Photoexcitation of Fe3 O Nodes in MOF Drives Water Oxidation at pH=1 When Ru Catalyst Is Present.

Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco-friendly solar fuels. However, systems with light-driven water oxidation reaction (WOR) at pH=1 are rare. Broadly used [Ru(bpy)3 ]2+ (bpy=2,2'-bipyridine) photosensitizer has a fixed +1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe2 O3 , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe-based metal-organic framework (MOF) water oxidation photoelectrocatalysts active at pH=1 are presented. Fe-MIL-126 and Fe MOF-dcbpy structures were formed with 4,4'-biphenyl dicarboxylate (bpdc), 2,2'-bipyridine-5,5'-dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metal-based catalysts via coordination to 2,2'-bipyridine fragments. Fe-based MOFs were doped with Ru-based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H2 O)2 ]2+ WOC. Materials were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra-red (FTIR) spectroscopy, resonance Raman, X-ray absorption spectroscopy, fs optical pump-probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, FeIII and RuIII oxidation states are present, indicating rate-limiting electron transfer in MOF. Fe3 O nodes emerge as photosensitizers able to drive prolonged O2 evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru-WOC modification for faster WOC catalysis, or Ru-WOC substitution to 3d metal-based systems. The findings give further insight for development of light-driven water splitting systems based on Earth-abundant metals.

Extinction risk of the endemic vascular flora of Kauai, Hawaii, based on IUCN assessments.

The International Union for Conservation of Nature's Red List of Threatened Species (IUCN Red List) is the world's most comprehensive information source on the global conservation status of species. Governmental agencies and conservation organizations increasingly rely on IUCN Red List assessments to develop conservation policies and priorities. Funding agencies use the assessments as evaluation criteria, and researchers use meta-analysis of red-list data to address fundamental and applied conservation science questions. However, the circa 143,000 IUCN assessments represent a fraction of the world's biodiversity and are biased in regional and organismal coverage. These biases may affect conservation priorities, funding, and uses of these data to understand global patterns. Isolated oceanic islands are characterized by high endemicity, but the unique biodiversity of many islands is experiencing high extinction rates. The archipelago of Hawaii has one of the highest levels of endemism of any floristic region; 90% of its 1367 native vascular plant taxa are classified as endemic. We used the IUCN's assessment of the complete single-island endemic (SIE) vascular plant flora of Kauai, Hawaii, to assess the proportion and drivers of decline of threatened plants in an oceanic island setting. We compared the IUCN assessments with federal, state, and other local assessments of Kauai species or taxa of conservation concern. Finally, we conducted a preliminary assessment for all 1044 native vascular plants of Hawaii based on IUCN criterion B by estimating area of occupancy, extent of occurrence, and number of locations to determine whether the pattern found for the SIE vascular flora of Kauai is comparable to the native vascular flora of the Hawaiian Islands. We compared our results with patterns observed for assessments of other floras. According to IUCN, 256 SIE vascular plant taxa are threatened with extinction and 5% are already extinct. This is the highest extinction risk reported for any flora to date. The preliminary assessment of the native vascular flora of Hawaii showed that 72% (753 taxa) is threatened. The flora of Hawaii may be one of the world's most threatened; thus, increased and novel conservation measures in the state and on other remote oceanic islands are urgently needed.

La Lista Roja de la Unión Internacional para la Conservación de la Naturaleza (Lista Roja UICN) es la fuente más completa a nivel mundial de información sobre el estado de conservación de las especies. Las agencias gubernamentales y las organizaciones para la conservación dependen cada vez más de las valoraciones en esta lista para desarrollar sus políticas y prioridades de conservación; también los organismos de financiamiento usan las valoraciones como criterios de evaluación y los investigadores aplican metaanálisis a los datos de la lista para abordar preguntas fundamentales y aplicadas a las ciencias de la conservación. Sin embargo, las casi 143,000 valoraciones de la UICN representan sólo una fracción de la biodiversidad mundial y están sesgadas en cuanto a la cobertura regional y de organismos. Estos sesgos pueden afectar a las prioridades de conservación, al financiamiento y al uso de estos datos para entender los patrones globales. Las islas oceánicas aisladas se caracterizan por un alto endemismo, aunque la biodiversidad única de muchas de estas islas está experimentando un índice elevado de extinciones. El archipiélago de Hawái tiene uno de los niveles más altos de endemismo de cualquier región florística con el 90% de los 1,367 taxones nativos de flora vascular clasificado como endémico. Usamos las valoraciones de la UICN para todas las plantas vasculares endémicas de una sola isla (ESI) en Kauai, Hawái, para evaluar la proporción y los impulsores de la declinación de plantas amenazadas en el entorno de una isla oceánica. Comparamos las valoraciones de la UICN con las federales, estatales y otras valoraciones locales de las especies o taxones de Kauai que son de importancia para la conservación. Por último, realizamos una valoración preliminar para las 1,044 especies de plantas vasculares nativas de Hawái con base en el criterio B de la UICN mediante la estimación del área de ocupación, la extensión de la ocurrencia y el número de localidades para determinar si el patrón hallado para la flora vascular ESI de Kauai es comparable con la flora vascular nativa de las islas hawaianas. Comparamos nuestros resultados con los patrones observados en las valoraciones de otras floras. De acuerdo con la UICN, el 95% de los taxones de plantas vasculares ESI de Kauai están amenazadas y el 5% ya se encuentra extinto. A la fecha, este es el riesgo de extinción más alto reportado para cualquier flora. La valoración preliminar de la flora vascular nativa de Hawái mostró que el 72% (753 taxones) se encuentra amenazado. La flora de Hawái puede ser una de las más amenazadas a nivel mundial; por lo tanto, se necesitan urgentemente medidas novedosas e incrementadas en el estado y en otras islas oceánicas remotas.

