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One of the most intense air mass transformations on Earth happens when cold air flows from frozen surfaces to much warmer open water in cold-air outbreaks (CAOs), a process captured beautifully in satellite imagery. Despite the ubiquity of the CAO cloud regime over high-latitude oceans, we have a rather poor understanding of its properties, its role in energy and water cycles, and its treatment in weather and climate models. The Cold-Air Outbreaks in the Marine Boundary Layer Experiment (COMBLE) was conducted to better understand this regime and its representation in models. COMBLE aimed to examine the relations between surface fluxes, boundary layer structure, aerosol, cloud, and precipitation properties, and mesoscale circulations in marine CAOs. Processes affecting these properties largely fall in a range of scales where boundary layer processes, convection, and precipitation are tightly coupled, which makes accurate representation of the CAO cloud regime in numerical weather prediction and global climate models most challenging. COMBLE deployed an Atmospheric Radiation Measurement Mobile Facility at a coastal site in northern Scandinavia (69°N), with additional instruments on Bear Island (75°N), from December 2019 to May 2020. CAO conditions were experienced 19% (21%) of the time at the main site (on Bear Island). A comprehensive suite of continuous in situ and remote sensing observations of atmospheric conditions, clouds, precipitation, and aerosol were collected. Because of the clouds’ well-defined origin, their shallow depth, and the broad range of observed temperature and aerosol concentrations, the COMBLE dataset provides a powerful modeling testbed for improving the representation of mixed-phase cloud processes in large-eddy simulations and large-scale models.

Identification of the geographic extent of population boundaries, the distribution of genetic lineages, and the amount of genetic exchange among breeding groups is needed for effective conservation of vulnerable marine migratory species. This is particularly true of the flatback turtle (Natator depressus), which only breeds in Australia but has extensive migrations that can include international waters. This study investigated the phylogeography and genetic structure among 17 flatback turtle rookeries across their range by sequencing an 810 bp portion of the mitochondrial DNA in 889 samples and genotyping 10 microsatellite loci in 598 samples. There was low phylogenetic divergence among haplotypes and evidence of recent population expansion, likely in the late Pleistocene. A predominant haplotype was found across all rookeries, but other haplotype groups were regionally specific. In general, there was agreement in patterns of genetic differentiation in the mitochondrial DNA and microsatellite data, and in some pairwise comparisons a higher mutation rate of microsatellites provided stronger evidence of differentiation. These results suggest natal philopatry operates in the choice of breeding locations for males as well as females. Evidence of genetic connectivity among neighbouring rookeries led to the identification of seven genetic stocks. Geographic boundaries of rookeries used by genetic stocks varied widely (160–1,300 km), highlighting a need for field studies to better understand movement patterns. Hierarchical analysis of molecular variance identified significant genetic differentiation based upon genetic stock, nesting phenology (summer vs. winter nesters), and a west–east discontinuity across Torres Strait. A pattern of isolation by distance was identified, which was most strongly observed in the microsatellite data. In combination with tagging and telemetry studies, these results will allow better quantification of stock-specific threats along migratory routes and in foraging habitats. Implications of climate change will be stock specific and may depend upon the extent of genetic connectivity between neighbouring stocks.

Globally distributed marine taxa are well suited for investigations of biogeographic impacts on genetic diversity, connectivity, and population demography. The sea turtle genusThe online version contains supplementary material available at 10.1007/s10592-022-01465-3.

Advances in high-throughput sequencing (HTS) technologies coupled with increased interdisciplinary collaboration are rapidly expanding capacity in the scope and scale of wildlife genetic studies. While existing HTS methods can be directly applied to address some evolutionary and ecological questions, certain research goals necessitate tailoring methods to specific study organisms, such as high-throughput genotyping of the same loci that are comparable over large spatial and temporal scales. These needs are particularly common for studies of highly mobile species of conservation concern like marine turtles, where life history traits, limited financial resources and other constraints require affordable, adaptable methods for HTS genotyping to meet a variety of study goals. Here, we present a versatile marine turtle HTS targeted enrichment platform adapted from the recently developed Rapture (RAD-Capture) method specifically designed to meet these research needs. Our results demonstrate consistent enrichment of targeted regions throughout the genome and discovery of candidate variants in all species examined for use in various conservation genetics applications. Accurate species identification confirmed the ability of our platform to genotype over 1,000 multiplexed samples and identified areas for future methodological improvement such as optimization for low initial concentration samples. Finally, analyses within green turtles supported the ability of this platform to identify informative SNPs for stock structure, population assignment and other applications over a broad geographic range of interest to management. This platform provides an additional tool for marine turtle genetic studies and broadens capacity for future large-scale initiatives such as collaborative global marine turtle genetic databases.

