Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II) : Arresting kinetics, autocatalysis, and mechanisms

The ICIQ Foundation and The Spanish Government (Grant CTQ2011-25418 and the Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319) are thankfully acknowledged for support of this work. F.M.M. is grateful to the Government of Spain (MICINN) for the FPI Ph.D. Scholarship (BES-2012-054922). S.A.M. and D.M. thank the EPSRC for support through award EP/J010677/1.[(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph[BOND]X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph[BOND]I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph[BOND]I oxidative addition.Publisher PDFPeer reviewe

Analycity and smoothing effect for the coupled system of equations of Korteweg - de Vries type with a single point singularity

We study that a solution of the initial value problem associated for the coupled system of equations of Korteweg - de Vries type which appears as a model to describe the strong interaction of weakly nonlinear long waves, has analyticity in time and smoothing effect up to real analyticity if the initial data only has a single point singularity at $x=0.

Silver-Catalyzed C-C Bond Formation between Methane and Ethyl Diazoacetate in Supercritical CO2

Even in the context of hydrocarbons’ general resistance to selective functionalization, methane’s volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH4) with ethyl diazoacetate (N2CHCO2Et) to yield ethyl propionate (CH3CH2CO2Et). The use of supercritical carbon dioxide (scCO2) as the solvent is key to the reaction’s success. Although the catalyst is only sparingly soluble in CH4/CO2 mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.Ministerio de Ciencia e Innovación (grants CTQ2008-00042-BQU, CTQ2007-65251-BQU, and CTQ2007-30762-E), the European Research Area Chemistry Programme (2nd call “Chemical activation of carbon dioxide and methane” contract no. 1736154), the Consolider Ingenio 2010 (grants CSD2006-003 and CSD2007-00006), the Institut de Chimie of the CNRS, the Junta de Andalucía (P07-FQM-2870), and the Generalitat Velenciana (ACOMP/2010/155).We dedicate this work to Professor Ernesto Carmona. Support for this work was provided by the Ministerio de Ciencia e Innovacion (grants CTQ2008-00042-BQU, CTQ2007-65251-BQU, and CTQ2007-30762-E), the European Research Area Chemistry Programme (2nd call "Chemical activation of carbon dioxide and methane" contract no. 1736154), the Consolider Ingenio 2010 (grants CSD2006-003 and CSD2007-00006), the Institut de Chimie of the CNRS, the Junta de Andalucia (P07-FQM-2870), and the Generalitat Velenciana (ACOMP/2010/155). We thank the Servicio Central de Soporte a la Investigacion Experimental (Universidad de Valencia) for access to the instrumental facilities and J. de la Rosa and A. Sanchez de la Campa (Universidad de Huelva) for ICP-MS analyses

Desenvolvimento de um roteiro conceitual para a gestão da biodiversidade e dos serviços ecossistêmicos no Caribe mexicano

Coral reefs and mangroves support rich biodiversity and provide ecosystem services that range from food, recreational benefits and coastal protection services, among others. They are one of the most threatened ecosystems by urbanization processes. In this context, we developed a conceptual framework for the management of biodiversity and ecosystem services for these coastal environments. We based our workflow on two sections: “Information base” and “Governance” and use the Puerto Morelos Coastal region as a case study for coastal protection. Puerto Morelos is between two of the most touristic destinations of Mexico (Playa del Carmen and Cancun) that has experienced an increase of population in the past four decades resulting in an intensification of multiple threats to its ecosystems. We characterized the two ecosystems with a “Management Units” strategy. An expert-based ecosystem services matrix was also described in order to connect mangroves and coral reef ecosystems with the multiple beneficiaries. Then an ecosystem model (conceptual model and Global Biodiversity model) was developed. The conceptual model was useful in understanding the interplay processes between systems regarding the ecosystem service of “Coastal Protection”. The Global Biodiversity model evidenced the human-induced shifts in the biodiversity for mangrove and coral reefs ecosystems. Also, a projection for 2035 of “best” and “worst” scenarios was applied using GLOBIO3. A DPSIR conceptual framework was used to analyze environmental problems regarding ecosystem services maintenance. Finally, we evaluated a set of policies associated with these ecosystems that favor coastal protection integrity. This framework facilitates the identification of the most relevant processes and controls about the provision of coastal protection service. It can also be useful to better target management actions and as a tool to identify future management needs to tackle the challenges preventing more effective conservation of coastal environments.Recifes de coral e manguezais possuem rica biodiversidade e fornecem serviços ecossistêmicos, tais como, alimento, recreação, proteção costeira, entre outros. Esses ecossistemas encontram-se entre os mais ameaçados pelos processos de urbanização. Nesse contexto, desenvolvemos um roteiro conceitual para a gestão da biodiversidade e dos serviços ecossistêmicos desses ambientes costeiros. Organizamos nossa sequência de passos de trabalho em duas seções: “Base de informações” e “Governança” e usamos a região costeira da cidade de Puerto Morelos (México) como um estudo de caso para analisar o serviço de proteção de costa. Puerto Morelos encontra-se entre dois dos destinos mais turísticos do México (Playa del Carmen e Cancún), e portanto sua população vem aumentando nas últimas quatro décadas, resultando na intensificação de múltiplas ameaças para os ecossistemas. Primeiramente, caracterizamos os dois ecossistemas identificando-os como “Unidades de Gestão”, detalhando seus principais componentes e processos. Através de uma “Matriz de serviços ecossistêmicos”, construída com base na opinião de especialistas, foram sistematizados os principais serviços ecossistêmicos prestados pelos manguezais e recifes de corais aos múltiplos beneficiários. Em seguida, foi desenvolvida uma modelagem do sistema (e ecossistemas) através de sua representação na forma de um modelo conceitual e um modelo numérico de Biodiversidade Global. O modelo conceitual facilitou a compreensão dos processos de interação entre sistemas em relação ao serviço “Proteção Costeira”. O modelo numérico evidenciou as mudanças induzidas pelo homem na biodiversidade dos ecossistemas de manguezal e recifes de coral. Além disso, uma projeção dos cenários “melhor” e “pior” foi desenvolvida para 2035 usando GLOBIO3. A Estrutura conceitual DPSIR foi aplicada para analisar problemas ambientais relacionados à manutenção dos serviços ecossistêmicos. Finalmente, avaliamos um conjunto de políticas públicas associadas a esses ecossistemas e que favorecem a integridade da proteção costeira. Portanto, o roteiro facilitou a identificação dos principais processos e controles para a provisão de um serviço ecossistêmico. Além disso, pode ser útil para direcionar melhor as ações de gerenciamento, bem como, uma ferramenta para identificar necessidades futuras de planejamento e gestão para enfrentar desafios que permitam uma conservação mais eficaz dos ambientes costeiros.Fil: Sánchez Quinto, Andrés. Universidad Nacional Autónoma de México; MéxicoFil: Costa, Julliet Correa da. Universidade Federal de Santa Catarina; BrasilFil: Zamboni, Nadia Selene. Universidade Federal do Rio Grande do Norte; BrasilFil: Sanches, Fábio H. C.. Universidade Federal de Sao Paulo; BrasilFil: Principe, Silas C.. Universidade de Sao Paulo; BrasilFil: Viotto, Evangelina del Valle. Provincia de Entre Ríos. Centro de Investigaciones Científicas y Transferencia de Tecnología a la Producción. Universidad Autónoma de Entre Ríos. Centro de Investigaciones Científicas y Transferencia de Tecnología a la Producción. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Centro de Investigaciones Científicas y Transferencia de Tecnología a la Producción; ArgentinaFil: Casagranda, Maria Elvira. Universidad Nacional de Tucumán. Instituto de Ecología Regional. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Ecología Regional; ArgentinaFil: Lima, Francisco A. da Veiga. Universidade Federal de Santa Catarina; BrasilFil: Possamai, Bianca. Universidade Federal Do Rio Grande.; BrasilFil: Faroni Perez, Larisse. Universidade Federal de Juiz de Fora; Brasi

