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The electrons that nature uses to reduce CO2 during photosynthesis come from water oxidation at the oxygen-evolving complex of photosystem II. Molecular catalysts have served as models to understand its mechanism, in particular the O-O bond-forming reaction, which is still not fully understood. Here we report a Ru(IV) side-on peroxo complex that serves as a 'missing link' for the species that form after the rate-determining O-O bond-forming step. The Ru(IV) side-on peroxo complex (eta(2)-1(IV)-OO) is generated from the isolated Ru(IV) oxo complex (1(IV)=O) in the presence of an excess of oxidant. The oxidation (IV) and spin state (singlet) of eta(2)-1(IV)-OO were determined by a combination of experimental and theoretical studies. O-18- and H-2-labelling studies evidence the direct evolution of O-2 through the nucleophilic attack of a H2O molecule on the highly electrophilic metal-oxo species via the formation of eta(2)-1(IV)-OO. These studies demonstrate water nucleophilic attack as a viable mechanism for O-O bond formation, as previously proposed based on indirect evidence.

The photocatalytic and electrocatalytic conversion of CO

The electrochemical behavior of fac-[Mn(pdbpy)(CO)3 Br] (pdbpy=4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine) (1) in acetonitrile under Ar, and its catalytic performances for CO2 reduction with added water, 2,2,2-trifluoroethanol (TFE), and phenol are discussed in detail. Preparative-scale electrolysis experiments, carried out at -1.5 V versus the standard calomel electrode (SCE) in CO2 -saturated acetonitrile, reveal that the process selectivity is extremely sensitive to the acid strength, producing CO and formate in different faradaic yields. A detailed spectroelectrochemical (IR and UV/Vis) study under Ar and CO2 atmospheres shows that 1 undergoes fast solvolysis; however, dimer formation in acetonitrile is suppressed, resulting in an atypical reduction mechanism in comparison with other reported MnI catalysts. Spectroscopic evidence of Mn hydride formation supports the existence of different electrocatalytic CO2 reduction pathways. Furthermore, a comparative investigation performed on the new fac-[Mn(ptbpy)(CO)3 Br] (ptbpy=4-phenyl-6-(phenyl-3,4,5-triol)-2,2'-bipyridine) catalyst (2), bearing a bipyridyl derivative with OH groups in different positions to those in 1, provides complementary information about the role that the local proton source plays during the electrochemical reduction of CO2 .

The electrochemical reduction of carbon dioxide (CO2) powered by renewable energy is an attractive sustainable approach to mitigate CO(2)emissions and to produce fuels or value-added chemicals. In order to tackle the challenges related to selectivity, activity, overpotential and durability, transition metal-based catalysts have been widely investigated in the last decades. In an effort to bridge the gap between the fields of homogeneous and heterogeneous catalysis, this review aims to survey the main strategies explored for the rational design of a wide variety of different metal catalysts, ranging from molecular systems to single-atom and nanostructured catalysts. Transition metal complexes containing heme and non-heme ligands have been selected to discuss the recent advances in the understanding of the structure-function relationship in molecular homogeneous catalysis as well as to summarize the main approaches proposed for the heterogenization or confinement of molecular catalysts on conductive surfaces. The main strategies to minimize catalyst cost are also presented, leading to atomically dispersed molecular-like M-N(x)moieties embedded on 2D conducting materials. The superior performances of single-atom catalysts (SACs) and the structural similarity with their molecular analogs, suggest that transition metal catalysts containing well-defined sites may be intrinsically more active and selective towards CO(2)conversion than the bulk heterogeneous materials. Finally, design approaches for metal nanoparticles (NPs) based on size, shape, and support tuning are summarized and compared to novel strategies based on the interaction with surface-bonded organic molecules. The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO(2)reduction.