Extensive regions of marine boundary layer cloud impact the radiative balance through their significant shortwave albedo while having little impact on outgoing longwave radiation. Despite this importance, these cloud systems remain poorly represented in large-scale models due to difficulty in representing the processes that drive their lifecycle and coverage. In particular, the mesoscale organization, and cellular structure of marine boundary clouds has important implications for the subsequent cloud feedbacks. In this study, we use long-term (2013–2018) observations from the Atmospheric Radiation Measurement (ARM) Facility's Eastern North Atlantic (ENA) site on Graciosa Island, Azores, Portugal to identify cloud cases with open- or closed-cellular organization. More than 500 hours of each organization type are identified. The ARM observations are combined with reanalysis and satellite products to quantify the cloud, precipitation, aerosol, thermodynamic and large-scale synoptic characteristics associated with these cloud types. Our analysis shows that both cloud organization populations occur during similar sea surface temperature conditions, but the open-cell cases are distinguished by stronger cold-air advection and large-scale subsidence compared to the closed-cell cases, consistent with their formation during cold-air outbreaks. We also find that the open-cell cases were associated with deeper boundary layers, stronger low-level winds, and higher-rain rates compared to their closed-cell counterparts. Finally, raindrops with diameters larger than one millimeter were routinely recorded at the surface during both populations, with a higher number of large drops during the open-cellular cases. The similarities and differences noted herein provide important insights into the environmental and cloud characteristics during varying marine boundary layer cloud mesoscale organization and will be useful for the evaluation of model simulations for ENA marine clouds.

This study suggests a new approach on how diurnal precipitation is modulated by the nighttime events developed over Central Amazon using data from the Observations and Modelling of the Green Ocean Amazon (GoAmazon 2014/5) field campaign in the Central Amazon as well as radar and satellite data. Local observations of cloud occurrences, soil temperature, surface fluxes, and planetary boundary layer characteristics are coupled with satellite data to identify physical mechanisms that control the diurnal rainfall in Amazonas during the wet and dry season. This is accomplished by evaluating the atmospheric properties during the nocturnal periods from the days prior to rainfall and non-raining events. Comparisons between non-rainy and rainy transitions are presented for the wet (January to April) and dry (June to September) seasons. The results suggest that wet season diurnal precipitation is modulated mainly by night-time cloud coverage and local effects such as turbulence, while dry season rain events are mainly controlled by large-meso scale circulation.

Assessments of fisheries by‐catch on marine megafauna are important for developing effective management strategies. For sea turtles, impacts may be evident in nesting population trends, but generally only after a lag, as turtles are slow to mature. We examined 850 loggerhead turtle (Caretta caretta) by‐catch samples collected over 14 years throughout the western North Atlantic to identify source nesting populations. We identified proportions of turtles from 19 distinct management units (MUs), using mitochondrial DNA and mixed stock analysis, considering population size. We found a significant split in the distribution of small versus large loggerheads to the north and south of Cape Hatteras, North Carolina (latitude 35°N). North of Cape Hatteras, large turtles came from south‐east Florida (SEFL; 44% ± 15%) and the northern United States (33% ± 16%) MUs, while south of Cape Hatteras, the major contributors were Central East Florida (52% ± 20%) and south‐east Florida (SEFL; 41% ± 20%). Small turtles in the north came from Central East Florida (64% ± 14%), and in the south, south‐east Florida had the highest representation (56% ± 25%). There was little contribution from Mediterranean and Cape Verde populations, indicating low risk from western North Atlantic by‐catch to MUs in the Mediterranean. Understanding where threats may impact source populations is important, particularly for larger size turtles, as these individuals have the highest reproductive value. These findings allow more informed threat assessments to be conducted for loggerhead turtles considering spatial and demographic structure.

Reaction of the complex [(TpPh,Me)FeII(NCMe)3]BF4, where TpPh,Me = hydrotris(3-phenyl,5-methyl-1-pyrazolyl)borate, with the iodonium heteroylide PhI═NTs (1.5 equiv) is proposed to result in the insertion of N-tosylnitrene into one C–H bond at the ortho ring position of a 3-pyrazole phenyl substituent; subsequent deprotonation of the nascent aniline and one-electron oxidation of iron forms TsNH2 (0.5 equiv) as a coproduct. The covalent ligand modification and oxidation results in an intense purple-brown anilinato–iron(III) LMCT chromophore. This intramolecular reaction is utilized as a consistent clock to determine relative rates of competitive intermolecular nitrene transfer to added substrates, specifically to para-substituted styrenes and thioanisoles. Prior addition of substrate to the reaction of PhI═NTs with the iron(II) complex attenuates the CT absorbance of the equilibrium solution. Fitting of the concentration-dependent absorption data gives the ratio of intra- versus intermolecular nitrene trans...

A “second-generation” scorpionate ligand was utilized to prepare the nickel(II) borohydride complex [(TpPh,Me)Ni(η3-BH4)], wherein the borohydride was coordinated through two bridging B–H bonds, leaving two terminal B–H bonds uncoordinated as determined by X-ray crystallography. The distorted square-pyramidal complex is paramagnetic (S = 1), with 18 valence electrons, and contrasts with a previously reported 20-electron pseudo-octahedral “first-generation” analogue, [(TpMe,Me)Ni(η4-BH4)] (P. J. Desrochers, et al. Inorg. Chem. 2003, 42, 7945–7950). These distinct borohydride coordination modes were distinguished by FTIR spectroscopy, and rationalized by DFT calculations on simplified models, [(Tp)Ni(ηn-BH4)] (n = 3, 4). The difference in borohydride hapticities is attributed to the steric effect of the scorpionate 3-pyrazole phenyl substituents disposed proximally to the metal, thus demonstrating the subtle versatility of Trofimenko's scorpionate ligands in controlling ligand field geometries. The precursor complex [(TpPh,Me)Ni(κ2-NO3)] was also prepared and characterized.

