Chemistry of a Nitrosyl Ligand ¿:¿-Bridging a Ditungsten Center: rearrangement and N–O Bond cleavage reactions

The novel nitrosyl-bridged complex [W2Cp2(μ-PtBu2)(μ-κ:η-NO)(CO)(NO)](BAr4) [Ar = 3,5-C6H3(CF3)2] was prepared in a multistep procedure starting from the hydride [W2Cp2(μ-H)(μ-PtBu2)(CO)4] and involving the new complexes [W2Cp2(μ-PtBu2)(CO)4](BF4), [W2Cp2(μ-PtBu2)(CO)2(NO)2](BAr4), and [W2(μ-κ:η5-C5H4)Cp(μ-PtBu2)(CO)(NO)2] as intermediates, which follow from reactions with HBF4·OEt2, NO, and Me3NO·2H2O, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with [N(PPh3)2]Cl, with concomitant NO rearrangement into the terminal coordination mode, to give [W2ClCp2(μ-PtBu2)(CO)(NO)2], and underwent N–O and W–W bond cleavages upon the addition of CNtBu to give the mononuclear phosphinoimido complex [WCp(NPtBu2)(CNtBu)2](BAr4). Another N–O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex [W2Cp2(N)(μ-O)(μ-OPtBu2)(NO)](BAr4), likely resulting from a N–O bond cleavage step following decarbonylation

Water erosion in a Yellow-Red Ultisol under different patterns of simulated rain

Visou-se, neste trabalho, determinar as perdas de solo, água e nutrientes em um Argissolo Vermelho-Amarelo submetido a quatro diferentes padrões de chuva simulada. O estudo foi conduzido no Campo Experimental da Embrapa-Agrobiologia, localizado no município de Seropédica, RJ, e consistiu na aplicação de chuvas simuladas com diferentes padrões caracterizados como avançado (AV), intermediário (IN), atrasado (AT) e constante (CT), em uma área amostral de 0,80 m de largura por 1,0 m de comprimento. As chuvas tiveram duração de 60 min com uma lâmina total aplicada de 30 mm e um pico de 110 mm h-1, para os padrões de intensidade variável. Os resultados obtidos possibilitaram concluir que após 60 min de chuva simulada as perdas de solo e água observadas para o padrão atrasado foram, em média, superiores em 61,6, 46,4 e 13,6%, respectivamente, para o CT, AV e IN (solo), e de 42,0, 19,0 e 19,0%, respectivamente, para o AV, IN e CT (água) e as perdas de nutrientes não diferiram entre os padrões de precipitação, sendo mais influenciadas pelas perdas de água escoada superficialmente que pelo material sólido em suspensão.This study was carried out in order to determine the soil, water and nutrient losses in a Yellow-Red Ultisol, under four different patterns of simulated rainfall. The experiment was conducted at the Embrapa Agrobiologia experimental field, located in the municipality of Seropédica, Rio de Janeiro, Brazil. The study consisted in the application of simulated rains using variable rainfall intensity classified in different patterns as: advanced (AD), intermediate (IN), delayed (DE), and constant (CT), in plots 0.8 m wide and 1.0 m long. The rain had a duration of 60 min, with a total applied depth of 30 mm, and a peak of 110 mm h-1, for the variable intensity patterns. With the results obtained it was possible to verify that after 60 min of simulated DE pattern provided losses higher than CT, AD and IN, in 61.6, 46.4 and 13.6%, respectively (soil), and 42.0, 19.0 and 19.0% (run-off), respectively, for the AD, IN and CT patterns; and the nutrients losses did not differ among the rainfall patterns, being more affected by water run-off than solid material in suspension

Polymer co-crystalline films for photonics

Robust syndiotactic polystyrene (sPS) films exhibiting highly stable co-crystalline phases can be obtained with a large variety of low-molecular-mass chromophore guest molecules. In this report different aspects relative to the structure and the optical properties of these films are described. In particular, possible applications of these films as fluorescent materials, as optical memories (based on the co-crystallization of photoreactive guest molecules), as non-linear optical materials (with polar guests) and as chiro-optical memories (based on temporary co-crystals with chiral guest molecules) are presented