Automation of flexible surgical instruments requires the development of robotic technologies capable of small-scale power transmission. Magnetic actuation has successfully been used for that purpose. Nevertheless, current systems for magnetic actuation suffer from small workspaces or poor bandwidth of magnetic field control. In this work, we design, develop, and test a novel magnetic actuation system called Advanced Robotics for Magnetic Manipulation (ARMM). The ARMM system employs a 6 DoF mobile electromagnetic coil capable of generating prescribed magnetic fields and gradients. The mobile coil approach allows for easy scaling of the actuation workspace, which depends on the range of robotic arm, and in our case spans up to 1.3 m. Due to limited end-effector payload of the robotic arm used in the ARMM system, the mobile coil has been designed using an optimization routine. For a given mass and heat dissipation constraints, this routine provides the coil geometry that maximizes the average magnetic field generated in the target region. Since the Vacoflux core of the fabricated coil saturates within operational conditions, we propose an actuation strategy employing an online-updated iterative map technique. Using this map, the ARMM system allows for precise generation of prescribed magnetic fields and gradients at the point of interest, while taking into account the effects of the non-linearities due to core saturation. The strategy is validated experimentally, showing the average error of 2.34% for magnetic field and 7.20% for the magnetic field gradient.

The chemical inertness of abundant and commercially available alkyl chlorides precludes their widespread use as reactants in chemical transformations. Presented in this work is a metallaphotoredox methodology to achieve the catalytic intramolecular reductive cyclization of unactivated alkyl chlorides with tethered alkenes. The cleavage of strong C(sp3)@Cl bonds is mediated by a highly nucleophilic lowvalent cobalt or nickel intermediate generated by visible-light photoredox reduction employing a copper photosensitizer. The high basicity and multidentate nature of the ligands are key to obtaining efficient metal catalysts for the functionalization of unactivated alkyl chlorides.

Ponencia presentada en: VI Simposio Nacional de Predicción, celebrado en los servicios centrales de AEMET, en Madrid, del 17 al 19 de septiembre de 2018. La iniciativa MedCOF forma parte de la red de los Foros Climáticos Regionales de Perspectivas del Clima (RCOF, por sus siglas en inglés) y su ámbito de actuación se centra en la región mediterránea. Los RCOF están reconocidos como uno de los principales elementos del Marco Mundial de Servicios Climáticos (GFCS, por sus siglas en inglés) liderado por la OMM. MedCOF se lanzó en junio de 2013 y desde entonces ha venido elaborando dos predicciones estacionales consensuadas anuales (verano e invierno) para todo el Mediterráneo. MedCOF incluye a 34 países con sus respectivos servicios meteorológicos nacionales, así como centros de investigación activos en el campo de la predicción estacional. El objetivo general de MedCOF es reforzar la colaboración entre los países mediterráneos y, en particular, entre las Asociaciones Regionales I y VI de la OMM, para desarrollar capacidades del Sistema de Información de Servicios Climáticos en el marco del GFCS. En particular, MedCOF tiene como prioridades: i) la explotación óptima de todos los recursos de información sobre predicción estacional; ii) la necesidad de proporcionar una respuesta coordinada y acordada de todos los servicios meteorológicos de la región ante la creciente demanda de información a escala estacional; iii) organización de actividades de formación y iv) aumentar la cooperación en tareas que requieren recursos que en muchos casos exceden las capacidades de los servicios meteorológicos individuales. En esta comunicación se describirá en detalle el funcionamiento y desarrollo pasado de esta iniciativa y su posible evolución en el marco de la reformulación que se pretende dar a los RCOF desde la OMM.

We report here the first purely organometallic fac‐[MnI(CO)3(bis‐MeNHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields (η CO≈95 %) in anhydrous CH3CN. Under the same conditions, a maximum turnover frequency (TOFmax) of 2100 s−1 was measured by cyclic voltammetry, which clearly exceeds the values reported for other manganese‐based catalysts. Moreover, the addition of water leads to the highest TOFmax value (ca. 320 000 s−1) ever reported for a manganese‐based catalyst. A MnI tetracarbonyl intermediate was detected under catalytic conditions for the first time.