Difficult as it is to imagine today, in 1937 America's two leading media companies fought over the right to perform Shakespeare for an American radio audience in an attempt to bring prestige to their networks. The resulting fourteen broadcasts are among the more remarkable recreations of Shakespeare of their time. This lively and engaging book shows the cultural dominance of radio in the 1930s, and tells the story of why the networks each wanted to lord Shakespeare's prestige over the other, how they put their series together, the critical reception, and the cultural impact and legacies of the broadcasts.

Summary Climate change affects species and ecosystems around the globe [1]. The impacts of rising temperature are particularly pertinent in species with temperature-dependent sex determination (TSD), where the sex of an individual is determined by incubation temperature during embryonic development [2]. In sea turtles, the proportion of female hatchlings increases with the incubation temperature. With average global temperature predicted to increase 2.6°C by 2100 [3], many sea turtle populations are in danger of high egg mortality and female-only offspring production. Unfortunately, determining the sex ratios of hatchlings at nesting beaches carries both logistical and ethical complications. However, sex ratio data obtained at foraging grounds provides information on the amalgamation of immature and adult turtles hatched from different nesting beaches over many years. Here, for the first time, we use genetic markers and a mixed-stock analysis (MSA), combined with sex determination through laparoscopy and endocrinology, to link male and female green turtles foraging in the Great Barrier Reef (GBR) to the nesting beach from which they hatched. Our results show a moderate female sex bias (65%–69% female) in turtles originating from the cooler southern GBR nesting beaches, while turtles originating from warmer northern GBR nesting beaches were extremely female-biased (99.1% of juvenile, 99.8% of subadult, and 86.8% of adult-sized turtles). Combining our results with temperature data show that the northern GBR green turtle rookeries have been producing primarily females for more than two decades and that the complete feminization of this population is possible in the near future.

Hawksbill turtle (Eretmochelys imbricata) populations have experienced global decline because of a history of intense commercial exploitation for shell and stuffed taxidermied whole animals, and harvest for eggs and meat. Improved understanding of genetic diversity and phylogeography is needed to aid conservation. In this study, we analyzed the most geographically comprehensive sample of hawksbill turtles from the Indo-Pacific Ocean, sequencing 766 bp of the mitochondrial control region from 13 locations (plus Aldabra, n = 4) spanning over 13500 km. Our analysis of 492 samples revealed 52 haplotypes distributed in 5 divergent clades. Diversification times differed between the Indo-Pacific and Atlantic lineages and appear to be related to the sea-level changes that occurred during the Last Glacial Maximum. We found signals of demographic expansion only for turtles from the Persian Gulf region, which can be tied to a more recent colonization event. Our analyses revealed evidence of transoceanic migration, including connections between feeding grounds from the Atlantic Ocean and Indo-Pacific rookeries. Hawksbill turtles appear to have a complex pattern of phylogeography, showing a weak isolation by distance and evidence of multiple colonization events. Our novel dataset will allow mixed-stock analyses of hawksbill turtle feeding grounds in the Indo-Pacific by providing baseline data needed for conservation efforts in the region. Eight management units are proposed in our study for the Indo-Pacific region that can be incorporated in conservation plans of this critically endangered species.

Abstract. This is study provides an overview of precipitation processes and their sensitivities to environmental conditions, in the Central Amazon Basin, during the GoAmazon2014/5 and ACRIDICON-CHUVA experiments. Taking advantage of the numerous measuring platforms and instruments systems operating during both campaigns sampling cloud structure and environmental conditions during 2014 and 2015, the rainfall variability among seasons, aerosol loading, land surface type, and topography have carefully been characterized. Differences between the wet and dry seasons were examined from a variety of different perspectives. The rain rate distribution, the total amount of rainfall, and the raindrop size distribution (the mean mass-weighted diameter) were quantified for the two seasons. The dry season has a higher average rain rate than the wet season and reflects more intense rain. While the cumulative wet season rainfall amount was four times larger than the total dry season rainfall, reflecting in large total rainfall accumulation. The typical size and life cycle of the Amazon cloud clusters (observed by satellite) and rain cells (observed by radar) were examined, as well their differences among the seasons. Moreover, we analyse the monthly mean thermodynamical and dynamical variables, measured by radiosondes to elucidate the differences in rainfall characteristics during the wet and dry seasons. The sensitivity of rainfall to the atmospheric aerosol loading is discussed with regard to the mean mass-weighted diameter and rain rate. This topic was evaluated during the wet season only due to the insignificant statistics of rainfall events for different ranges of aerosol loadings and the low frequency of precipitation events during the dry season. The aerosol impacts on the cloud droplet diameter is different for small and large drops. For the wet season, we observe no dependence on land surface type on the rain rate. However, during the dry season, urban areas exhibit the largest rain rate tail distribution, and deforested regions have the lowest mean rain rate. Airplane measurements were performed to characterize and contrast cloud microphysical properties and processes over forested and deforested regions. The vertical motion turned out to be uncorrelated with cloud droplet sizes, but the cloud droplets number concentration revealed a linear relationship to the vertical motion. Clouds over forest exhibit larger droplets than clouds over pastures at all cloud levels. Finally, the connections between topography and rain rate were evaluated, showing a higher rain rate over higher elevations for the dry season.

