive immune response, and the most polymorphic genes in the vertebrate genome, especially in passerine birds. This diversity is thought to be influenced by exposure to pathogens which can vary in relation to numerous factors. Migratory behaviour may be a particularly important trait to consider because migratory birds are exposed to a greater number of different pathogens and parasites at both breeding (i.e. temperate) and overwintering (i.e. tropical and subtropical) areas, as well as at stopover sites during migration. Thus, migrants are predicted to have greater MHC diversity than residents. We compared MHC variation, at both class I and II, and levels of haemosporidian infection between one resident and two migratory populations of the common yellowthroat (Geothlypis trichas). We found that residents were less likely to be infected with haemosporidian parasites and had lower MHC diversity at class I; however, variation at MHC class II was greater in residents than migrants, contrary to our prediction. These patterns were not likely to be caused by differences in population demography as genomewide heterozygosity (based on 9225 single nucleotide polymorphisms) was high in all three populations and not correlated with MHC variation. Our different results for MHC class I and II suggest that studies of immune gene variation in relation to life history need to consider that there could be different selection pressures arising from intracellular (class I) and extracellular (class II) pathogens in different populations.

Factors influencing food choice of athletes at international competition events.

Although the nutrient requirements and dietary intake of athletes have been thoroughly investigated, little is known about the influences on their food choice, particularly prior to and during competition. This study sought to investigate factors that influence food selection of athletes at two similar international competition events: the Melbourne 2006 and Delhi 2010 Commonwealth Games. A secondary aim was to explore differences in these factors between at each event given the culturally diverse locations. A survey developed for this study was distributed to athletes in the village dining hall at both events. Athletes scored a selection of factors influencing food choice on a scale of 1 (not important) to 5 (very important). A total of 769 individuals completed the questionnaire in total, with 351 (46%) from Delhi and 418 (54%) from Melbourne. Overall, athletes rated nutrient composition (M = 4.22), stage of competition (M = 4.09), time of day (M = 4.02) and familiarity of the food (M = 4.07) higher than sensory properties (smell M = 3.88; visual appearance M = 3.22) when making a food selection. Visual appearance (p = 0.01), stage of competition (p < 0.001) and time of day (p = 0.01) had greater influence in Delhi than Melbourne. Overall, a significantly higher proportion of female athletes rated smell (p < 0.001) and familiar food (p < 0.001) as important compared to males. The stage of competition and nutrition composition was rated as very important by the greatest proportion of athletes from weight category sports (61.9%) and endurance sports (57.9%) respectively. The influence of the coach and team mates was less of an influence than other factors, but more so for athletes from Non-Western regions. Further investigation of the various determinants and motives for food section of athletes from a range of sports and cultures is warranted.

Guidelines for Use of the Approximate Beta-Poisson Dose-Response Model.

For dose-response analysis in quantitative microbial risk assessment (QMRA), the exact beta-Poisson model is a two-parameter mechanistic dose-response model with parameters α>0 and ß>0, which involves the Kummer confluent hypergeometric function. Evaluation of a hypergeometric function is a computational challenge. Denoting PI(d) as the probability of infection at a given mean dose d, the widely used dose-response model PI(d)=1-(1+dß)-α is an approximate formula for the exact beta-Poisson model. Notwithstanding the required conditions α<<ß and ß>>1, issues related to the validity and approximation accuracy of this approximate formula have remained largely ignored in practice, partly because these conditions are too general to provide clear guidance. Consequently, this study proposes a probability measure Pr(0 < r < 1 | α̂, ß̂) as a validity measure (r is a random variable that follows a gamma distribution; α̂ and ß̂ are the maximum likelihood estimates of α and ß in the approximate model); and the constraint conditions ß̂>(22α̂)0.50 for 0.02<α̂<2 as a rule of thumb to ensure an accurate approximation (e.g., Pr(0 < r < 1 | α̂, ß̂) >0.99) . This validity measure and rule of thumb were validated by application to all the completed beta-Poisson models (related to 85 data sets) from the QMRA community portal (QMRA Wiki). The results showed that the higher the probability Pr(0 < r < 1 | α̂, ß̂), the better the approximation. The results further showed that, among the total 85 models examined, 68 models were identified as valid approximate model applications, which all had a near perfect match to the corresponding exact beta-Poisson model dose-response curve.

