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Abstract: Manganese(II) complexes [Mn(L)X2] were prepared and characterized, where L is a neutral di-Schiff base ligand incorporating pyridylimine donor arms, including (1R,2R)-N,N′-bis(2-pyridylmethylidene)-1,2-diphenylethylenediimine (L1), (1R,2R)-N,N′-bis(6-methyl-2-pyridylmethylidene)-1,2-cyclohexyldiimine (L2), or (1R,2R)-, (1S,2S)- or racemic N,N′-bis(2-pyridylmethylidene)-1,2-cyclohexyldiimine (L3), and X− = or Cl−. Product complexes were structurally characterized, specifically including [Mn(R,R-L1)(NCCH3)3](ClO4)2, [Mn(R,R-L2)(OH2)2](ClO4)2 and racemic [Mn(L3)Cl2]. The first of these complexes features a heptacoordinate ligand field in a distorted pentagonal bipyramid, and the latter two are hexacoordinate, but retain equatorially monovacant pentagonal bipyramidal structures. Complexes [Mn(L3)X2] (X− =Cl−, ) were reacted with the primary phosphine FcCH2PH2 (Fc=–C5H4FeC5H5), H2O and ethyldiazoacetate (EDA). The first two substrates prompted reactivity at a single ligand imine bond, resulting in hydrophosphination and hydrolysis, respectively. Complexes of the derivative ligands were also structurally characterized. Evidence for EDA activation was obtained by electrospray ionization mass spectrometry, but catalytic carbene transfer was not obtained. [ABSTRACT FROM AUTHOR]

Abstract: Ligation of nickel(II) by Trofimenko’s hydrotris(3,5-dimethyl-1-pyrazolyl)borate anion (TpMe,Me) and zwitterionic organoxanthate or dithiocarbamate co-ligands affords neutral high-spin pentacoordinate complexes with formally trianionic N3S2 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) d8 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. [Copyright &y& Elsevier]

The solvated iron(II) salt [Fe(NCMe) 6 ](BF 4 ) 2 (Me = methyl) is shown to be a bifunctional catalyst with respect to aziridination of styrene. The salt serves as an active catalyst for nitrene transfer from PhINTs to styrene to form 2-phenyl-N-tosylaziridine (Ph = phenyl; Ts = tosyl, -S{O} 2 -p-C 6 H 4 Me). The iron(II) salt also acts as a Lewis acid in non-coordinating CH 2 Cl 2 solution, to catalyze heterolytic CN bond cleavage of the aziridine and insertion of dipolarophiles. The 1,3-zwitterionic intermediate is presumably supported by interaction of the metal dication with the anion, and by resonance stabilization of the carbocation. Nucleophilic dipolarophiles then insert to give a five-membered heterocyclic ring. The result is a two-step cycloaddition, formally [2 + 1 + 2], that is typically regiospecific, but not stereospecific. This reaction mechanism was confirmed by conducting a series of one-step, [3 + 2] additions of unsaturated molecules into pre-formed 2-phenyl-N-tosylaziridine, also catalyzed by [Fe(NCMe) 6 ](BF 4 ) 2 . Relevant substrates include styrenes, carbonyl compounds and alkynes. These yield five-membered heterocylic rings, including pyrrolidines, oxazolidines and dihydropyrroles, respectively. The reaction scope appears limited only by the barrier to formation of the dipolar intermediate, and by the nucleophilicity of the captured dipolarophile. The bifunctionality of an inexpensive, earth-abundant and non-toxic catalyst suggests a general strategy for one-pot construction of heterocyclic rings, as demonstrated specifically for pyrrolidine ring formation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Globally distributed marine taxa are well suited for investigations of biogeographic impacts on genetic diversity, connectivity, and population demography. The sea turtle genus Lepidochelys includes the wide-ranging and abundant olive ridley ( L. olivacea ), and the geographically restricted and 'Critically Endangered' Kemp's ridley ( L. kempii ). To investigate their historical biogeography, we analyzed a large dataset of mitochondrial DNA (mtDNA) sequences from olive (n = 943) and Kemp's (n = 287) ridleys, and genotyped 15 nuclear microsatellite loci in a global sample of olive ridleys (n  =  285). We found that the ridley species split ~ 7.5 million years ago, before the Panama Isthmus closure. The most ancient mitochondrial olive ridley lineage, located in the Indian Ocean, was dated to ~ 2.2 Mya. Both mitochondrial and nuclear markers revealed significant structure for olive ridleys between Atlantic (ATL), East Pacific (EP), and Indo-West Pacific (IWP) areas. However, the divergence of mtDNA clades was very recent (< 1 Mya) with low within- clade diversity, supporting a recurrent extinction-recolonization model for these ocean regions. All data showed that ATL and IWP groups were more closely related than those in the EP, with mtDNA data supporting recent recolonization of the ATL from the IWP. Individual olive ridley dispersal between the ATL, EP, and IN/IWP could be interpreted as more male- than female-biased, and genetic diversity was lowest in the Atlantic Ocean. All populations showed signs of recent expansion, and estimated time frames were concordant with their recent colonization history. Investigating species abundance and distribution changes over time is central to evolutionary biology, and this study provides a historical biogeographic context for marine vertebrate conservation and management., Supplementary Information: The online version contains supplementary material available at 10.1007/s10592-022-01465-3., Competing Interests: Competing interestsWe have no conflicts of interest to disclose., (© The Author(s) 2022, corrected publication 2022.)

