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Mononuclear C-scorpionate copper(II) complexes [CuCl2{κ3-RC(R1-pz)3}[R = R1 = H (1), R = CH2OH, R1 = H (2) and the new R = H, R1 = 3,5-Me2 (3)] supported on sucrose derived hydrochars are the first recyclable tris(pyrazol-1-yl)methane catalysts used so far for the selective oxidation of styrene to benzaldehyde. Remarkably, a benzaldehyde yield of over 60% (100% selectivity) with a TOF = 1.3 × 104 was obtained after only 5 min reaction in homogeneous conditions. The immobilization of 1–3 at functionalized hydrochars led to solvent-free recyclable catalytic systems for the mentioned reaction, that, although leading to slightly modest benzaldehyde yields (up to 52%), require much lower amounts of oxidant than the homogeneous analogs. The effects of scorpionate properties as well as of reaction parameters (e.g., reaction time, amount of catalyst and oxidant or type of solvent) on the performance of the above catalytic systems are discussed.

The aim of this study was to analyze the predictive risk factors for self-harm in adolescents with and without suicidal ideation. 600 adolescents answered a questionnaire about self-harm and suicidal behaviors. A logistic regression analysis was conducted. Over half of the individuals with deliberate self-harm (DSH) presented significant suicide risk. There was a direct association between DSH and suicide attempts, with almost the totality of the adolescents with suicide attempts also reporting DSH. According to the prediction model, suicidal ideation and diversity of DSH behaviors are significant predictors of suicide attempts, with an augmentation in the diversity of DSH behaviors and suicidal ideation predicting suicide attempts. Depression and anxiety appeared also as significant predictors of suicide attempts in adolescent self-harmers. Considering that the majority of the sample was not from a clinical setting, an alarming finding was that one third of the total sample was at suicide risk. These results place DSH as a key variable for early intervention. info:eu-repo/semantics/publishedVersion

The ultra-fast, selective and eco-friendly synthesis of benzaldehyde (70% yield, TOF 1.4 × 104 h−1, 5 min) from styrene is achieved by using [CuCl2{κ3-HC(pz)3}] (pz = pyrazol-1-yl) as a reusable catalyst. This C-homoscorpionate Cu(II) complex is the first one of its class to be used as catalyst for the oxidation of styrene to benzaldehyde.

Catalytic efficiency of tetrabutylammonium salts of sandwich tungstophosphates B‐α‐[M 4 (H 2 O) 2 (PW 9 O 34 ) 2 ] n− , M = Co II , Mn II , Fe III , was studied in the oxidation of ( R )-(+)-limonene, geraniol, linalool, linalyl acetate, carveol, and cis -cyclooctene with hydrogen peroxide, in acetonitrile. Oxidation of ( R )-(+)-limonene gave limonene-1,2-diol as main product. Epoxidation of linalool takes place preferentially at the more substituted 6,7-double bond, the corresponding 6,7-epoxide reacting further, yielding furano- and pyrano-oxides, via intramolecular cyclization. Oxidation of linalyl acetate occurred preferentially at the more substituted 6,7-double bond for Mn 4 (PW 9 ) 2 , affording 6,7-epoxide at 82% selectivity. Linalyl acetate 1,2-epoxide was the major product with 51% and 77% selectivity for Co 4 (PW 9 ) 2 and Fe 4 (PW 9 ) 2 , respectively. Oxidation of carveol occurred with very good conversions in the presence of Mn 4 (PW 9 ) 2 , Co 4 (PW 9 ) 2 and Fe 4 (PW 9 ) 2 , yielding carvone and carveol 1,2-epoxide in similar amounts. Oxidation of cis -cyclooctene gave only the epoxide, while oxidation of geraniol at room temperature afforded 2,3-epoxygeraniol as the major product.

The catalytic activity of the iron(II) C-scorpionate complexes [FeCl2{HC(pz)3}] 1 (pz = pyrazol-1-yl) and [FeCl2{HOCH2C(pz)3}] 2, and of their precursor FeCl2·2H2O 3, towards cyclohexane oxidation with tert-butyl hydroperoxide was evaluated and compared in different media: acetonitrile, ionic liquids (1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [bmim][FAP]), supercritical carbon dioxide (scCO2), and scCO2/[bmim][X] (X = PF6 or FAP) mixtures. The use of such alternative solvents led to efficient and selective protocols for the oxidation of cyclohexane. Moreover, tuning the alcohol/ketone selectivity was possible by choosing the suitable solvent.

The tetrabutylammonium (TBA) salt of a Keggin-type polyoxometalate (POM), with the chemical formula TBA4H2[BW11Mn(H2O)O39]{\textperiodcentered}H2O, TBABW11Mn, was evaluated as a catalyst in the oxidation by hydrogen peroxide of several organosulfur compounds, namely benzothiophene (BT), 2-methylbenzothiophene (2-MBT), 3-methylbenzothiophene (3-MBT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-diethyldibenzothiophene (4,6-DEDBT), in acetonitrile at room temperature. All compounds were oxidized to their corresponding sulfones with high conversion and selectivity. Following the excellent results achieved, the BW11Mn/H2O2 in CH3CN system was tested in the oxidation of model fuels (MFs) consisting of a mixture of BTs and DBTs in hexane (MF1 containing mainly BTs and MF2 containing predominantly DBTs). In both cases, the organosulfur compounds from the model fuels were fully converted into their corresponding sulfones. Envisaging the development of a promising desulfurization procedure, the extraction of sulfur compounds from MF2 was attempted after the catalytic oxidation process. More than 98 mol% was removed using an ethanol/H2O mixture.