Routine cloud, precipitation and thermodynamic observations collected by the ARM Mobile Facility (AMF) and Aerial Facility (AAF) during the two-year DOE ARM Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign are summarized. These observations quantify the diurnal to large-scale thermodynamic regime controls on the clouds and precipitation over the undersampled, climatically important, Amazon basin region. The extended ground deployment of cloud-profiling instrumentation enabled a unique look at multiple cloud regime controls at high temporal and vertical resolution. This longer-term ground deployment coupled with two short-term aircraft intensive observing periods allowed new opportunities to better characterize cloud and thermodynamic observational constraints as well as cloud radiative impacts for modeling efforts within typical Amazon ‘wet’ and ‘dry’ seasons.

The complex processes involved with animal migration have long been a subject of biological interest, and broad-scale movement patterns of many marine turtle populations still remain unresolved. While it is widely accepted that once marine turtles reach sexual maturity they home to natal areas for nesting or reproduction, the role of philopatry to natal areas during other life stages has received less scrutiny, despite widespread evidence across the taxa. Here we report on genetic research that indicates that juvenile hawksbill turtles ( Eretmochelys imbricata ) in the eastern Pacific Ocean use foraging grounds in the region of their natal beaches, a pattern we term natal foraging philopatry. Our findings confirm that traditional views of natal homing solely for reproduction are incomplete and that many marine turtle species exhibit philopatry to natal areas to forage. Our results have important implications for life-history research and conservation of marine turtles and may extend to other wide-ranging marine vertebrates that demonstrate natal philopatry.

Marine turtles migrate across long distances, exhibit complex life histories, and occupy habitats that are difficult to observe. These factors present substantial challenges to understanding fundamental aspects of their biology or assessing human impacts, many of which are important for the effective conservation of these threatened and endangered species. The early development and application of genetic tools made important contributions to understanding marine turtle population and evolutionary biology, such as providing evidence of regional natal homing by breeding adults, establishing connectivity between rookeries and foraging habitats, and determining phylogeography and broad scale stock structure for most marine turtle species. Recent innovations in molecular technologies, statistical methods, and creative application of genetic tools have significantly built upon this knowledge to address key questions in marine turtle biology and conservation management. Here, we evaluate the latest major advances and potential of marine turtle genetic applications, including improved resolution and large-scale syntheses of population structure, connectivity and phylogeography, estimation of key demographic rates such as age to maturity and operational or breeding sex ratios, insight into reproductive strategies and behavior, and assessment of differential human impacts among populations. We then discuss remaining challenges and emerging capabilities, such as rapid, multiplexed genotyping, and investigation of the genomic underpinnings of adaptive variation afforded by high-throughput sequencing technologies.

Pseudotetrahedral scorpionato halide complexes [(TpPh,Me)Ni–X] [TpPh,Me = hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate] were synthesized by metathesis of Tl(TpPh,Me) and NiX2 (X = Cl, Br, I). Pyrazole adducts [(TpPh,Me)Ni(HpzPh,Me)(X)] (X = Cl, I) were also obtained. [(TpPh,Me)Ni–X] (X = Br, I) are isomorphous with previously reported [(TpPh,Me)Ni–Cl], and a new solvated pseudo-polymorph [(TpPh,Me)Ni–Cl]·2CH2Cl2 was found in this work. Ni–X bond lengths correspond to ionic radii of the halide ions, but some variations in Ni–Cl and Ni–N bond lengths are respectively attributed to bending of the chloride from the ideal threefold HB···Ni axis and to the size of the 3-pyrazole substituents. Electronic spectra were rationalized by means of time-dependent (TD) DFT calculations on simplified C3v-symmetric [(Tp)Ni–X] models. Exogenous pyrazole binds to give the pentacoordinate adducts [(TpPh,Me)Ni(HpzPh,Me)(X)] (X = Cl, I). We obtained a crystal structure of the iodide adduct, as well as that of [(TpPh,Me)Ni(HpzPh,Me)(Cl)]·0.5MeCN, isomorphous with a previously reported aquo monosolvate. A hallmark of adduct formation is an intramolecular N–H···X hydrogen bond between the added pyrazole and the adjacent halide ligand, thus giving rise to a strong IR absorption band. The stretching frequency correlates to the N(H)···X separation for the range of known adducts.

Climate, behavior, ecology, and oceanography shape patterns of biodiversity in marine faunas in the absence of obvious geographic barriers. Marine turtles are an example of highly migratory creatures with deep evolutionary lineages and complex life histories that span both terrestrial and marine environments. Previous studies have focused on the deep isolation of evolutionary lineages (>3 mya) through vicariance; however, little attention has been given to the pathways of colonization of the eastern Pacific and the processes that have shaped diversity within the most recent evolutionary time. We sequenced 770 bp of the mtDNA control region to examine the stock structure and phylogeography of 545 green turtles from eight different rookeries in the central and eastern Pacific. We found significant differentiation between the geographically separated nesting populations and identified five distinct stocks (F ST = 0.08-0.44, P < 0.005). Central and eastern Pacific Chelonia mydas form a monophyletic group containing 3 subclades, with Hawaii more closely related to the eastern Pacific than western Pacific populations. The split between sampled central/eastern and western Pacific haplotypes was estimated at around 0.34 mya, suggesting that the Pacific region west of Hawaii has been a more formidable barrier to gene flow in C. mydas than the East Pacific Barrier. Our results suggest that the eastern Pacific was colonized from the western Pacific via the Central North Pacific and that the Revillagigedos Islands provided a stepping-stone for radiation of green turtles from the Hawaiian Archipelago to the eastern Pacific. Our results fit with a broader paradigm that has been described for marine biodiversity, where oceanic islands, such as Hawaii and Revillagigedo, rather than being peripheral evolutionary "graveyards", serve as sources and recipients of diversity and provide a mechanism for further radiation.