Marine low clouds play an important role in the climate system, and their properties are sensitive to cloud condensation nuclei concentrations. While new particle formation represents a major source of cloud condensation nuclei globally, the prevailing view is that new particle formation rarely occurs in remote marine boundary layer over open oceans. Here we present evidence of the regular and frequent occurrence of new particle formation in the upper part of remote marine boundary layer following cold front passages. The new particle formation is facilitated by a combination of efficient removal of existing particles by precipitation, cold air temperatures, vertical transport of reactive gases from the ocean surface, and high actinic fluxes in a broken cloud field. The newly formed particles subsequently grow and contribute substantially to cloud condensation nuclei in the remote marine boundary layer and thereby impact marine low clouds.

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., (© 2019 John Wiley & Sons Ltd.)

Reaction of the complex [(Tp Ph,Me )Fe II (NCMe) 3 ]BF 4 , where Tp Ph,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 TsNH 2 (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 transfer. Because the former is independent of substrate, ratios for various substrates are directly comparable, and this approach enables acquisition of data for a single substrate under nearly stoichiometric, as opposed to competitive catalytic, conditions. Hammett analyses of such data are consistent with an electrophilic intermediate consistent with known or suspected imidoiron(IV) complexes. Because this intermediate was not observed directly, plausible geometric and electronic structures were modeled and assessed using density functional theory.

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., (Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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., Competing Interests: We declare we have no competing interests.

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.

Despite the long debate of whether or not multiple mating benefits the offspring, studies still show contradictory results. Multiple mating takes time and energy. Thus, if females fertilize their eggs with a single mating, why to mate more than once? We investigated and inferred paternal identity and number of sires in 12 clutches (240 hatchlings) of green turtles (Chelonia mydas) nests at Tortuguero, Costa Rica. Paternal alleles were inferred through comparison of maternal and hatchling genotypes, and indicated multiple paternity in at least 11 of the clutches (92%). The inferred average number of fathers was three (ranging from 1 to 5). Moreover, regression analyses were used to investigate for correlation of inferred clutch paternity with morphological traits of hatchlings fitness (emergence success, length, weight and crawling speed), the size of the mother, and an environmental variable (incubation temperature). We suggest and propose two different comparative approaches for evaluating morphological traits and clutch paternity, in order to infer greater offspring survival. First, clutches coded by the exact number of fathers and second by the exact paternal contribution (fathers who gives greater proportion of the offspring per nest). We found significant differences (P < 0.05) in clutches coded by the exact number of fathers for all morphological traits. A general tendency of higher values in offspring sired by two to three fathers was observed for the length and weight traits. However, emergence success and crawling speed showed different trends which unable us to reach any further conclusion. The second approach analysing the paternal contribution showed no significant difference (P > 0.05) for any of the traits. We conclude that multiple paternity does not provide any extra benefit in the morphological fitness traits or the survival of the offspring, when analysed following the proposed comparative statistical methods.

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.