AVONET: morphological, ecological and geographical data for all birds

Functional traits offer a rich quantitative framework for developing and testing theories in evolutionary biology, ecology and ecosystem science. However, the potential of functional traits to drive theoretical advances and refine models of global change can only be fully realised when species‐level information is complete. Here we present the AVONET dataset containing comprehensive functional trait data for all birds, including six ecological variables, 11 continuous morphological traits, and information on range size and location. Raw morphological measurements are presented from 90,020 individuals of 11,009 extant bird species sampled from 181 countries. These data are also summarised as species averages in three taxonomic formats, allowing integration with a global phylogeny, geographical range maps, IUCN Red List data and the eBird citizen science database. The AVONET dataset provides the most detailed picture of continuous trait variation for any major radiation of organisms, offering a global template for testing hypotheses and exploring the evolutionary origins, structure and functioning of biodiversity

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Hybrid Solid Polymer Electrolytes Based on Epoxy Resins, Ionic Liquid, and Ceramic Nanoparticles for Structural Applications

Solid polymer electrolytes (SPE) and composite polymer electrolytes (CPE) serve as crucial components in all-solid-state energy storage devices. Structural batteries and supercapacitors present a promising alternative for electric vehicles, integrating structural functionality with energy storage capability. However, despite their potential, these applications are hampered by various challenges, particularly in the realm of developing new solid polymer electrolytes that require more investigation. In this study, novel solid polymer electrolytes and composite polymer electrolytes were synthesized using epoxy resin blends, ionic liquid, lithium salt, and alumina nanoparticles and subsequently characterized. Among the formulations tested, the optimal system, designated as L70P30ILE40Li1MAl2 and containing 40 wt.% of ionic liquid and 5.7 wt.% of lithium salt, exhibited exceptional mechanical properties. It displayed a remarkable storage modulus of 1.2 GPa and reached ionic conductivities of 0.085 mS/cm at 60 °C. Furthermore, a proof-of-concept supercapacitor was fabricated, demonstrating the practical application of the developed electrolyte system

Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II):Arresting kinetics, autocatalysis, and mechanisms

[(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph[BOND]X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph[BOND]I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph[BOND]I oxidative addition

New Co and Mn Catalysts Bearing ONO Ligands Containing Nucleophile for the Coupling of CO2 and Propylene Oxide

A series of novel ONO ligands bearing an ionic pendant-armed (hereinafter indicated as ONONu, where Nu corresponds to an anionic nucleophile) were synthesized, characterized, and successfully coordinated to cobalt and manganese precursors. New air-stable cobalt (III) complexes (1–6) and manganese (II) complexes (7 and 8) were obtained and characterized. Single crystal X-ray diffraction analysis of the Co(III) compound 5 confirmed the presence of two quaternized ligands coordinated to the metal and iodide as counterion. These novel complexes were revealed to be active catalysts in the coupling reaction of carbon dioxide and propylene oxide (PO) in different degrees of success. Among these, the manganese complex 8 afforded the best results towards the formation of propylene carbonate (PC) with a productivity of 256 kg PC/(kg cat·h), achieving a TON of 4860