A new family of cobalt complexes with the general formula [CoII(OTf)2(Y,XPyMetacn)] (1R,Y,XPyMetacn ¼ 1-[(4-X-3,5-Y-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, (X ¼ CN (1CN), CO2Et (1CO2Et), Cl (1Cl), H(1H), NMe2 (1NMe2)) where (Y ¼ H, and X ¼ OMe when Y ¼ Me (1DMM)) is reported. We found that the electronic tuning of the Y,XPyMetacn ligand not only has an impact on the electronic and structural properties of the metal center, but also allows for a systematic water-reduction-catalytic control. In particular, the increase of the electron-withdrawing character of the pyridine moiety promotes a 20-fold enhancement of the catalytic outcome. By UV-Vis spectroscopy, luminescence quenching studies and Transient Absorption Spectroscopy (TAS), we have studied the direct reaction of the photogenerated [IrIII(ppy)2(bpyc )] (PSIr) species to form the elusive CoI intermediates. In particular, our attention is focused on the effect of the ligand architecture in this elemental step of the catalytic mechanism. Finally, kinetic isotopic experiments together with DFT calculations provide complementary information about the rate-determining step of the catalytic cycle We would like to thank the European Commission for the ERCCG-2014-648304 (J.Ll.-F) project. The financial support from ICIQ Foundation and CELLEX Foundation through the CELLEXICIQ high throughput experimentation platform and the Starting Career Program is gratefully acknowledged. We also thank CERCA Programme (Generalitat de Catalunya); The MINECO is acknowledged for a FPU fellowship to A.C (AP2012- 6436) and ICIQ-IPMP program (F.F.) and Severo Ochoa Excellence Accreditation 2014–2018 (SEV-2013-0319). J.M.L. is grateful for financial support from the Spanish MINECO CTQ2014-52525-P and the Catalan DIUE 2014SGR931. J.P-P. gratefully acknowledge CTQ2014-60174-P (partially co-financed with FEDER funds), Maria de Maeztu (MDM-2015-0538), RyC contract to MGB) and Fundación Ramón Areces for financial support

The effect of a local proton source on the activity of a bromotricarbonyl Mn redox catalyst for CO2 reduction has been investigated. The electrochemical behaviour of the novel complex [fac-Mn(dhbpy)(CO)3Br] (dhbpy = 4-phenyl-6-(1,3-dihydroxybenzen-2-yl) 2,2'-bipyridine), containing two acidic OH groups in the proximity of the metal centre, under a CO2 atmosphere showed a sustained catalysis in homogeneous solution even in the absence of Brønsted acids.

An integrated experimental–theoretical approach for the solid-state NMR investigation of a series of hydrogen-storage materials is illustrated. Seven experimental room-temperature structures of groups I and II metal hydrides and borohydrides, namely, NaH, LiH, NaBH4, MgH2, CaH2, Ca(BH4)2, and LiBH4, were computationally optimized. Periodic lattice calculations were performed by means of the plane-wave method adopting the density functional theory (DFT) generalized gradient approximation (GGA) with the Perdew–Burke–Ernzerhof (PBE) functional as implemented in the Quantum ESPRESSO package. Projector augmented wave (PAW), including the gauge-including projected augmented-wave (GIPAW), methods for solid-state NMR calculations were used adopting both Rappe–Rabe–Kaxiras–Joannopoulos (RRKJ) ultrasoft pseudopotentials and new developed pseudopotentials. Computed GIPAW chemical shifts were critically compared with the experimental ones. A good agreement between experimental and computed multinuclear chemical shift...

