Diazo ester insertion in N-H bonds of amino acid derivatives and insulin catalyzed by water-soluble iron and ruthenium porphyrin complexes (FeTSPPCl) as application of carbenoid transfer in aqueous media

International audienceThe metal complex FeTSPPCl (5,10,15,20-tetrakis)-(4-sulfonato-phenyl)-porphyrin-iron(III) chloride is an active catalyst for carbenoid insertion in N–H bonds of aminoacid derivatives in aqueous media. A variety of diazoacetates and methyl diazophosphonate were used as carbenoid precursors. The commercially available iron porphyrin complex can also selectively catalyze alkylation of the N-terminus of insulin (chain B

Effects of hospital facilities on patient outcomes after cancer surgery: an international, prospective, observational study

Background Early death after cancer surgery is higher in low-income and middle-income countries (LMICs) compared with in high-income countries, yet the impact of facility characteristics on early postoperative outcomes is unknown. The aim of this study was to examine the association between hospital infrastructure, resource availability, and processes on early outcomes after cancer surgery worldwide.Methods A multimethods analysis was performed as part of the GlobalSurg 3 study-a multicentre, international, prospective cohort study of patients who had surgery for breast, colorectal, or gastric cancer. The primary outcomes were 30-day mortality and 30-day major complication rates. Potentially beneficial hospital facilities were identified by variable selection to select those associated with 30-day mortality. Adjusted outcomes were determined using generalised estimating equations to account for patient characteristics and country-income group, with population stratification by hospital.Findings Between April 1, 2018, and April 23, 2019, facility-level data were collected for 9685 patients across 238 hospitals in 66 countries (91 hospitals in 20 high-income countries; 57 hospitals in 19 upper-middle-income countries; and 90 hospitals in 27 low-income to lower-middle-income countries). The availability of five hospital facilities was inversely associated with mortality: ultrasound, CT scanner, critical care unit, opioid analgesia, and oncologist. After adjustment for case-mix and country income group, hospitals with three or fewer of these facilities (62 hospitals, 1294 patients) had higher mortality compared with those with four or five (adjusted odds ratio [OR] 3.85 [95% CI 2.58-5.75]; p<0.0001), with excess mortality predominantly explained by a limited capacity to rescue following the development of major complications (63.0% vs 82.7%; OR 0.35 [0.23-0.53]; p<0.0001). Across LMICs, improvements in hospital facilities would prevent one to three deaths for every 100 patients undergoing surgery for cancer.Interpretation Hospitals with higher levels of infrastructure and resources have better outcomes after cancer surgery, independent of country income. Without urgent strengthening of hospital infrastructure and resources, the reductions in cancer-associated mortality associated with improved access will not be realised

Competing structures in (In,Ga)Se and (In,Ga)2Se3 semiconductors

International audienceThe electronic structure of four polytypes (β, γ, δ and ε) of hexagonal GaSe and InSe is cal-culated from first principles, using the WIEN2k and VASP codes and PBEsol prescription for theexchange-correlation potential, aiming specifically at elucidating the crystallographic parametersand comparing the energy placement of corresponding competing structures.Further on, the compounds with different composition of the same constituents, namely theordered-vacancies systems Ga2 Se3 and In2Se3, were subject to a similar study, of which the relaxedcrystal structure data for three different phases is reported. Comparison is done with the nomi-nal wurtzite structure over which the cation vacancies are introduced, and the relaxation patterndiscussed

Crystal structure and energy bands of (Ga/In)Se and Cu(In,Ga)Se 2 semiconductors in comparison

International audienceCrystallographic and electronic structures of binary compounds GaSe and InSe, known to exist in several polytype modifications, are discussed in comparison with those of chalcopyrite-type CuInSe2, CuGaSe2, and their solid solutions. The results are obtained within the density-functional theory (DFT), using two calculation codes, WIEN2k and VASP. The van der Waals interaction, important in stabilizing the structure of the layer compounds GaSe and InSe, was taken into account in the VASP calculation along the scheme of Grimme. For obtaining more realistic electronic band structures than is possible with the conventional generalized gradient approximation (GGA), the modified Becke–Johnson (mBJ) exchange–correlation (XC) potential was used, as implemented in the WIEN2k code. The results of two computer codes were compared in what concerns the optimization of the ground-state structures. The similarities in electronic structures of the systems studied are discussed under an angle of general trends proper to the compounds of Cu–(In,Ga)–Se composition

