Photo-generation of H2 by Heterometallic Complexes

Multiple and different metals in a complex can accomplish single and sequential multi-step reactions, providing valuable procedures to obtain chemicals in one-pot synthetic routes. Biology has shown how cooperative catalysis is a powerful method for the synthesis of complicated molecules. One of the most attractive targets for current chemists is the synthesis of H2 by a simple and economical procedure, mainly if it is produced from water using visible light as the energy source. This review aims to show how heterometallic complexes have been recently used to catalyze the photochemical production of H2

Monitoring spin-crossover phenomena via Re(I) luminescence in hybrid Fe(II) silica coated nanoparticles

Financial support from Projects CTQ2014-56312-P and PGC2018-102052-B-C21 financed by MCIN/AEI/10.13039/501100011033/FEDER "Una manera de hacer Europa", the Junta de Andalucia (FQM-195), Feder project A-FQM-172UGR18 and the University of Granada is gratefully acknowledged. I.-F. Diaz-Ortega and J.-R Jimenez are also thankful to the Junta de Andalucia for Postdoctoral research fellowships.Bare (1) and silica coated (1@SiO2) spin crossover (SCO) nanoparticles based on the polymer {[Fe (NH2Trz)3](BF4)2}n have been prepared following a water-in-oil synthetic procedure. For 1, the critical temperatures of the spin transition are TC↓ = 214.6 K and TC↑ = 220.9 K. For 1@SiO2, the abruptness of the transition is enhanced and the critical temperatures are centred at room temperature (TC↓ = 292.1 K and TC↑ = 296.3 K). An inert Re(I) complex of formula [Re(phen)(CO)3(PETES)](PF6) (phen = 1, 10-phenanthroline; PETES = 2(4-pyridylethyl)triethoxysilane) (Re) was also synthesized yielding intense green emission centred at λem = 560 nm. The grafting of this complex on the silica shell of 1@SiO2 led to a bifunctional SCO-luminescence composite (1@SiO2/Re) whose luminescence properties were tuned by the spin state switching. Temperature-variable photophysical studies showed that luminescence and spin transition were synchronized through a radiative (trivial) energy transfer mechanism between the Re(I) and the Fe(II)-LS (LS, Low Spin) centres.FEDER "Una manera de hacer Europa" CTQ2014-56312-P PGC2018-102052-B-C21Junta de Andalucia FQM-195European Commission A-FQM-172UGR18University of GranadaJunta de Andaluci

Evolving trends in the management of acute appendicitis during COVID-19 waves. The ACIE appy II study

Background: In 2020, ACIE Appy study showed that COVID-19 pandemic heavily affected the management of patients with acute appendicitis (AA) worldwide, with an increased rate of non-operative management (NOM) strategies and a trend toward open surgery due to concern of virus transmission by laparoscopy and controversial recommendations on this issue. The aim of this study was to survey again the same group of surgeons to assess if any difference in management attitudes of AA had occurred in the later stages of the outbreak. Methods: From August 15 to September 30, 2021, an online questionnaire was sent to all 709 participants of the ACIE Appy study. The questionnaire included questions on personal protective equipment (PPE), local policies and screening for SARS-CoV-2 infection, NOM, surgical approach and disease presentations in 2021. The results were compared with the results from the previous study. Results: A total of 476 answers were collected (response rate 67.1%). Screening policies were significatively improved with most patients screened regardless of symptoms (89.5% vs. 37.4%) with PCR and antigenic test as the preferred test (74.1% vs. 26.3%). More patients tested positive before surgery and commercial systems were the preferred ones to filter smoke plumes during laparoscopy. Laparoscopic appendicectomy was the first option in the treatment of AA, with a declined use of NOM. Conclusion: Management of AA has improved in the last waves of pandemic. Increased evidence regarding SARS-COV-2 infection along with a timely healthcare systems response has been translated into tailored attitudes and a better care for patients with AA worldwide

Photography-based taxonomy is inadequate, unnecessary, and potentially harmful for biological sciences

The question whether taxonomic descriptions naming new animal species without type specimen(s) deposited in collections should be accepted for publication by scientific journals and allowed by the Code has already been discussed in Zootaxa (Dubois & Nemésio 2007; Donegan 2008, 2009; Nemésio 2009a–b; Dubois 2009; Gentile & Snell 2009; Minelli 2009; Cianferoni & Bartolozzi 2016; Amorim et al. 2016). This question was again raised in a letter supported by 35 signatories published in the journal Nature (Pape et al. 2016) on 15 September 2016. On 25 September 2016, the following rebuttal (strictly limited to 300 words as per the editorial rules of Nature) was submitted to Nature, which on 18 October 2016 refused to publish it. As we think this problem is a very important one for zoological taxonomy, this text is published here exactly as submitted to Nature, followed by the list of the 493 taxonomists and collection-based researchers who signed it in the short time span from 20 September to 6 October 2016