Reactions of [Ni0(COD)2] (COD = 1,5-cyclooctadiene) with meta-chloroperoxybenzoic acid, phenyl-N-tosylimidoiodinane or 2-(tert-butylsulfonyl)iodosylbenzene were performed in THF solution in the presence of one equivalent of tris(3,5-dimethylpyrazol-1-yl)methane (Tpm∗), yielding the product complexes [Tpm∗NiII(OH2)(3-ClC6H4CO2)2] (2), [(Tpm∗)2NiII][NiII(NHTs)4] (3), and [Tpm∗NiII(OH)2(OH2)] (4), respectively. Products 2–4 arise from oxidation of solvated [Ni0(COD)2], with subsequent ligation of Tpm∗ and substrate fragments leading to assembly of disparate octahedral nickel(II) centers. For comparative purposes, the previously reported complex [(Tpm∗)NiII(OH2)Cl2] (1) was also obtained from Tpm∗ and NiCl2. All complexes were characterized spectroscopically, and complexes 1–3 were also structurally characterized by X-ray crystallography.

Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni(detu)4Cl2 (detu = N,N'-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173-333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519-520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni(detu)4](2+) centers with distorted planar ligation of nickel(II) to the four sulfur atoms, with an average Ni-S bond length of 2.226(3) A. The nickel ion was displaced out-of-plane by 0.334 A toward a proximal apical chloride at a nonbonding distance of 3.134(1) A. Asymmetry in the trans S-Ni-S angles was coupled to a monoclinic ↔ tetragonal lattice distortion (T(1/2) = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel(II) with approach of the proximal chloride at higher temperatures (T(1/2) = 383 ± 18 K), which is consistent with a contraction of -0.096(4) A in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni(dmtu)4Cl](+) model (dmtu = N,N'-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni-S bond lengths of 2.45 A and an apical Ni-Cl bond of 2.43 A. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution.

Fisheries that operate at large spatial scales and with high intensity have the potential to impact highly migratory species, and it is important to characterize threats to specific breeding populations of these species. We used many‐to‐many mixed‐stock analysis (MSA) (n = 408) and microsatellite assignment testing (n = 397) to determine source populations for leatherback turtles (Dermochelys coriacea) caught as bycatch in the U.S. pelagic longline fishery from 2002 to 2012 in the western North Atlantic. Within the United States, we had bycatch samples from the majority of statistical fishing areas: Gulf of Mexico (GOM), Northeast Distant (NED), Caribbean (CAR), Florida East Coast (FEC), Mid Atlantic Bight (MAB), Northeast Coastal (NEC), South Atlantic Bight (SAB) and Sargasso (SAR). We determined the proportions of turtles from each of nine nesting stocks in the Atlantic in each of the sampled areas. These nesting stocks included Brazil, Costa Rica, Florida, Trinidad, French Guiana, St. Croix, Ghana, Gabon, and South Africa. The MSA revealed that the NED had a lower relative proportion of turtles from Costa Rica than other areas and that the GOM had the highest relative proportion of turtles from Costa Rica. No turtles were assigned to the African rookeries, lending further evidence that turtles from that region forage elsewhere and therefore may not be affected by western North Atlantic fisheries. This work contributes to the ongoing assessment of threats to leatherback turtles in the Regional Management Unit (RMU) of the western North Atlantic, and draws attention to the disproportionate number of turtles from Costa Rica being caught in the Gulf of Mexico; Costa Rica is one of the only populations in the northern Atlantic that is not experiencing significant increases in nest numbers. This approach should be useful in determining population‐specific threats to other highly migratory protected species that may depend on segregated foraging areas either within or among species.

Migratory marine species present challenges for conservation because of complex threats within their pelagic dispersal zones, including coastal foraging areas and extensive migration pathways, or at breeding grounds. To better understand the connectivity between green turtle rookeries and foraging populations, we sequenced the mtDNA control region of 987 turtles from 6 major foraging grounds on a ~2300 km longitudinal transect off eastern Australia, and used mixed stock analysis (MSA) to estimate their natal origins. We investigated variation in natal origins within different size classes and over spatial and temporal scales and compared this to approximately 30 yr of mark-recapture data. For adult turtles, we found that the northern Great Barrier Reef (nGBR) genetic stock dominated in the northern feeding grounds while the southern Great Barrier Reef (sGBR) and Coral Sea stocks dominated in the south, with a changeover of dominating stock occurring between 14° and 20°S. However, at the 3 most northern feeding grounds, we found an unexpected decrease (17-30%) in the proportion of nGBR turtles among small immature turtles relative to large immatures and adults. Four possible hypotheses were explored, with the 2 most plausible being that (1) small immature turtles from the sGBR and other rookeries first settle in nGBR feeding grounds, but later shift to other feeding grounds as they mature, or (2) a reduced hatching success for decades from the main nGBR rookery at Raine Island has resulted in reduced recruitment into the nGBR feeding ground from this stock. These results may indicate an alarming reduction in hatching success at the largest known green turtle rookery in the world.