Room-temperature columnar mesophases of nickel-bis(dithiolene) metallomesogens

International audienceDiscotic nickel dithiolene complexes are prepared by sulfuration of original benzil proligands appended with gallate fragments carrying long carbon chains (n = 8, 12, 16), separated from the dithiolene core by ester or amide linkers. The electronic properties of these functional nickel dithiolene complexes were studied by cyclic voltammetry and UV-vis spectroscopy. The thermotropic properties were investigated by a combination of POM observations, DSC analysis and X-ray diffraction experiments. The neutral dithiolene complexes, denoted CnesterNi and CnamideNi, all exhibit columnar phases over large temperature ranges including room temperature. CnesterNi complexes form columnar mesophases of rectangular (pseudo-hexagonal) and hexagonal symmetry whereas the amide linkage in CnamideNi complexes strongly stabilizes hexagonal columnar mesophases far below room temperature, as illustrated by C12amideNi which displays a Colh mesophase from −18 up to +177 °C. The role of hydrogen bonding between the amide functions in the stabilisation of the mesophases in CnamideNi complexes and their benzil precursors was confirmed by IR spectroscopy. Moreover, the C8amideNi compound exhibits a cubic phase, stable over [similar]50 °C, from 155 to 203 °C. Models for the arrangements within the different columnar mesophases are proposed and discussed

In Situ Alkylation of Reconstructed Human Epidermis by Methyl Methanesulfonate: A Quantitative HRMAS NMR Chemical Reactivity Mapping

International audienc

Effect of Nitrile-Functionalization of Imidazolium-Based Ionic Liquids on Their Transport Properties, Both Pure and Mixed with Lithium Salts.

CAPLUS AN 2014:2146289(Journal; Online Computer File)International audienceThe influence of the presence of a nitrile group in the cation of imidazolium-based ionic liquids on their transport properties was investigated. As these liquids can be used as electrolytes in lithium ion batteries, their mixtures with lithium salts were also considered. 1-Butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide, [C1C4Im][NTf2], 1-butylnitril-3-methylimidazolium bis(trifluoromethylsulphonyl)imide, [C1C3CNIm][NTf2], and their mixtures with bis(trifluoromethylsulphonyl)imide lithium, Li[NTf2], were studied. Their mass transport properties (viscosity, ionic conductivity, self-diffusion) were experimentally determined. NMR spectroscopy was also used to explore molecular organization and interactions in these systems. The addition of a cyano group increases the viscosity and the ionicity of the liquid. The effect of lithium ion is more pronounced on [C1C3CNIm][NTf2], with interactions between Li+ and the nitrile group

Global variation in postoperative mortality and complications after cancer surgery: a multicentre, prospective cohort study in 82 countries

Background: 80% of individuals with cancer will require a surgical procedure, yet little comparative data exist on early outcomes in low-income and middle-income countries (LMICs). We compared postoperative outcomes in breast, colorectal, and gastric cancer surgery in hospitals worldwide, focusing on the effect of disease stage and complications on postoperative mortality. Methods: This was a multicentre, international prospective cohort study of consecutive adult patients undergoing surgery for primary breast, colorectal, or gastric cancer requiring a skin incision done under general or neuraxial anaesthesia. The primary outcome was death or major complication within 30 days of surgery. Multilevel logistic regression determined relationships within three-level nested models of patients within hospitals and countries. Hospital-level infrastructure effects were explored with three-way mediation analyses. This study was registered with ClinicalTrials.gov, NCT03471494. Findings: Between April 1, 2018, and Jan 31, 2019, we enrolled 15 958 patients from 428 hospitals in 82 countries (high income 9106 patients, 31 countries; upper-middle income 2721 patients, 23 countries; or lower-middle income 4131 patients, 28 countries). Patients in LMICs presented with more advanced disease compared with patients in high-income countries. 30-day mortality was higher for gastric cancer in low-income or lower-middle-income countries (adjusted odds ratio 3·72, 95% CI 1·70–8·16) and for colorectal cancer in low-income or lower-middle-income countries (4·59, 2·39–8·80) and upper-middle-income countries (2·06, 1·11–3·83). No difference in 30-day mortality was seen in breast cancer. The proportion of patients who died after a major complication was greatest in low-income or lower-middle-income countries (6·15, 3·26–11·59) and upper-middle-income countries (3·89, 2·08–7·29). Postoperative death after complications was partly explained by patient factors (60%) and partly by hospital or country (40%). The absence of consistently available postoperative care facilities was associated with seven to 10 more deaths per 100 major complications in LMICs. Cancer stage alone explained little of the early variation in mortality or postoperative complications. Interpretation: Higher levels of mortality after cancer surgery in LMICs was not fully explained by later presentation of disease. The capacity to rescue patients from surgical complications is a tangible opportunity for meaningful intervention. Early death after cancer surgery might be reduced by policies focusing on strengthening perioperative care systems to detect and intervene in common complications. Funding: National Institute for Health Research Global Health Research Unit