S-CimWaRe es el resultado de un grupo de trabajo multidisciplinar impulsado por AEMET y la Direccion General del Agua creado con el objetivo de desarrollar un servicio climatico experimental para el apoyo a la gestion de los embalses en Espana. Este proyecto forma parte de las actividades de implementacion en Espana del Marco Mundial de Servicios Climaticos y se desarrolla como un caso de estudio dentro del proyecto europeo FP7 EUPORIAS que trabaja en el desarrollo de sistemas de prevision de impactos a escala estacional y decadal para el apoyo a la toma de decisiones dependientes del clima. En S-ClimWaRe se han seleccionado 4 embalses de las cuencas del Duero, Tajo, Ebro y Guadalquivir en los que se esta probando la utilizacion de las predicciones climaticas estacionales (Pouget et al., 2015). El proyecto combina datos de observacion hidrologicos y meteorologicos, el sistema estadistico de prediccion estacional de aportaciones que se describe en este documento y un modelo de prevision de riesgos de los embalses, SIMRISK, que fue desarrollado por la Universidad Politecnica de Valencia (Andreu et al., 1996). Asi mismo, el proyecto contempla la formacion en los temas que se van desarrollando, actividades de divulgacion y un activo foro de encuentro entre los agentes implicados. Este documento es un extracto del documento de referencia que con el titulo “Sistema Estadistico de Prediccion Estacional para la Gestion de los Embalses en Espana” sera pub

The effects of the highly fluorescent 4-piperidinyl-1,8-naphthalimide (PNI) chromophore on the CO2 reduction catalytic properties of rhenium-based catalysts are investigated herein. In particular, the electro- and photocatalytic CO2 reduction features of [Re(CO)3(bpy)Cl] (bpy = 2,2′-bipyridine) are compared with the activity of [Re(CO)3(phen–PNI)Cl] (phen = 1,10-phenanthroline), which is known for its long excited-state lifetime. Moreover, another Re complex, namely [Re(CO)3(bpy–Ph–PNI)Cl], has been synthesized and tested as an electro- and photocatalyst. The catalytic properties of the selected compounds were studied by means of electrochemical (cyclic voltammetry and controlled-potential electrolysis) and photophysical measurements together with DFT calculations. [Re(CO)3(bpy–Ph–PNI)Cl] showed good electrocatalytic efficiency toward selective CO2 reduction to CO, as well as reduced electrocatalytic overpotential.

Tetracarbonyl complexes of low-valent Group VI transition metals (Mo and W), containing diimine bidentate ligands, namely W(CO)4(4,6-diphenyl-2,2′-bipyridine) (1), W(CO)4(6-(2,6-dimethoxyphenyl)-4-phenyl-2,2′-bipyridine) (2), Mo(CO)4(2,2′-dipyridylamine) (3), and W(CO)4(2,2′-dipyridylamine) (4), were synthesized and tested as homogeneous catalysts for the electrochemical reduction of CO2 in nonaqueous media. Cyclic voltammetry performed under a CO2 atmosphere, revealed that these complexes have significant catalytic activity in acetonitrile, and gas chromatographic measurements together with exhaustive electrolysis showed that CO is the major reduction product. Mechanistic insights were obtained by IR-spectroelectrochemical measurements. The substantially different electrocatalytic performances obtained for the two classes of catalysts are compared and discussed.