International audience; In 2010, an international group of 35 sea turtle researchers refined an initial list of more than 200 research questions into 20 metaquestions that were considered key for management and conservation of sea turtles. These were classified under 5 categories: reproductive biology, biogeography, population ecology, threats and conservation strategies. To obtain a picture of how research is being focused towards these key questions, we undertook a systematic review of the peer-reviewed literature (2014 and 2015) attributing papers to the original 20 questions. In total, we reviewed 605 articles in full and from these 355 (59%) were judged to substantively address the 20 key questions, with others focusing on basic science and monitoring. Progress to answering the 20 questions was not uniform, and there were biases regarding focal turtle species, geographic scope and publication outlet. Whilst it offers some meaningful indications as to effort, quantifying peer-reviewed literature output is obviously not the only, and possibly not the best, metric for understanding progress towards informing key conservation and management goals. Along with the literature review, an international group based on the original project consortium was assigned to critically summarise recent progress towards answering each of the 20 questions. We found that significant research is being expended towards global priorities for management and conservation of sea turtles. Although highly variable, there has been significant progress in all the key questions identified in 2010. Undertaking this critical review has highlighted that it may be timely to undertake one or more new prioritizing exercises. For this to have maximal benefit we make a range of recommendations for its execution. These include a far greater engagement with social sciences, widening the pool of contributors and focussing the questions, perhaps disaggregating ecology and conservation.

Scorpionate complexes of the middle to late 3d transition metals [(L)M(NCMe)3](BF4)n (M = Mn, Fe, Co, Ni: 1M, L = tris(3,5-dimethylpyrazol-1-yl)methane, TpmMe,Me, n = 2; 2M, L = tris(3-phenylpyrazol-1-yl)methane, TpmPh, n = 2; 3M except 3Mn, L = hydrotris(3,5-dimethylpyrazol-1-yl)borate, [TpMe,Me]−, n = 1; 4M, L = hydrotris(3-phenyl-5-methylpyrazol-1-yl)borate, [TpPh,Me]−, n = 1) were examined as catalysts for styrene aziridination and THF amination using phenyl-N-tosyliodinane as a nitrene donor. [(TpmMe,Me)Fe(NCMe)3](BF4)2 (1Fe) was identified as the most active catalyst, giving nearly quantitative nitrene transfer yields at 5 mol % loadings. The reactivity of 1Fe with a wider range of organic substrates was also explored, and a striking observation was strong selectivity for aromatic rather than benzylic amination for alkylaromatic substrates.

Pseudotetrahedral nickel(II) phenolate complexes Tp(R,Me)Ni-OAr (Tp(R,Me) = hydrotris(3-R-5-methylpyrazol-1-yl)borate; R = Ph {1a}, Me {1b}; OAr = O-2,6-(i)Pr(2)C(6)H(3)) were synthesized as models for nickel-substituted copper amine oxidase apoenzyme, which utilizes an N(3)O (i.e., His(3)Tyr) donor set to activate O(2) within its active site for oxidative modification of the tyrosine residue. The bioinspired synthetic complexes 1a,b are stable in dilute CH(2)Cl(2) solutions under dry anaerobic conditions, but they decompose readily upon exposure to O(2) and H(2)O. Aerobic decomposition of 1a yields a range of organic products consistent with formation of phenoxyl radical, including 2,6-diisopropyl-1,4-benzoquinone, 3,5,3',5'-tetraisopropyl-4,4'-diphenodihydroquinone, and 3,5,3',5'-tetraisopropyl-4,4'-diphenoquinone, which requires concurrent O(2) reduction. The dimeric product complex di[hydro{bis(3-phenyl-5-methylpyrazol-1-yl)(3-ortho-phenolato-5-methylpyrazol-1-yl)borato}nickel(II)] (2) was obtained by ortho C-H bond hydroxylation of a 3-phenyl ligand substituent on 1a. In contrast, aerobic decomposition of 1b yields a dimeric complex [Tp(Me,Me)Ni](2)(μ-CO(3)) (3) with unmodified ligands. However, a unique organic product was recovered, assigned as 3,4-dihydro-3,4-dihydroxy-2,6-diisopropylcyclohex-5-enone on the basis of (1)H NMR spectroscopy, which is consistent with dihydroxylation (i.e., addition of H(2)O(2)) across the meta and para positions of the phenol ring. Initial hydrolysis of 1b yields free phenol and the known complex [Tp(Me,Me)Ni(μ-OH)](2), while hydrolysis of 1a yields an uncharacterized intermediate, which subsequently rearranges to the new sandwich complex [(Tp(Ph,Me))(2)Ni] (4). Autoxidation of the released phenol under O(2) was observed, but the reaction was slow and incomplete. However, both 4 and the in situ hydrolysis intermediate derived from 1a react with added H(2)O(2) to form 2. A mechanistic scheme is proposed to account for the observed product formation by convergent oxygenation and hydrolytic autoxidation pathways, and hypothetical complex intermediates along the former were modeled by DFT calculations. All new complexes (i.e., 1a,b and 2-4) were fully characterized by FTIR, (1)H NMR, and UV-vis-NIR spectroscopy and by X-ray crystallography.

