One-electron pseudo-potential investigation of NO(X 2 Π)–Ar n clusters ( n = 1,2,3,4)

International audienc

In silico exploration of O-H^…X²⁺ (X = Cu, Ag, Hg) interaction, targeted adsorption zone, charge density iso-surface, O-H proton analysis and topographic parameters theory for calix[6]arene and calix[8]arene as model

In this work, the best adsorption targeted zones of the metal cations Ag2+, Cu2+ and Hg2+ at the surfaces or inside, outside the cavity of the calix[6] (CX[6]), calix[8]arene (CX[8]), NUBMOM (NUB-.) and LAYKUR (LAY-.) have been discussed. For X2+=Ag, Cu and Hg adsorbed onto the surface of CX[6,8], NUB-., and LAY-. and the morphologies of these complexes have been explained, the specific chosen surface structure has interfacial chemical properties to facilitate the stabilization of the cation in each targeted zone. The stability mechanisms have been investigated for the specific systems to understand the role of the cooperativity of the O…H (forming a donor-acceptor couple) bonding interactions for good selectivity to the cation in each host-guest in the acetonitrile solvent medium and the gas phase. For this purpose, all the host-guests chemical structures were investigated by the IR spectroscopy and O-H proton approach. The UV–visible absorption spectroscopy and the total DOS Orbital showed that all molecules possess a maximum absorption band in the range between 0.5 and 3.5 eV assigned to π–π* or n-π* transitions, the minimum band is characterized for the CX[6,8]-Cu2+, NUB-.Cu2+ and LAY-.Cu2+, while the highest band is specified for the complexation with the cation Ag2+. The Hirshfeld surface and the molecular electrostatic potential topography have demonstrated the selected targeted zone for the most stable configurations. The nature and the type of interaction formed between the chosen cation and the targeted area of the CX[6,8], NUB-. and LAY-. were typically studied by the Atom in Molecules (AIM) approach via non-covalent interaction (NCI) analyses. According to theoretical calculations, Cu2+, Ag2+ and Hg2+ cations were complexed with CX[6] and CX[8]-arenes in endo and exo-type form. In the endo complexes, it has been observed that Cu2+and Ag2+ cations enter the lower rim space where calixarene hydroxyl groups are located and form a complex in square planer geometry, as expected. This situation shows that the copper cation is planarly located in the calixarene core. These results show that the theoretical results are in good agreement with the experimental ones. In addition, our simulations point out the calix[6] arene and calix[8]arene were complexed with cations by “pinched” conformation, corresponding to best stable state

In silico exploration of O-H…X2+ (X = Cu, Ag, Hg) interaction, targeted adsorption zone, charge density iso-surface, O-H proton analysis and topographic parameters theory for calix[6]arene and calix[8]arene as model

International audienceIn this work, the best adsorption targeted zones of the metal cations Ag2+, Cu2+ and Hg2+ at the surfaces or inside, outside the cavity of the calix[6] (CX[6]), calix[8]arene (CX[8]), NUBMOM (NUB-.) and LAYKUR (LAY-.) have been discussed. For X2+=Ag, Cu and Hg adsorbed onto the surface of CX[6,8], NUB-., and LAY-. and the morphologies of these complexes have been explained, the specific chosen surface structure has interfacial chemical properties to facilitate the stabilization of the cation in each targeted zone. The stability mechanisms have been investigated for the specific systems to understand the role of the cooperativity of the O center dot center dot center dot H (forming a donor-acceptor couple) bonding interactions for good selectivity to the cation in each host-guest in the acetonitrile solvent medium and the gas phase. For this purpose, all the host-guests chemical structures were investigated by the IR spectroscopy and O-H proton approach. The UV-visible absorption spectroscopy and the total DOS Orbital showed that all molecules possess a maximum absorption band in the range between 0.5 and 3.5 eV assigned to pi-pi* or n-pi* transitions, the minimum band is characterized for the CX[6,8]-Cu2+, NUB-.Cu2+ and LAY-.Cu2+, while the highest band is specified for the complexation with the cation Ag2+. The Hirshfeld surface and the molecular electrostatic potential topography have demonstrated the selected targeted zone for the most stable configurations. The nature and the type of interaction formed between the chosen cation and the targeted area of the CX[6,8], NUB-. and LAY-. were typically studied by the Atom in Molecules (AIM) approach via non-covalent interaction (NCI) analyses. According to theoretical calculations, Cu2+, Ag2+ and Hg2+ cations were complexed with CX[6] and CX [8]-arenes in endo and exo-type form. In the endo complexes, it has been observed that Cu2+ and Ag2+ cations enter the lower rim space where calixarene hydroxyl groups are located and form a complex in square planer geometry, as expected. This situation shows that the copper cation is planarly located in the calixarene core. These results show that the theoretical results are in good agreement with the experimental ones. In addition, our simulations point out the calix[6] arene and calix[8]arene were complexed with cations by "pinched" conformation, corresponding to best stable state. (C) 2021 Elsevier B.V. All rights reserved

