Iron homo- and heterobimetallic complexes supported by a symmetrical dinucleating ligand.

The selective synthesis of biomimetic Fe/Mn complexes able to mimic the geometry and catalytic activity of enzymes possessing this cofactor is still a challenge. Herein, we discuss the stepwise synthesis, characterization, and magnetic properties of a Fe(II)/Mn(II) species and related Fe(II)/Fe(II) complexes.

Study of curtaining effect reduction methods in Inconel 718 using a plasma focused ion beam.

The curtaining effect is a common challenge in focused ion beam (FIB) surface preparation. This study investigates methods to reduce this effect during plasma FIB milling of Inconel 718 (nickel-based superalloy). Platinum deposition, silicon mask and XeF gas injection were explored as potential solutions.

Thermal Evaluation of Silica-Based Insulated Magnet Wires from the Sol-Gel Process.

The conventional enameling process used in the fabrication of magnet wires requires harmful processes and products. The target of the industry in the actual context of electrification is to increase the electrical machines' efficiency. Indeed, the electrical insulation systems (EIS) of an electrical machine undergo various environmental constraints that can shorten their lifespans.

Binding, Release and Functionalization of Intact Pnictogen Tetrahedra Coordinated to Dicopper Complexes.

The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu (μ,η  : η -MeCN)][X] (X=weakly coordinating anion, NTf (1 a), FAl[OC F (C F )] (1 b), Al[OC(CF ) ] (1 c)) was replaced by white phosphorus (P ) or yellow arsenic (As ) to yield [(DPFN)Cu (μ,η  : η -E )][X] (E=P (2 a-c), As (3 a-c)). The molecular structures in the solid state reveal novel coordination modes for E tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E tetrahedra.

Role of growth hormone in hepatic and intestinal triglyceride-rich lipoprotein metabolism.

Background: Elevated plasma concentrations of hepatic- and intestinally-derived triglyceride-rich lipoproteins (TRL) are implicated in the pathogenesis of atherosclerotic cardiovascular disease and all-cause mortality. Excess of TRL is the driving cause of atherogenic dyslipidemia commonly occurring in insulin-resistant individuals such as patients with obesity, type 2 diabetes and metabolic syndrome. Interestingly, growth hormone (GH)-deficient individuals display similar atherogenic dyslipidemia, suggesting an important role of GH and GH deficiency in the regulation of TRL metabolism.

A Dicopper Nitrenoid by Oxidation of a CuCu Core: Synthesis, Electronic Structure, and Reactivity.

A dicopper nitrenoid complex was prepared by formal oxidative addition of the nitrenoid fragment to a dicopper(I) center by reaction with the iminoiodinane PhINTs (Ts = tosylate). This nitrenoid complex, (DPFN)Cu(μ-NTs)[NTf] (DPFN = 2,7-bis(fluorodi(2-pyridyl)methyl)-1,8-naphthyridine), is a powerful H atom abstractor that reacts with a range of strong C-H bonds to form a mixed-valence Cu(I)/Cu(II) μ-NHTs amido complex in the first example of a clean H atom transfer to a dicopper nitrenoid core. In line with this reactivity, DFT calculations reveal that the nitrenoid is best described as an iminyl (NR radical anion) complex.

A Combination of Single Nucleotide Polymorphisms is Associated with the Interindividual Variability of Cholesterol Bioavailability in Healthy Adult Males.

Scope: Cholesterol bioavailability displays a high interindividual variability, partly due to genetic factors. Existing studies have focused on single nucleotide polymorphisms (SNPs) analyzed individually, which only explained a minor fraction of the variability of this complex phenotype. The aim is to identify a combination of SNPs associated with a significant part of the variability in cholesterol bioavailability.

Bimetallics in a Nutshell: Complexes Supported by Chelating Naphthyridine-Based Ligands.

Bimetallic motifs are a structural feature common to some of the most effective and synthetically useful catalysts known, including in the active sites of many metalloenzymes and on the surfaces of industrially relevant heterogeneous materials. However, the complexity of these systems often hampers detailed studies of their fundamental properties. To glean valuable mechanistic insight into how these catalysts function, this research group has prepared a family of dinucleating 1,8-naphthyridine ligands that bind two first-row transition metals in close proximity, originally designed to help mimic the proposed active site of metal oxide surfaces.

A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes.

Reduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X-ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar "bow tie" configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H and CO .

Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex.

A dicopper complex featuring a symmetrically bridging nitrile ligand and supported by a binucleating naphthyridine-based ligand, [Cu( : -MeCN)DPFN](NTf), was treated with phosphaalkynes (RC[triple bond, length as m-dash]P, isoelectronic analogues of nitriles) to yield dicopper complexes that exhibit phosphaalkynes in rare : binding coordination modes. X-ray crystallography revealed that these unusual "tilted" structures exist in two isomeric forms (R "up" R "sideways"), depending on the steric profile of the phosphaalkyne's alkyl group (R = Me, Ad, or Bu). Only one isomer is observed in both solution and the solid state for R = Me (sideways) and Bu (up).