The complex Tp(Ph,Me)NiS(2)CNMe(2) [Tp(Ph,Me) = hydrotris(3-phenyl-5-methyl-1-pyrazolyl)borate] features a bioinspired N(3)S(2) ligand set supporting a five-coordinate, trigonally distorted square-pyramidal geometry in the solid state. Spin crossover of Ni(II) was demonstrated by temperature-dependent X-ray crystallography and magnetic susceptibility measurements. The crystal lattice contains two independent molecules (i.e., Ni1 and Ni2). At 293 K, the observed bond lengths and susceptibility are consistent with high-spin (S = 1) Ni(II), and both molecules exhibit relatively short axial Ni-N bonds and long Ni-N and Ni-S equatorial bonds. At 123 K, the Ni1 complex remains high-spin, but the Ni2 molecule substantially crosses to a structurally distinct diamagnetic (S = 0) state with significant elongation of the axial Ni-N bond and offsetting contraction of the equatorial bonds. The temperature-dependent susceptibility data were fit to a spin equilibrium at Ni2 [ΔH° = 1.13(2) kcal/mol and ΔS° = +7.3(1) cal mol(-1) K(-1)] consistent with weak coupling to lattice effects. Cooling below 100 K results in crossover of the Ni1 complex.

Manganese(II) complexes (Mn(L)X2) were prepared and characterized, where L is a neutral di-Schiff base

Context An understanding of the genetic stock structure of wide-ranging marine species is necessary for sound conservation management. Eretmochelys imbricata is Critically Endangered globally, but is among the least studied marine turtles. Reduced population sizes, its long-distance migratory nature between feeding and nesting habitats and poor understanding of its stock structure, biology and anthropogenic impact(s) pose challenges to developing effective conservation strategies for regional conspecifics. Aims Quantification of the population connectivity between specific feeding areas and regional nesting populations is needed for threat assessment and development of mitigation actions. Methods Here, we sequenced the mitochondrial DNA (mtDNA) of 91 immature and adult foraging E. imbricata individuals captured at the Howick Group of islands in the far-northern section of the Great Barrier Reef (nGBR), Queensland, Australia. We used a Bayesian mixed-stock analysis (MSA) approach to determine the contribution of nine regional genetically characterised breeding populations to this feeding aggregation. Key results The MSA estimated that a majority (83%; 95% CI = 70–92%) of feeding E. imbricata had originated from nesting beaches in the Bismarck–Solomon Sea region, whereas only 15% (95% CI = 6–25%) had originated from nGBR rookeries. International reproductive migrations were also corroborated by the return of 18 uniquely numbered titanium flipper tags that had been applied to E. imbricata found foraging in the Howick Group and had swum to rookeries within the Bismarck–Solomon Sea region. These 18 turtles represent 86% of all migration tag–recaptures from the Howick Group. Conclusions We postulate that recent increases in nesting populations within the Solomon Islands may be due to the high level of protection afforded to foraging turtles within the Great Barrier Reef. Implications An understanding of the connectivity between specific feeding areas and nesting populations is necessary to determine threats to animals over their entire life history and, therefore, allow the development of sound conservation management actions.

Several derivatives of the pseudotetrahedral phenylthiolate complex Tp(Me,Me)Ni-SPh (1), Tp(Me,Me-) = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, were prepared incorporating substituted arylthiolates, including a series of ortho-substituted ligands Tp(Me,Me)Ni-SR (R = 2,6-Me(2)C(6)H(3), 2; 2,4,6-Me(3)C(6)H(2), 3; 2,4,6- (i)Pr(3)C(6)H(2), 4; and 2,6-Ph(2)C(6)H(3), 5) and a series of para-substituted complexes (R = C(6)H(4)-4-OMe, 6; C(6)H(4)-4-Me, 7; and C(6)H(4)-4-Cl, 8). The products were characterized by (1)H NMR and UV-vis spectroscopy. Spectra of 6-8 were consistent with retention of a common structure across the para-substituted series with modest perturbation of the spectral features of 1 assisting their assignment. In contrast, spectra of 2-5 were indicative of a significant change in configuration across the ortho-disubstituted series. The structure of complex 5 was determined by X-ray crystallography and a distinctive arylthiolate ligation mode was found, in which the N(3)S ligand field was significantly distorted toward a sawhorse, compared to a more common trigonal pyramidal shape (e.g., 1). Moreover, the arylthiolate substituent rotated from a vertical orientation co-directional with the pyrazole rings and disposed between two of them in 1, to a horizontal orientation perpendicular to and over a single pyrazole ring in 5. This reorientation is necessary to accommodate the large ortho substituents of the latter complex. The divergent Ni-S coordination modes result in distinct (1)H NMR and electronic spectra that were rationalized by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. These results demonstrate rich coordination chemistry for arylthiolates that can be elicited by steric manipulation at the periphery of pseudotetrahedral ligand fields.