Systematic OR Block Allocation at a Large Academic Medical Center: Comprehensive Review on a Data-driven Surgical Scheduling Strategy.

OBJECTIVE: To alleviate the surgical patient flow congestion in the perioperative environment without additional resources. BACKGROUND: Massachusetts General Hospital experienced increasing overcrowding of the perioperative environment in 2008. The Post-Anesthesia Care Unit would often be at capacity, forcing patients to wait in the operating room. The cause of congestion was traced back to significant variability in the surgical inpatient-bed occupancy across the days of the week due to elective surgery scheduling practices. METHODS: We constructed an optimization model to find a rearrangement of the elective block schedule to smooth the average inpatient census by reducing the maximum average occupancy throughout the week. The model was revised iteratively as it was used in the organizational change process that led to an implementable schedule. RESULTS: Approximately 21% of the blocks were rearranged. The setting of study is very dynamic. We constructed a hypothetical scenario to analyze the patient population most representative of the circumstances under which the model was built. For this group, the patient volume remained constant, the average census peak decreased by 3.2% (P < 0.05), and the average weekday census decreased by 2.8% (P < 0.001). When considering all patients, the volume increased by 9%, the census peak increased 1.6% (P < 0.05), and the average weekday census increased by 2% (P < 0.001). CONCLUSIONS: This work describes the successful implementation of a data-driven scheduling strategy that increased the effective capacity of the surgical units. The use of the model as an instrument for change and strong managerial leadership was paramount to implement and sustain the new scheduling practices.

Experimental evidence that brighter males sire more extra-pair young in tree swallows.

Across taxa, extra-pair mating is widespread among socially monogamous species, but few studies have identified male ornamental traits associated with extra-pair mating success, and even fewer studies have experimentally manipulated male traits to determine whether they are related directly to paternity. As a consequence, there is little experimental evidence to support the widespread hypothesis that females choose more ornamented males as extra-pair mates. Here, we conducted an experimental study of the relationship between male plumage colour and fertilization success in tree swallows (Tachycineta bicolor), which have one of the highest levels of extra-pair mating in birds. In this study, we experimentally dulled the bright blue plumage on the back of males (with nontoxic ink markers) early in the breeding season prior to most mating. Compared with control males, dulled males sired fewer extra-pair young, and, as a result, fewer young overall. Among untreated males, brighter blue males also sired more extra-pair young, and in paired comparisons, extra-pair sires had brighter blue plumage than the within-pair male they cuckolded. These results, together with previous work on tree swallows, suggest that extra-pair mating behaviour is driven by benefits to both males and females.

Specific alleles at immune genes, rather than genome-wide heterozygosity, are related to immunity and survival in the critically endangered Attwater's prairie-chicken.

The negative effects of inbreeding on fitness are serious concerns for populations of endangered species. Reduced fitness has been associated with lower genome-wide heterozygosity and immune gene diversity in the wild; however, it is rare that both types of genetic measures are included in the same study. Thus, it is often unclear whether the variation in fitness is due to the general effects of inbreeding, immunity-related genes or both. Here, we tested whether genome-wide heterozygosity (20 990 SNPs) and diversity at nine immune genes were better predictors of two measures of fitness (immune response and survival) in the endangered Attwater's prairie-chicken (Tympanuchus cupido attwateri). We found that postrelease survival of captive-bred birds was related to alleles of the innate (Toll-like receptors, TLRs) and adaptive (major histocompatibility complex, MHC) immune systems, but not to genome-wide heterozygosity. Likewise, we found that the immune response at the time of release was related to TLR and MHC alleles, and not to genome-wide heterozygosity. Overall, this study demonstrates that immune genes may serve as important genetic markers when monitoring fitness in inbred populations and that in some populations specific functional genes may be better predictors of fitness than genome-wide heterozygosity.