Foi desenvolvido projeto de pesquisa clínica e radiográfica para avaliar a influência do ângulo formado entre a superfície dental e a crista óssea na determinação da profundidade de sondagem do sulco gengival e complementarmente no comportamento da margem gengival por vestibular de dentes molares inferiores inclinados para mesial. Para tanto foram incluídos 30 sítios mesiais e 30 distais no grupo teste, com igual número de sítios controles de molares inferiores com inclinação normal. Nos dentes que forneceram esses sítios também foi feita a determinação da profundidade do sulco gengival na região vestibular central do dente, identificando-se a qualidade e quantidade de gengiva ceratinizada, respectivamente pela metodologia de Kan et al. (2010) e pela mensuração com sonda periodontal da distância da margem gengival à junção mucogengival. Foram incluídos pacientes periodontal e sistemicamente saudáveis, excluindo-se pacientes que tivessem sido submetidos a procedimentos ósseos regenerativos prévios nas áreas de interesse, diabéticos relutantes ao controle médico, usuários de drogas e/ou álcool, portadores de alterações sistêmicas que interfiram no metabolismo ósseo (como por exemplo, osteoporose e hiperparatireoidismo). Os exames foram realizados por examinador competente, devidamente calibrado. Para análise radiográfica as imagens foram transferidas para o computador, realizando-se as mensurações dos ângulos interessados com o programa de computador MB-Ruler Pro (MB-Software solutions). A análise estatística foi realizada no programa GraphPad Prism versão 5.03 para Windows (GraphPad, Usa). Os resultados obtidos em linhas gerais mostraram que houve influência significativa do ângulo entre a superfície dental e a crista óssea (p > 0,0001) na determinação do sulco gengival proximal em áreas de dentes inclinados, porém não há essa influência na profundidade de sondagem do sulco gengival por vestibular para áreas com qualidade e quantidade de gengiva comparáveis ao controle (p=0,08). A despeito desses resultados, não se encontrou correlação definida entre nenhum dos parâmetros de interesse analisados. Dentro dos limites do estudo os resultados também evidenciaram que, embora possam ocorrer variações desses parâmetros, a saúde periodontal pode ser mantida pelo indivíduo nas condições analisadas. A clinical and radiographic research project was developed to assess the influence of the angle formed between the tooth surface and the alveolar bone crest in determining the probing depth of the gingival sulcus and complementary also to evaluate the behavior of the buccal gingival margin of mesially inclined molars. Therefore, 30 mesial and 30 distal sites of inclined lower molars were included in the test group, with an equal number of sites of lower molars with normal inclination in the control group. In addition in all the teeth of both test and control groups the depth of the clinical gingival sulcus at the central buccal region of the tooth was assessed by measuring with a periodontal probe, identifying the quality of the keratinized gingiva through the methodology of Kan et al. (2010) and determining the width of keratinized gingiva by measuring the distance from the free gingival margin to the mucogingival junction. The study was done in systemic and periodontally healthy individuals, excluding patients who had undergone bone-regenerative procedures in the areas of interest, diabetics reluctant to medical control, alcohol and / or drug users, and individuals suffering from systemic conditions that might interfere with bone metabolism (like osteoporosis and hyperparathyroidism). The examinations were performed by a competent and properly calibrated examiner. The radiographic images were then transferred to a computer in order to analyze the measurements of the involved angles with the computer program MB-Ruler Pro (MB-Software solutions). Statistical analysis was performed using GraphPad Prism version 5.03 for Windows (GraphPad, Usa). The results in general showed that there was significant influence of the angle between the tooth surface and the alveolar bone crest on the depth of the gingival sulcus in proximal areas of inclined teeth (p > 0,0001), but there was no such influence in the probing depth of the buccal gingival sulcus of these inclined molars provided that the quality and quantity of gingiva were similar to controls comprised by molars with normal inclination (p=0,08). Despite this significance, there was no definite correlation between any of the analyzed parameters of interest. The results also showed that, although there may be variations of these parameters, within the limits of this study the conditions of periodontal health can be maintained by the individual.

We report here the first purely organometallic fac-[MnI (CO)3 (bis-Me NHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields (ηCO ≈95 %) in anhydrous CH3 CN. Under the same conditions, a maximum turnover frequency (TOFmax ) of 2100 s-1 was measured by cyclic voltammetry, which clearly exceeds the values reported for other manganese-based catalysts. Moreover, the addition of water leads to the highest TOFmax value (ca. 320 000 s-1 ) ever reported for a manganese-based catalyst. A MnI tetracarbonyl intermediate was detected under catalytic conditions for the first time.