Ligation of nickel(II) by Trofimenko’s hydrotris(3,5-dimethyl-1-pyrazolyl)borate anion (Tp Me,Me ) and zwitterionic organoxanthate or dithiocarbamate co-ligands affords neutral high-spin pentacoordinate complexes with formally trianionic N 3 S 2 ligand fields, similar to that of the nickel-dependent superoxide dismutase active site. Given this analogy to NiSOD, the structure, dynamics, and redox properties of the product complexes were examined. X-ray structures revealed rotation of the dithioacid chelates against the scorpionate face, giving coordination geometries between square pyramidal and trigonal bipyramidal limits. The complexes accordingly adopt paramagnetic ( S = 1) d 8 electron configurations, but magnetic susceptibilities suggest partial isomerization to a diamagnetic state in solution. The complexes also exhibit quasi-reversible one-electron redox couples at potentials suitable for SOD activity.

This article evaluates the usefulness of `authenticity' for a theological analysis of selfhood. In his Ethics of Authenticity , Charles Taylor makes a case for the retrieval of authenticity which seems to invite a theological account of the self, one he stops short of offering. Taylor's argument is expounded, and a preliminary critique is offered. The theological possibility invited by Taylor is then examined by means of a reading of John 4:1—34. With John we conclude that while authenticity may begin and frame such a discussion, knowledge of the truth of the self is given by divine revelation.

Five new pseudotetrahedral nickel(II) arylthiolate complexes Tp (R,Me)Ni-SR' [(Tp (R,Me)) (-) = 2,2,2-kappa (3)-hydridotris(3-R,5-methylpyrazolyl)borate; R = Me, R' = C 6H 5 (Ph), 2,4,6-C 6H 2(CH 3) 3 (Mes); R = Ph, R' = C 6H 5 (Ph), 2,4,6-C 6H 2(CH 3) 3 (Mes), and 2,6-C 6H 3(CH 3) 2 (Xyl)] were prepared by metathesis reactions of known chloride complexes with sodium arylthiolate salts in THF. The new products were fully characterized. The effect of increasing bulk of substituents at the proximal 3-pyrazolyl and ortho-thiolate positions represented in this series was evident in spectroscopic studies (UV-vis-NIR, (1)H NMR) of the product complexes. Increased steric contact induced red-shifting of nickel-thiolate ligand to metal charge transfer (LMCT) bands and enhanced contact shifts of arylthiolate protons with the paramagnetic ( S = 1) nickel(II) ion. These spectroscopic effects arise from structural distortion of the nickel(II)-thiolate bond revealed by X-ray crystal structure determinations of the structural extremes of the series, Tp (Me,Me)Ni-SPh and Tp (Ph,Me)Ni-SXyl. The distortion consists of a significantly increased tilting of the Ni-S bond from an ideal trigonal axis and increased linearity of the Ni-S-R angle that alters covalency of the Ni-S coordinate bond. Reactivity of the nickel-thiolate linkage toward electrophilic alkylation with MeI is also significantly affected, showing enhanced rates according to two distinct competing mechanisms, direct bimolecular alkylation of intact complex and rate-limiting unimolecular dissociation of free thiolate. Possible biochemical relevance of these observations to tetrahedral nickel(II) centers in metalloenzymes is considered.

Low-spin mononuclear (alkylperoxo)iron(III) complexes decompose by peroxide O-O bond homolysis to form iron(IV) species. We examined the kinetics of previously reported homolysis reactions for (alkylperoxo)iron(III) intermediates supported by TPA (tris(2-pyridylmethyl)amine) in CH3CN solution and promoted by pyridine N-oxide, and by BPMCN (N,N-bis(2-pyridylmethyl)-N,N-dimethyl-trans-1,2-diaminocyclohexane) in its cis-beta configuration in CH3CN and CH2Cl2, as well as for the previously unreported chemistry of TPA and 5-Me3TPA intermediates in acetone. Each of these reactions forms an oxoiron(IV) complex, except for the beta-BPMCN reaction in CH2Cl2 that yields a novel (hydroxo)(alkylperoxo)iron(IV) product. Temperature-dependent rate measurements suggest a common reaction trajectory for each of these reactions and verify previous theoretical estimates of a ca. 60 kJ/mol enthalpic barrier to homolysis. However, both the tetradentate supporting ligand and exogenous ligands in the sixth octahedral coordination site significantly perturb the homolyses, such that observed rates can vary over 2 orders of magnitude at a given temperature. This is manifested as a compensation effect in which increasing activation enthalpy is offset by increasingly favorable activation entropy. Moreover, the applied kinetic model is consistent with geometric isomerism in the low-spin (alkylperoxo)iron(III) intermediates, wherein the alkylperoxo ligand is coordinated in either of the inequivalent cis sites afforded by the nonheme ligands.

The prevention and relief of suffering has long been a core medical concern. But while this is a laudable goal, some question whether medicine can, or should, aim for a world without pain, sadness, anxiety, despair or uncertainty. To explore these issues, we invited experts from six of the world’s major faith traditions to address the following question. Is there value in suffering? And is something lost in the prevention and/or relief of suffering? While each of the perspectives provided maintains that suffering should be alleviated and that medicine’s proper role is to prevent and relieve suffering by ethical means, it is also apparent that questions regarding the meaning and value of suffering are beyond the realm of medicine. These perspectives suggest that medicine and bioethics have much to gain from respectful consideration of religious discourse surrounding suffering.