Fundamental parameters related to selenium kα and kβ emission x-ray spectra

This research was funded in part by FCT (Portugal) under research center grants UID/FIS/04559/2020 (LIBPhys) and UID/MULTI/04046/2020 (BioISI). This work was also funded through the project PTDC/FIS-AQM/31969/2017, "Ultra-high-accuracy x-ray spectroscopy of transition metal oxides and rare earths." J.M. and J.P.S acknowledge the support of EMPIR, under Contract No. 17FUN02MetroMMC. The EMPIR initiative is co-funded by the European Union's Horizon 2020 research and innovation programme and the EMPIR participating States.We present relativistic ab initio calculations of fundamental parameters for atomic selenium, based on the Multiconfiguration Dirac-Fock method. In detail, fluorescence yields and subshell linewidths, both of K shell, as well as Kβ to Kα intensity ratio are provided, showing overall agreement with previous theoretical calculations and experimental values. Relative intensities were evaluated assuming the same ionization cross-section for the K-shell hole states, leading to a statistical distribution of these initial states. A method for estimating theoretical linewidths of X-ray lines, where the lines are composed by a multiplet of fine-structure levels that are spread in energy, is proposed. This method provides results that are closer to Kα1,2 experimental width values than the usual method, although slightly higher discrepancies occur for the Kβ1,3 lines. This indicates some inaccuracies in the calculation of Auger rates that have a higher contribution for partial linewidths of the subshells involved in the Kβ1,3 profile. Apart from this, the calculated value of Kβ to Kα intensity ratio, which is less sensitive to Auger rates issues, is in excellent agreement with recommended values.publishersversionpublishe

What happens if you single out? An experiment

We present an experiment investigating the effects of singling out an individual on trust and trustworthiness. We find that (a) trustworthiness falls if there is a singled out subject; (b) non-singled out subjects discriminate against the singled out subject when they are not responsible of the distinct status of this person; (c) under a negative frame, the singled out subject returns significantly less; (d) under a positive frame, the singled out subject behaves bimodally, either selecting very low or very high return rates. Overall, singling out induces a negligible effect on trust but is potentially disruptive for trustworthiness

Feasibility study of culture of the Pacific oyster Crassostrea gigas (Thunberg, 1793) in different Galician rias (northwest Spain): First biological results

Batches of the Pacific oyster Crassostrea gigas (Thunberg, 1793) have been experimentally cultivated in three rías from Galicia (northwest Spain) using two different techniques: raft and intertidal culture. Performance of these batches was assessed by analysing the growth, mortality and quality of the oysters produced. First results suggested a good growth in the majority of the raft-cultured batches and in the intertidal zone with commercial oysters after 14 months. Mortality was low ( 15 %), especially in intertidal culture. Oysters were affected by blisters and mud worms, but without impairment to their market acceptability.Los problemas que la producción ostrícola tradicional gallega tiene planteados han puesto en peligro la continuidad del sector. En el marco de exploración de una alternativa parcial que contribuya a superarlos, se ha llevado a cabo el cultivo experimental de varios lotes de ostra rizada Crassostrea gigas (Thunberg, 1793) en tres rías gallegas empleando dos técnicas diferentes: cultivo en batea y en zona intermareal. Se evaluó el rendimiento de los mismos mediante el análisis del crecimiento, la mortalidad y la calidad de las ostras producidas. Los primeros resultados mostraron un crecimiento adecuado en la mayor parte de los lotes cultivados, produciéndose ostras comerciales en 14 meses de cultivo, tanto en batea como en intermareal. La mortalidad fue baja en general (inferior al 15 %), especialmente en el cultivo intermareal. Las ostras se vieron afectadas por poliquetos perforadores y por anomalías de calcificación, pero sin llegar a condicionar su aceptabilidad comercial.Instituto Español de Oceanografí

The Best and Worst of Contracts Decisions: An Anthology

Five hundred years ago, the common law of contract was without substance. It was form-procedure. Plaintiffs picked a form of action, and common law judges made sure someone besides themselves answered all the hard questions; the parties, a jury, or a ritual determined the winner and the remedy. Judges ran a switch on a conflicts-resolution railway. Thomas More, when Chancellor of England (1529-33), urged judges to lay tracks and control the trains. The problem, he said, was that the judges, by the verdict of the jury[,] cast off all quarrels from themselves. The judges soon assumed greater authority, taking responsibility for the law\u27s substance. The consideration requirement was in place by 1539, and judges afterwards imposed doctrine upon doctrine. Over centuries, they created the common law of contract. That law is now mature, more or less, meaning that judges have tools to fix what they want to fix, and feel free to do so. The law they created-the common law of contract-is a remarkable intellectual and political achievement