Collaborative effect of Csnk1a1 haploinsufficiency and mutant p53 in Myc induction can promote leukemic transformation

It is still not fully understood how genetic haploinsufficiency in del(5q) myelodysplastic syndrome (MDS) contributes to malignant transformation of hematopoietic stem cells. We asked how compound haploinsufficiency for Csnk1a1 and Egr1 in the common deleted region on chromosome 5 affects hematopoietic stem cells. Additionally, Trp53 was disrupted as the most frequently comutated gene in del(5q) MDS using CRISPR/Cas9 editing in hematopoietic progenitors of wild-type (WT), Csnk1a1–/+, Egr1–/+, Csnk1a1/Egr1–/+ mice. A transplantable acute leukemia only developed in the Csnk1a1–/+ Trp53–edited recipient. Isolated blasts were indefinitely cultured ex vivo and gave rise to leukemia after transplantation, providing a tool to study disease mechanisms or perform drug screenings. In a small-scale drug screening, the collaborative effect of Csnk1a1 haploinsufficiency and Trp53 sensitized blasts to the CSNK1 inhibitor A51 relative to WT or Csnk1a1 haploinsufficient cells. In vivo, A51 treatment significantly reduced blast counts in Csnk1a1 haploinsufficient/Trp53 acute leukemias and restored hematopoiesis in the bone marrow. Transcriptomics on blasts and their normal counterparts showed that the derived leukemia was driven by MAPK and Myc upregulation downstream of Csnk1a1 haploinsufficiency cooperating with a downregulated p53 axis. A collaborative effect of Csnk1a1 haploinsufficiency and p53 loss on MAPK and Myc upregulation was confirmed on the protein level. Downregulation of Myc protein expression correlated with efficient elimination of blasts in A51 treatment. The “Myc signature” closely resembled the transcriptional profile of patients with del(5q) MDS with TP53 mutation.</p

International Nosocomial Infection Control Consortiu (INICC) report, data summary of 43 countries for 2007-2012. Device-associated module

We report the results of an International Nosocomial Infection Control Consortium (INICC) surveillance study from January 2007-December 2012 in 503 intensive care units (ICUs) in Latin America, Asia, Africa, and Europe. During the 6-year study using the Centers for Disease Control and Prevention's (CDC) U.S. National Healthcare Safety Network (NHSN) definitions for device-associated health care–associated infection (DA-HAI), we collected prospective data from 605,310 patients hospitalized in the INICC's ICUs for an aggregate of 3,338,396 days. Although device utilization in the INICC's ICUs was similar to that reported from ICUs in the U.S. in the CDC's NHSN, rates of device-associated nosocomial infection were higher in the ICUs of the INICC hospitals: the pooled rate of central line–associated bloodstream infection in the INICC's ICUs, 4.9 per 1,000 central line days, is nearly 5-fold higher than the 0.9 per 1,000 central line days reported from comparable U.S. ICUs. The overall rate of ventilator-associated pneumonia was also higher (16.8 vs 1.1 per 1,000 ventilator days) as was the rate of catheter-associated urinary tract infection (5.5 vs 1.3 per 1,000 catheter days). Frequencies of resistance of Pseudomonas isolates to amikacin (42.8% vs 10%) and imipenem (42.4% vs 26.1%) and Klebsiella pneumoniae isolates to ceftazidime (71.2% vs 28.8%) and imipenem (19.6% vs 12.8%) were also higher in the INICC's ICUs compared with the ICUs of the CDC's NHSN