Discrimination of dynamically and post-dynamically recrystallized grains based on EBSD data: application to Inconel 718.

The importance of angular resolution in EBSD analyses is discussed based on an Inconel 718 sample containing several populations of recrystallized grains, with subtle differences in dislocation contents. Classical EBSD analyses (with angular resolution in the range of 0.5-1°) do not allow for distinguishing recrystallized grains grown dynamically or post-dynamically.

Selective Synthesis of a Series of Isostructural M Cu Heterobimetallic Complexes Spontaneously Assembled by an Unsymmetrical Naphthyridine-Based Ligand.

Metal-metal cooperation is integral to the function of many enzymes and materials, and model complexes hold enormous potential for providing insights into the capabilities of analogous multimetallic cores. However, the selective synthesis of heterobimetallic complexes still presents a significant challenge, especially for systems that hold the metals in close proximity and feature open or reactive coordination sites for both metals. To address this issue, a rigid, naphthyridine-based dinucleating ligand featuring distinct binding environments was synthesized.

Titanocene-Mediated Dinitrile Coupling: A Divergent Route to Nitrogen-Containing Polycyclic Aromatic Hydrocarbons.

A general synthetic strategy for the construction of large, nitrogen-containing polycyclic aromatic hydrocarbons (PAHs) is reported. The strategy involves two key steps: (1) a titanocene-mediated reductive cyclization of an oligo(dinitrile) precursor to form a PAH appended with di(aza)titanacyclopentadiene functionality; (2) a divergent titanocene transfer reaction, which allows final-step installation of one or more o-quinone, diazole, or pyrazine units into the PAH framework. The new methodology enables rational, late-stage control of HOMO and LUMO energy levels and thus photophysical and electrochemical properties, as revealed by UV/vis and fluorescence spectroscopy, cyclic voltammetry, and DFT calculations.

Impact of bariatric surgery on apolipoprotein C-III levels and lipoprotein distribution in obese human subjects.

Background: Elevated apolipoprotein C-III (apoC-III) has been postulated to contribute to the atherogenic dyslipidemia seen in obesity and insulin-resistant states, mainly by impairing plasma triglyceride-rich lipoprotein (TRL) metabolism. Bariatric surgery is associated with improvements of several obesity-associated metabolic abnormalities, including a reduction in plasma triglycerides (TGs) and an increase in plasma high-density lipoprotein cholesterol (HDL-C).

Objectives: We investigated the specific effect of bariatric surgery on apoC-III concentrations in plasma, non-HDL, and HDL fractions in relation to lipid profile parameters evolution.

Icteric human samples: Icterus index and method of estimating an interference-free value for 16 biochemical analyses.

Background: Hemolysis, Icterus, and Lipemia constituting the HIL index, are the most common causes of interference with accurate measurement in biochemistry. This study focuses on bilirubin interference, aiming to identify the analyses impacted and proposing a way to predict nominal interference-free analyte concentrations, based on both analyte level and Icterus Index (I ).

Methods: Sixteen common analytes were studied: alanine aminotransferase (ALT), albumin (ALB), alkaline phosphatase (ALP), amylase (AMY), aspartate aminotransferase (AST), total cholesterol (CHOLT), creatinine (CREA, enzymatic method), fructosamine (FRUC), gamma-glutamyl transferase (GGT), HDL cholesterol (HDLc), total iron (Iron), lipase (LIP), inorganic phosphorus (Phos), total protein (PROT), triglycerides (TG), and uric acid (UA).

A chronicle of the changes undergone by a maritime territory, the Bay of Toulon (Var Coast, France), and their consequences on PCB contamination.

This study evaluated the distribution of polychlorinated biphenyls (PCBs) in 39 surface sediment samples and four cores collected in Toulon Bay, a semiclosed area submitted to various anthropogenic inputs. The concentration of PCBs in the superficial sediment samples ranged from 1.7 to 2530 ng g(-1) dry weight.

Effects of bariatric surgery on hepatic and intestinal lipoprotein particle metabolism in obese, nondiabetic humans.

Objective: The dyslipidemia of obesity and other insulin-resistant states is characterized by the elevation of plasma triglyceride-rich lipoproteins (TRL) of both hepatic (apoB-100-containing very low-density lipoprotein) and intestinal (apoB-48-containing chylomicrons) origin. Bariatric surgery is a well-established and effective modality for the treatment of obesity and is associated with improvements in several metabolic abnormalities associated with obesity, including a reduction in plasma triglycerides. Here, we have investigated the effect of bariatric surgery on TRL metabolism.