Synthetic approaches to phosphasugars (2-oxo-1,2- oxaphosphacyclanes) using the anomeric alkoxyl radical β‑fragmentation reaction as the key step

The anomeric alkoxyl radical β-fragmentation (ARF) of carbohydrates possessing an electron-withdrawing group (EWG) at C2, promoted by PhI(OAc)2/I2, gives rise to an acyclic iodide through which a pentavalent atom of phosphorus can be introduced via the Arbuzov reaction. After selective hydrolysis and subsequent cyclization, the phosphonate or phosphinate intermediates can be converted into 2- deoxy-1-phosphahexopyranose and 2-deoxy-1-phosphapentopyranose sugars. The ARF of carbohydrates with an electron-donor group (EDG) at C2 proceeds by a radical-polar crossover mechanism, and the cyclization occurs by nucleophilic attack of a conveniently positioned phosphonate or phosphinate group to the transient oxocarbenium ion. This alternative methodology leads to 5-phosphasugars with a 4-deoxy-5-phosphapentopyranose framework. The structure and conformation of the 2-oxo-1,2-oxaphosphinane and 2-oxo-1,2-oxaphospholane ring systems in different carbohydrate models have been studied by NMR and X-ray crystallography

Water and soil losses under different patterns of simulated rainfall and soil cover conditions

Este trabalho foi realizado com o objetivo de determinar as perdas de solo e água em um Argissolo Vermelho-Amarelo, submetido a quatro diferentes padrões de precipitação de chuva simulada e duas condições de cobertura: área com solo descoberto e com palhada após plantio de milho. O experimento foi conduzido no Campo Experimental da Embrapa-Agrobiologia, localizado no município de Seropédica-RJ, e consistiu na aplicação de chuvas simuladas com diferentes padrões, caracterizados como avançado (AV), intermediário (IN), atrasado (AT) e constante (CT), em uma área amostral de 0,80 m de largura por 1,0 m de comprimento. Utilizando um simulador de chuvas portátil, foram aplicadas chuvas com 30 mm de lâmina total durante 60 minutos. Nos padrões com intensidade variada, o pico de precipitação foi de 110 mm h-1. Os resultados obtidos possibilitaram concluir que a cobertura do solo com resíduos de milho reduziu substancialmente as taxas e perdas de água e solo, principalmente para o padrão de chuva constante, indicando que a palhada deixada sobre o solo após a colheita auxilia de maneira efetiva no controle da erosão.This study was carried out in order to determine the soil and water losses in a Yellow-red Ultisol, under four different rainfall patterns and two conditions of soil cover: area with soil uncovered and with straw after corn planting. The experiment was conducted at the experimental field of Embrapa Agrobiologia, located at Seropedica municipality, State of Rio de Janeiro, Brazil. The treatments consisted in application of simulated rainfall using variable intensity classified in different patterns as: advanced (AV), intermediate (IN), delayed (AT), and constant (CT), in a plots with 0.8 m of width and 1.0 m of length. Using a portable rainfall simulator rainfall with 30 mm total depth during 60 minutes was applied. For the patterns with varied intensity, the peak of precipitation was 110 mm h(-1). The results showed the cover of the soil with corn stubble substantially reduced the rates and the soil and water losses, mainly for the pattern of constant rainfall, indicating that the residues left on the ground after harvest helps effectively in the erosion control

Programa de internacionalización de los productos de “Finca La Isla”.

Dentro del proyecto 3J04 “Inteligencia Cultural y Comercial para los Negocios Internacionales”, se realizó el programa de internacionalización de varios productos naturales de la empresa “Finca La Isla”. Estos van desde: Miel, Jengibre, Vainilla, Cúrcuma, Canela, entre otros. El proyecto se centró en la exportación de la miel en dos destinos: Alemania y Turquía, centrándose en las ferias Internacionales de la Anuga 2023, en Cologne, y Apimondia 2022 en Estambul. El proyecto nos llevó a crear un brochure, en donde se pueden encontrar diferentes aspectos económicos, culturales, sociales, políticos, y de mercado, para que el empresario tenga en cuenta todo antes de iniciar la inversión. Nos dividimos en dos equipos de trabajo, cada uno enfocado en un paísITESO, A.C