Spontaneous Splenic Rupture in Atypical Pneumonia From Mycoplasma Infection.

Splenic rupture is a potentially life-threatening condition, often associated with chest or abdominal trauma. Atraumatic splenic rupture (ASR) is quite rare. When reported, it is usually attributed to underlying pathological conditions such as malignant neoplastic disorders, viral infections, or inflammatory processes. Here, we report a case of ASR in a patient that was attributed to Mycoplasma pneumoniae infection. This was supported by the diagnosis of atypical pneumonia secondary to M. pneumoniae, presence of multiple pseudoaneurysms in the spleen, and presence of cold agglutinins indicating an inflammatory state likely due to systemic vasculitis. Additionally, the lack of recent trauma further corroborated the mycoplasma infection as the driving force behind the splenic rupture.

Biotic and anthropogenic forces rival climatic/abiotic factors in determining global plant population growth and fitness.

Multiple, simultaneous environmental changes, in climatic/abiotic factors, interacting species, and direct human influences, are impacting natural populations and thus biodiversity, ecosystem services, and evolutionary trajectories. Determining whether the magnitudes of the population impacts of abiotic, biotic, and anthropogenic drivers differ, accounting for their direct effects and effects mediated through other drivers, would allow us to better predict population fates and design mitigation strategies. We compiled 644 paired values of the population growth rate (λ) from high and low levels of an identified driver from demographic studies of terrestrial plants. Among abiotic drivers, natural disturbance (not climate), and among biotic drivers, interactions with neighboring plants had the strongest effects on λ However, when drivers were combined into the 3 main types, their average effects on λ did not differ. For the subset of studies that measured both the average and variability of the driver, λ was marginally more sensitive to 1 SD of change in abiotic drivers relative to biotic drivers, but sensitivity to biotic drivers was still substantial. Similar impact magnitudes for abiotic/biotic/anthropogenic drivers hold for plants of different growth forms, for different latitudinal zones, and for biomes characterized by harsher or milder abiotic conditions, suggesting that all 3 drivers have equivalent impacts across a variety of contexts. Thus, the best available information about the integrated effects of drivers on all demographic rates provides no justification for ignoring drivers of any of these 3 types when projecting ecological and evolutionary responses of populations and of biodiversity to environmental changes.

An enigmatic Hawaiian moth is a missing link in the adaptive radiation of Schiedea.

Shifts in pollination may drive adaptive diversification of reproductive systems within plant lineages. The monophyletic genus Schiedea is a Hawaiian lineage of 32 extant species, with spectacular diversity in reproductive systems. Biotic pollination is the presumed ancestral condition, but this key element of the life history and its role in shaping reproductive systems has remained undocumented. We observed floral visitors to two species of Schiedea and conducted field experiments to test pollinator effectiveness. We used choice tests to compare attraction of pollinators to species hypothesized to be biotically vs wind-pollinated. Pseudoschrankia brevipalpis (Erebidae), a recently described moth species known only from O'ahu, visited hermaphroditic Schiedea kaalae and S. hookeri and removed nectar from their unique tubular nectary extensions. Pseudoschrankia brevipalpis effectively pollinates S. kaalae; single visits to emasculated flowers resulted in pollen transfer. In choice tests, P. brevipalpis strongly preferred these hermaphroditic species over two subdioecious species capable of wind pollination. A shift from biotic to abiotic pollination is clearly implicated in the diversification of reproductive systems within Schiedea. Abundant pollination by a previously unknown native moth in experimental and restored populations suggests the potential for restoration to re-establish native plant-pollinator interactions critical for production of outcrossed individuals with high fitness.