Merging C-C σ-bond activation of cyclobutanones with CO2 fixation via Ni-catalysis

A carboxylative Ni-catalyzed tandem C-C σ-bond activation of cyclobutanones followed by CO2-electrophilic trapping is documented as a direct route to synthetically valuable 3-indanone-1-acetic acids. The protocol shows an adequate functional group tolerance and useful chemical outcomes (yield up to 76%) when AlCl3 is adopted as an additive. Manipulations of the targeted cyclic scaffolds and a mechanistic proposal based on experimental evidence complete the investigation

Electrochemical C(sp3)-H functionalization of ethers via hydrogen-atom transfer by means of cathodic reduction

: The chemo- and stereoselective electrochemical allylation/alkylation of ethers is presented via a C(sp3)-H activation event. The electrosynthetic protocol enables the realization of a large library of functionalized ethers (35 examples) in high yields (up to 84%) via cathodic activation of a new type of redox-active carbonate (RAC), capable of triggering HAT (Hydrogen-Atom-Transfer) events through the generation of electrophilic oxy radicals. The process displayed high functional group tolerance and mild reaction conditions. A mechanistic elucidation via voltammetric analysis completes the study

Microwave Assisted Synthesis, Characterization and Antibacterial Study of Some Novel Schiff's Bases, Thaizolidinone and Chalcone Compounds Derived from Mefenamic Acid

This work involves synthesis of some new heterocyclic compounds including thaizolidinone compounds. The new Schiff bases derived from mefenamic acid, which was synthesized by microwave irradiation of mefenamic acid with hydrazine hydrate in absolute ethanol and this amino compound condensation with different aromatic aldehydes in absolute ethanol. Thaizolidinone compounds were synthesized by cycloaddition reaction of mercapto acetic acid to imine group of Schiff bases in dry benzene. The new chalcone derivatives synthesized by the reaction aldehyde with their compounds.  M.P., TLC, CHN, UV, FTIR and NMR spectroscopy has characterized all the synthesized compounds. The biological screening data of the synthesized compounds were also studied. Keywords: Schiff bases, thaizolidinone, chalcone, antibacterial

Diurnal cortisol and obesity in adolescents with and without Down syndrome

BackgroundThe prevalence of obesity in adolescents with Down syndrome (DS) far exceeds that in the general population. Cortisol, an adrenal hormone, can be obesogenic when dysregulated. However, the diurnal patterns of this hormone have not been examined among individuals with DS. Variations in adiposity may also mediate cortisol regulation. This study sought to examine diurnal cortisol patterns in adolescents with DS as well as associations between cortisol function and obesity.MethodA total of 32 adolescents, including 16 with DS and 16 controls with typical development (TD) of similar sex, age and Tanner pubertal stage (P > 0.05), participated in this preliminary study. Participants completed a dual‐energy X‐ray absorptiometry scan to measure body composition and collected saliva samples for cortisol measurements in the morning, afternoon and night. Linear mixed models with random intercepts and repeated measures were used to examine the daily trajectory of log‐transformed cortisol concentrations between adolescents with and without DS. A second model examined the interaction between DS and presence of elevated body fatness.ResultsAdolescents with DS had higher morning cortisol concentrations (intercept = 0.37 μg/dL), but this was not significantly different than in TD (0.35 μg/dL, P = 0.16). Cortisol significantly declined across hours (b = −0.026 μg/dL/h, P  0.05; d = 0.30).ConclusionsThis study is the first to examine diurnal cortisol in DS but is limited in sample size. These preliminary findings suggest that diurnal cortisol patterns are not significantly different between adolescents with DS and TD and that cortisol levels are not associated with adiposity in this population. Despite these non‐significant differences, youth with DS continue to be an ‘at‐risk’ population for paediatric obesity in need of clinical intervention.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/151976/1/jir12682_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/151976/2/jir12682.pd

Visible-Light Assisted Covalent Surface Functionalization of Reduced Graphene Oxide Nanosheets with Arylazo Sulfones