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

Influencia de los ligandos en imanes monomoleculares de iones lantánidos: Estudio magneto-estructural y teórico

Este trabajo de investigación se enfoca dentro del área del Magnetismo Molecular y la Fotoquímica. Su objetivo principal es el análisis de como el cambio de los tipos de ligando presentes en la esfera de coordinación de iones lantánidos puede modificar las propiedades de MI de diversos complejos derivados de iones lantánidos que van desde aquellos de naturaleza mononuclear hasta aquellos de naturaleza trinuclear. El trabajo realizado se ha enfocado en el diseño racional, preparación, determinación estructural, estudios espectroscópicos, estudio de las propiedades magnéticas y estudios teóricos de tipo ab initio de una serie de complejos derivados de iones lantánidos que pueden clasificarse como: (i) complejos mononucleares homolépticos con ligandos polidentados que solamente contienen átomos donores de tipo N; (ii) complejos heterolépticos mononucleares obtenidos a partir de los complejos anteriores mediante la sustitución de uno de los ligandos N-donores de la esfera de coordinación; (iii) complejos heterolépticos dinucleares con ligandos puente bisbidentados no simétricos que contienen dos entornos de coordinación distintos para cada ión lantánidos; (iv) complejos dinucleares heterolépticos de tipo quiral con ligandos simétricos bisbidentados; (v) complejos heterolépticos trinucleares con topología triangular planar; (vi) complejos sintetizados a partir de dos unidades mononucleares en las que cada ión lantánido posee distintas esferas de coordinación y (vii) complejos mononucleares heterolépticos con simetría axial aproximada. Toda esta investigación básica tiene como objetivo generar nuevo conocimiento para poder diseñar MI con propiedades mejoradas. Actualmente podemos asegurar que esta es una de las áreas con mayor actividad dentro de la Química y Ciencia de los Materiales debido a las potenciales aplicaciones que las MI tienen en campos tan diversos como la espintrónica molecular, almacenamiento magnético de alta densidad y la generación de qubits para mejorar el mundo de la computación a nivel molecular.Tesis Univ. Granada. Programa Oficial de Doctorado en: Químic

Tuning magnetic anisotropy by the π-bonding features of the axial ligands and the electronic effects of gold(I) atoms in 2D {Co(L)2[Au(CN)2]2}n metal–organic frameworks with field-induced single-ion magnet behaviour

The assembly of a Co(II) salt with two [Au(CN)2]− anions and ancillary ligands L afforded 2D complexes of the general formula {Co(L)2[Au(CN)2]2}n (where L = DMSO (1), DMF (2), Py (3) and PyPhCO (4); PyPhCO is benzoylpyridine). The structure of these complexes consists of parallel sheets, which are built from edgesharing slightly distorted square-planar {NC–Au–CN–Co}4 units with the Co(II) ions located at the corners and the [Au(CN)2]− bridging anions at the edges. Co(II) atoms exhibit a slightly tetragonally distorted CoN4X2 coordination sphere (X = O, N), where the L molecules occupy the axial positions. These molecules are oriented in such a way that they penetrate the holes of neighbouring layers, giving rise in the case of 1, 2 and 4 to AB bilayers held together by Au⋯Au aurophilic interactions, whereas in 3, there are no aurophilic interactions between neighbouring layers, so they are not arranged in pairs but equally separated. Dc magnetic properties, HFEPR (high-frequency and -field EPR) and FIRMS (far-infrared magnetic spectroscopy) measurements and ab initio calculations demonstrate that Co(II) ions in compounds 1–4 possess large and positive D values (≳+70 cm−1). The experimental D values follow the same order as that established from ab initio calculations including gold(I) atoms: D (2) > D (4) > D (3) > D (1), which highlights the important role of Au(I) in determining the anisotropy of the Co(II) ions. All the complexes show fieldinduced slow relaxation of magnetization through a predominant Raman mechanism above 3 K. Neither the anisotropy order nor the Co(II)⋯Co(II) distances are clearly correlated with the phenomenological Ueff parameter (or the Raman parameters). This fact suggests that other factors, such as the flexibility of the axial ligands, could significantly contribute to the fast relaxation observed for these complexes.Ministerio de Economía y Competitividad (MINECO) CTQ2014-56312-PMinisterio de Educación, Cultura y Deporte PGC2018-102052-B-C21Junta de Andalucía FQM-195University of GranadaNational Science Foundation (NSF) DMR 1644779State of FloridaA-FQM-172-UGR1