Influence of diet and sample collection time on 77 laboratory tests on healthy adults.

Objectives: We studied the effect of a standardized breakfast or lunch before blood sampling on 77 analytes.

Design And Methods: The mean difference between assays from 20 healthy adults was calculated on blood samples taken before and after food intake. Significant differences were tested using two-tailed Student t-test and compared to the acceptable limits derived from analytical and intraindividual biological variation.

Cognitive abilities underlying second-language vocabulary acquisition in an early second-language immersion education context: a longitudinal study.

First-language (L1) and second-language (L2) lexical development has been found to be strongly associated with phonological processing abilities such as phonological short-term memory (STM), phonological awareness, and speech perception. Lexical development also seems to be linked to attentional and executive skills such as auditory attention, flexibility, and response inhibition. The aim of this four-wave longitudinal study was to determine to what extent L2 vocabulary acquired through the particular school context of early L2 immersion education is linked to the same cognitive abilities.

Growth hormone level at admission and its evolution during refeeding are predictive of short-term outcome in restrictive anorexia nervosa.

The growth hormone (GH)–insulin-like growth factor-1 (IGF-1) axis is dramatically altered in patients with anorexia nervosa (AN). The aim of the present study was to investigate whether GH and IGF-1 could be predictors of outcome in patients with a restrictive form of AN. Blood levels of GH, IGF-1, adipocytokines, ghrelin, insulin, glucose, and sex and thyroid hormones were measured in eleven women inpatients with AN and in ten healthy women controls.

Comparative in vitro performance of three small-volume valved holding chambers with beclomethasone/formoterol pressurized metered dose inhaler.

Background: The use of valved holding chambers (VHCs) with pressurized metered dose inhalers (pMDIs) is reported to reduce the oral deposition of inhaled drugs and to facilitate the handling of these devices by patients, especially children. Although the number of commercially available VHCs is increasing, the correct choice of VHC in clinical practice is important, because VHCs are not equally effective regarding medication delivery. Hence, we aimed to evaluate the use of three small-volume VHCs-Vortex(®), AeroChamber(®) Plus (ACP), and Able Spacer™ (AS)-along with a commercial pMDI containing a combination of beclomethasone and formoterol (Innovair(®)) frequently used by asthma patients.

Unacylated Ghrelin is associated with the isolated low HDL-cholesterol obese phenotype independently of insulin resistance and CRP level.

Background: Low plasma high-density lipoprotein-cholesterol (HDL-c) level is commonly present in obesity and represents an independent cardiovascular risk factor. However, obese patients are a very heterogeneous population and the factors and mechanisms that contribute to low HDL-c remain unclear. The aim of this study was to investigate the association between plasma HDL-c levels and plasma hormonal profiles (insulin, adiponectin, resistin, leptin and ghrelin) in subsets of class II and III obese patients.

Absence of acute inhibitory effect of insulin on chylomicron production in type 2 diabetes.

Objective: Overproduction of intestinally derived apoB-48-containing triglyceride-rich lipoproteins (TRLs) (chylomicrons) has recently been described in type 2 diabetes, as is known for hepatic TRL-apoB-100 (very-low-density lipoprotein) production. Furthermore, insulin acutely inhibits both intestinal and hepatic TRL production, whereas this acute inhibitory effect on very-low-density lipoprotein production is blunted in type 2 diabetes. It is not currently known whether this acute effect on chylomicron production is similarly blunted in humans with type 2 diabetes.

Cholesterol-absorber status modifies the LDL cholesterol-lowering effect of a Mediterranean-type diet in adults with moderate cardiovascular risk factors.

LDL-cholesterol (LDL-C) reduction may be achieved by various types of prudent diets, but their effects on surrogate markers of cholesterol absorption and synthesis have not been well studied in humans. We aimed to assess whether the extent of cholesterol absorption or synthesis, and cholesterol concentrations, are modified in adults when they shift from a Western-type diet (WD) to a combined low-fat, low-cholesterol/Mediterranean-type diet (LFCMD). Cholestanol and sitosterol, as well as desmosterol and lathosterol, surrogate markers of cholesterol absorption or synthesis, respectively, were quantified in the serum of 125 fasting, middle-aged participants at moderate cardiovascular risk.

Cholesterol absorption status and fasting plasma cholesterol are modulated by the microsomal triacylglycerol transfer protein -493 G/T polymorphism and the usual diet in women.

An important inter-individual variability in cholesterol absorption has been reported. It could result from polymorphisms in genes coding for proteins involved in the absorption process and in interaction with dietary intakes. To assess whether the extent of cholesterol absorption or synthesis is modified in adult women according to the -493 G/T polymorphism in the microsomal triglyceride transfer protein gene (MTP) and/or the habitual diet.