We present an environmentally benign methodology for the covalent functionalization (arylation) of reduced graphene oxide (rGO) nanosheets with arylazo sulfones. A variety of tagged aryl units were conveniently accommodated at the rGO surface via visible-light irradiation of suspensions of carbon nanostructured materials in aqueous media. Mild reaction conditions, absence of photosensitizers, functional group tolerance and high atomic fractions (XPS analysis) represent some of the salient features characterizing the present methodology. Control experiments for the mechanistic elucidation (Raman analysis) and chemical nanomanipulation of the tagged rGO surfaces are also reported

Multinuclear (1H, 31P, and 195Pt) NMR study and dynamical analysis of binuclear \ub5-hydrido \ub5-carbonyl Pt(I) cations with chelating diphosphines

The dynamic behaviour of the binuclear \u3bc-hydrido \u3bc-carbonyl cations with chelating diphosphines, [Pt2(P\u2013P)2-(\u3bc-H)(\u3bc-CO)]+ [P\u2013P = dppe, 1, dppp, 2, and dppb, 3] have been investigated by multinuclear (1H, 31P and 195Pt)variable temperature NMR spectroscopy. The 195Pt and 1H results are consistent with intramolecular mutual exchange of the P atoms with respect to the bridging ligands in all of the complexes 1\u20133. A detailed dynamical analysis carried out on complexes 2 and 3 shows that the dynamical process exchanges the P atoms within a single diphosphino ligand, and excludes the simultaneous P atom exchange in both ligands. The bite of the diphosphino ligands affects the rate of this process in the order 3 > 2 > 1. The process follows an activation law with \u394H\u2021 = 67 and 60 kJ mol^(-1) for 2 and 3, respectively, so that P\u2013Pt bond breaking should not be involved. The positive activation entropy (17\u201319 J K^(-1) mol^(-1) hints at a mechanism where the intermediate(s) have a less ordered structure than that of the stable complex. In accordance with the NMR results, two reactivity experiments provided further evidence of the intramolecular nature of the observed dynamics and exclude any equilibration path via Pt\u2013P and/or Pt\u2013Pt bond breaking. On these grounds, a mechanism involving rotation about a Pt\u2013Pt bond could be proposed

Analysis of ASTEC-Na capabilities for simulating a loss of flow CABRI experiment

Abstract This paper presents simulation results of the CABRI BI1 test using the code ASTEC-Na, currently under development, as well as a comparison of the results with available experimental data. The EU-JASMIN project (7th FP of EURATOM) centres on the development and validation of the new severe accident analysis code ASTEC-Na (Accident Source Term Evaluation Code) for sodium-cooled fast reactors whose owner and developer is IRSN. A series of experiments performed in the past (CABRI/SCARABEE experiments) and new experiments to be conducted in the new experimental sodium facility KASOLA have been chosen to validate the developed ASTEC-Na code. One of the in-pile experiments considered for the validation of ASTEC-Na thermal–hydraulic models is the CABRI BI1 test, a pure loss-of-flow transient using a low burnup MOX fuel pin. The experiment resulted in a channel voiding as a result of the flow coast-down leading to clad melting. Only some fuel melting took place. Results from the analysis of this test using SIMMER and SAS-SFR codes are also presented in this work to check their suitability for further code benchmarking purposes

LFR safety approach and main ELFR safety analysis results

This paper summarizes the approach to safety for the LFR systems, developed on the basis of the recommendations of the Generation IV International Forum (GIF) Risk and Safety Working Group (RSWG) and taking into account the fundamental safety objectives and the Defence-in-Depth approach, as described by IAEA Safety Guides, as well as the Safety quantitative objectives reported in the European Utilities Requirements (EUR). LEADER project activities are focused on the resolution of the key issues as they emerged from the 6th FP ELSY project attempting to reach a new industrial size European Lead-cooled Fast Reactor (ELFR) configuration. Apart from the safety approach, the main results of the ELFR safety transient analysis, where the most important design basis condition (DBC) and design extension condition (DEC) transient initiators were re-analyzed using the system codes RELAP5 (ENEA), TRACE-FRED (PSI), SIM-LFR (KIT) and SIMMER (CIRTEN), are summarized