Safety and efficacy of non-steroidal anti-inflammatory drugs to reduce ileus after colorectal surgery

Background: Ileus is common after elective colorectal surgery, and is associated with increased adverse events and prolonged hospital stay. The aim was to assess the role of non-steroidal anti-inflammatory drugs (NSAIDs) for reducing ileus after surgery. Methods: A prospective multicentre cohort study was delivered by an international, student- and trainee-led collaborative group. Adult patients undergoing elective colorectal resection between January and April 2018 were included. The primary outcome was time to gastrointestinal recovery, measured using a composite measure of bowel function and tolerance to oral intake. The impact of NSAIDs was explored using Cox regression analyses, including the results of a centre-specific survey of compliance to enhanced recovery principles. Secondary safety outcomes included anastomotic leak rate and acute kidney injury. Results: A total of 4164 patients were included, with a median age of 68 (i.q.r. 57\u201375) years (54\ub79 per cent men). Some 1153 (27\ub77 per cent) received NSAIDs on postoperative days 1\u20133, of whom 1061 (92\ub70 per cent) received non-selective cyclo-oxygenase inhibitors. After adjustment for baseline differences, the mean time to gastrointestinal recovery did not differ significantly between patients who received NSAIDs and those who did not (4\ub76 versus 4\ub78 days; hazard ratio 1\ub704, 95 per cent c.i. 0\ub796 to 1\ub712; P = 0\ub7360). There were no significant differences in anastomotic leak rate (5\ub74 versus 4\ub76 per cent; P = 0\ub7349) or acute kidney injury (14\ub73 versus 13\ub78 per cent; P = 0\ub7666) between the groups. Significantly fewer patients receiving NSAIDs required strong opioid analgesia (35\ub73 versus 56\ub77 per cent; P &lt; 0\ub7001). Conclusion: NSAIDs did not reduce the time for gastrointestinal recovery after colorectal surgery, but they were safe and associated with reduced postoperative opioid requirement

Safety of hospital discharge before return of bowel function after elective colorectal surgery

© 2020 BJS Society Ltd Published by John Wiley & Sons LtdBackground: Ileus is common after colorectal surgery and is associated with an increased risk of postoperative complications. Identifying features of normal bowel recovery and the appropriateness for hospital discharge is challenging. This study explored the safety of hospital discharge before the return of bowel function. Methods: A prospective, multicentre cohort study was undertaken across an international collaborative network. Adult patients undergoing elective colorectal resection between January and April 2018 were included. The main outcome of interest was readmission to hospital within 30 days of surgery. The impact of discharge timing according to the return of bowel function was explored using multivariable regression analysis. Other outcomes were postoperative complications within 30 days of surgery, measured using the Clavien–Dindo classification system. Results: A total of 3288 patients were included in the analysis, of whom 301 (9·2 per cent) were discharged before the return of bowel function. The median duration of hospital stay for patients discharged before and after return of bowel function was 5 (i.q.r. 4–7) and 7 (6–8) days respectively (P < 0·001). There were no significant differences in rates of readmission between these groups (6·6 versus 8·0 per cent; P = 0·499), and this remained the case after multivariable adjustment for baseline differences (odds ratio 0·90, 95 per cent c.i. 0·55 to 1·46; P = 0·659). Rates of postoperative complications were also similar in those discharged before versus after return of bowel function (minor: 34·7 versus 39·5 per cent; major 3·3 versus 3·4 per cent; P = 0·110). Conclusion: Discharge before return of bowel function after elective colorectal surgery appears to be safe in appropriately selected patients