Targeting epidermal growth factor receptor to recruit newly generated neuroblasts in cortical brain injuries

Abstract Background Neurogenesis is stimulated in the subventricular zone (SVZ) of mice with cortical brain injuries. In most of these injuries, newly generated neuroblasts attempt to migrate toward the injury, accumulating within the corpus callosum not reaching the perilesional area. Methods We use a murine model of mechanical cortical brain injury, in which we perform unilateral cortical injuries in the primary motor cortex of adult male mice. We study neurogenesis in the SVZ and perilesional area at 7 and 14 dpi as well as the expression and concentration of the signaling molecule transforming growth factor alpha (TGF-α) and its receptor the epidermal growth factor (EGFR). We use the EGFR inhibitor Afatinib to promote neurogenesis in brain injuries. Results We show that microglial cells that emerge within the injured area and the SVZ in response to the injury express high levels of TGF-α leading to elevated concentrations of TGF-α in the cerebrospinal fluid. Thus, the number of neuroblasts in the SVZ increases in response to the injury, a large number of these neuroblasts remain immature and proliferate expressing the epidermal growth factor receptor (EGFR) and the proliferation marker Ki67. Restraining TGF-α release with a classical protein kinase C inhibitor reduces the number of these proliferative EGFR+ immature neuroblasts in the SVZ. In accordance, the inhibition of the TGF-α receptor, EGFR promotes migration of neuroblasts toward the injury leading to an elevated number of neuroblasts within the perilesional area. Conclusions Our results indicate that in response to an injury, microglial cells activated within the injury and the SVZ release TGF-α, activating the EGFR present in the neuroblasts membrane inducing their proliferation, delaying maturation and negatively regulating migration. The inactivation of this signaling pathway stimulates neuroblast migration toward the injury and enhances the quantity of neuroblasts within the injured area. These results suggest that these proteins may be used as target molecules to regenerate brain injuries

Demographic, clinical, and functional determinants of antithrombotic treatment in patients with nonvalvular atrial fibrillation

Altres ajuts: Alliance Bristol-Myers Squibb/Pfizer.Background: This study assessed the sociodemographic, functional, and clinical determinants of antithrombotic treatment in patients with nonvalvular atrial fibrillation (NVAF) attended in the internal medicine setting. Methods: A multicenter, cross-sectional study was conducted in NVAF patients who attended internal medicine departments for either a routine visit (outpatients) or hospitalization (inpatients). Results: A total of 961 patients were evaluated. Their antithrombotic management included: no treatment (4.7%), vitamin K antagonists (VKAs) (59.6%), direct oral anticoagulants (DOACs) (21.6%), antiplatelets (6.6%), and antiplatelets plus anticoagulants (7.5%). Permanent NVAF and congestive heart failure were associated with preferential use of oral anticoagulation over antiplatelets, while intermediate-to high-mortality risk according to the PROFUND index was associated with a higher likelihood of using antiplatelet therapy instead of oral anticoagulation. Longer disease duration and institutionalization were identified as determinants of VKA use over DOACs. Female gender, higher education, and having suffered a stroke determined a preferential use of DOACs. Conclusions: This real-world study showed that most elderly NVAF patients received oral anticoagulation, mainly VKAs, while DOACs remained underused. Antiplatelets were still offered to a proportion of patients. Longer duration of NVAF and institutionalization were identified as determinants of VKA use over DOACs. A poor prognosis according to the PROFUND index was identified as a factor preventing the use of oral anticoagulation

Anuario del Centro de Estudios Martianos (Vol. 22 1999)

El Anuario del Centro de Estudios Martianos es la publicación insignia de esta institución y heredera directa del Anuario Martiano de la Biblioteca Nacional José Martí, que se publicó entre 1969 y 1977, bajo la dirección del poeta y ensayista Cintio Vitier. Desde que salió a la luz su primera entrega, en 1978, se han publicado treinta y cinco números, en los que aparecen artículos y ensayos de importantes estudiosos de la vida y obra del Apóstol, en Cuba y el resto del mundo. En sus secciones fijas (Otros textos de José Martí, Documentos, Estudios y aproximaciones, Vigencias, Publicaciones, Bibliografía, Constante) y los apartados especiales, los lectores pueden conocer disímiles temas del quehacer martiano internacional, en el año que termina además de mantenerse al tanto de las últimas contribuciones de los promotores e investigadores de la obra martiana en el orbe