The tetrabutylammonium (TBA) salts of the Keggin-type polyoxotungstates with general formula [XW11M(H2O)O-39]((n-m)-), where X = P, B or Si and M = Mn, Fe or Co, were evaluated as catalysts in the oxidation of styrene, alpha-methylstyrene, p-methylstyrene, alpha,p-dimethylstyrene, p-chlorostyrene, p-nitrostyrene, and p-methoxystyrene under mild conditions, using aqueous H2O2 as an eco-sustainable oxidant. In this study, the influence of the catalysts and of the different styrene substituents on the oxidation reaction profile was evaluated in terms of conversion and selectivity. For all the performed catalytic studies, the main product results from the oxidative cleavage of the vinyl double bond, except in the case of the oxidation of p-methoxystyrene catalysed by BW11Mn, for which p-methoxyphenol is the main product. The catalysts BW11Mn and SiW11Co give rise to 100% conversion for almost all of the substrates, excluding p-methoxystyrene and p-nitrostyrene for both catalysts and alpha,p-dimethylstyrene only in the case of BW11Mn. The selectivity for C=C cleavage products resulting from the oxidative cleavage of the vinyl double bond can be as high as 98%, reaching 98% conversion for p-nitrostyrene when SiW11Co was used as a catalyst. Possible pathways are discussed and the oxidation of a few presumed intermediates was carried out. The systematic study of several substituted styrene derivatives suggests a possible reactivity order for these compounds in the catalytic system considered.

IntroductionSeason of birth, an exogenous indicator of early life environment, has been related to higher risk of adverse psychiatric outcomes. According to literature, an excess of 5–8% of winter-spring births is found in individuals who later develop schizophrenia and bipolar disorder; this seasonal birth excess is also found in schizoaffective disorder (winter), major depression (March–May), and autism (March).ObjectivesThe objective of this study was to analyze the seasonal birth patterns of in-patients with psychiatric disorders.AimsUnderstand the relation between psychiatric disorders and season of birth during a 10 year period in a Portuguese University Hospital.MethodsAnalyze the birth date distribution of 2202 in-patients between 2007 and 2016 and compare with the psychiatric diagnosis.ResultsPatients’ diseases analyzed by birthday season: 60% of patients with schizoaffective disorder were born in winter-spring, 48.4% of mental retarded patients were born in autumn, 37% of dementia patients in winter, 77% of patients with delusional disorder in winter-spring, 78% of patients with Cluster A personality disorder in spring-summer and 71% of patients with substance abuse conditions in autumn-winter. No seasonal birth excess was found for bipolar affective disorder, schizophrenia, alcohol abuse, major depressive disorder or Cluster B personality disorder.ConclusionsOur sample data shows evidence for a potential link between season of birth and risk for schizoaffective disorder, dementia, mental retardation, Cluster A personality disorder, delusional disorder and substance abuse. The attempt to explain seasonal birth patterns in psychiatric illnesses could serve to clarify the etiological bases of such disorders.Disclosure of InterestThe authors have not supplied their declaration of competing interest.

Sodium tungstate dihydrate is a commercially available reagent, in the form of a crystalline white solid, which is usually used in the synthesis of inorganic compounds, namely in polyoxometalates synthesis. Sodium tungstate dihydrate can also be used as catalyst or as catalyst precursor in several organic reactions, namely epoxidation, cleavage of double bonds, oxidation of alcohols, amines, imines, and organosulfur compounds, haloge atio of aro ati o pou ds, sy thesis of β-arylvinyl bromides, and synthesis of 1-H-tetrazoles.

This paper focuses on the analysis of a floating wind turbine under multidirectional wave loading. Special attention is given to the different methods used to synthesize the multidirectional sea state. This analysis includes the double-sum and single-sum methods, as well as an equal-energy discretization of the directional spectrum. These three methods are compared in detail, including the ergodicity of the solution obtained. From the analysis, the equal-energy method proved to be the most computationally efficient while still retaining the ergodicity of the solution. This method was chosen to be implemented in the numerical code FAST. Preliminary results on the influence of these wave loads on a floating wind turbine showed significant additional roll and sway motion of the platform.

Offshore wind turbines are designed and analyzed using comprehensive simulation tools (or codes) that account for the coupled dynamics of the wind inflow, aerodynamics, elasticity, and controls of the turbine, along with the incident waves, sea current, hydrodynamics, mooring dynamics, and foundation dynamics of the support structure. This paper describes the latest findings of the code-to-code verification activities of the Offshore Code Comparison Collaboration Continuation project, which operates under the International Energy Agency Wind Task 30. In the latest phase of the project, participants used an assortment of simulation codes to model the coupled dynamic response of a 5-MW wind turbine installed on a floating semisubmersible in 200 m of water. Code predictions were compared from load case simulations selected to test different model features. The comparisons have resulted in a greater understanding of offshore floating wind turbine dynamics and modeling techniques, and better knowledge of the validity of various approximations. The lessons learned from this exercise have improved the participants’ codes, thus improving the standard of offshore wind turbine modeling.Copyright © 2014 by ASME

Sodium tungstate dihydrate is a commercially available reagent, in the form of a crystalline white solid, which is usually used in the synthesis of inorganic compounds, namely in polyoxometalates synthesis. Sodium tungstate dihydrate can also be used as catalyst or as catalyst precursor in several organic reactions, namely epoxidation, cleavage of double bonds, oxidation of alcohols, amines, imines, and organosulfur compounds, haloge atio of aro ati o pou ds, sy thesis of β-arylvinyl bromides, and synthesis of 1-H-tetrazoles.