Curriemaldonado4468

Halide abstraction of the carbene-coordinated pnictinidenes (MecAAC)EGa(Cl)L (E = As 1, Sb 2, Bi 3, MecAAC = [H2C(CMe2)2NDipp]C; L = HC[C(Me)NDipp]2; Dipp = 2,6-i-Pr2C6H3) yielded the series of cationic group 15 compounds [(MecAAC)EGaL][Al(ORF)4] (E = As 4, Sb 5; Al(ORF)4 = Al(OC(CF3)3)4) and [(MecAAC)EGaL][B(ArF)4] (E = Sb 6, Bi 7; B(ArF)4 = B[C6H3(CF3)2]4), which were characterized by heteronuclear NMR spectroscopy and sc-XRD. The electronic nature of the cations [(MecAAC)EGaL]+ is controlled by the central pnictogen atom, according to quantum chemical calculations. The calculations furthermore demonstrated that compounds containing the lighter pnictogens (E = N, P) are best described as heteronuclear allyl cations, whereas heavier pnictogen atoms (E = As, Sb, Bi) serve as a trap for the positive charge, resulting in carbene-stabilized heterovinyl-type structures.Membrane distillation (MD) has potential to become a competitive technology for managing hypersaline brine but not until the critical challenge of mineral scaling is addressed. The state-of-the-art approach for mitigating mineral scaling in MD involves the use of superhydrophobic membranes that are difficult to fabricate and are commercially unavailable. This study explores a novel operational strategy, namely, negative pressure direct contact membrane distillation (NP-DCMD) that can minimize mineral scaling with commercially available hydrophobic membranes and at the same time enhance the water vapor flux substantially. By applying a negative gauge pressure on the feed stream, NP-DCMD achieved prolonged resistance to CaSO4 scaling and a dramatic vapor flux enhancement up to 62%. The exceptional scaling resistance is attributable to the formation of a concave liquid-gas under a negative pressure that changes the position of the water-air interface to hinder interfacial nucleation and crystal growth. The substantial flux enhancement is caused by the reduced molecular diffusion resistance within the pores and the enhanced heat transfer kinetics across the boundary layer in NP-DCMD. Achieving substantial performance improvement in both the scaling resistance and vapor flux with commercial membranes, NP-DCMD is a significant innovation with vast potential for practical adoption due to its simplicity and effectiveness.Based on the exposure data sets from the Tracking Air Pollution in China (TAP, http//tapdata.org.cn/), we characterized the spatiotemporal variations in PM2.5 and O3 exposures and quantified the long- and short-term exposure related premature deaths during 2013-2020 with respect to the two-stage clean air actions (2013-2017 and 2018-2020). We find a 48% decrease in national PM2.5 exposure during 2013-2020, although the decrease rate has slowed after 2017. At the same time, O3 pollution worsened, with the average April-September O3 exposure increased by 17%. The improved air quality led to 308 thousand and 16 thousand avoided long- and short-term exposure related deaths, respectively, in 2020 compared to the 2013 level, which was majorly attributed to the reduction in ambient PM2.5 concentration. It is also noticed that with smaller PM2.5 reduction, the avoided long-term exposure associated deaths in 2017-2020 (13%) was greater than that in 2013-2017 (9%), because the exposure-response curve is nonlinear. learn more As a result of the efforts in reducing PM2.5-polluted days with the daily average PM2.5 higher than 75 μg/m3 and the considerable increase in O3-polluted days with the daily maximum 8 h average O3 higher than 160 μg/m3, deaths attributable to the short-term O3 exposure were greater than those due to PM2.5 exposure since 2018. Future air quality improvement strategies for the coordinated control of PM2.5 and O3 are urgently needed.A range of palladium complexes featuring electronically modified, imidazole-based abnormal N-heterocyclic carbene (aNHC) ligands have been prepared in the hopes of accessing a new class of cationic aNHC ligands electronically distinct from normal NHCs and aNHCs. These palladium complexes represent the first examples of transition metal-ligated aNHC complexes featuring a cationic moiety adjacent to the abnormal carbene center. It was anticipated that these design principles could facilitate electron transfer between the imidazolinylidene and the cationic heterocycle, thus reducing the electron density at the abnormal carbene center. However, this case study suggests that greater conformational restrictions that allow for heterocycle coplanarity are necessary to achieve significant electron transfer and enable access to a new class of cationic charge-appended aNHCs with unique electronic properties.An efficient protocol involving the transformation of sequentially generated recursive anions from heterocyclic precursors to orthogonally strap diynones through one pot transition-metal-free spirocyclopentannulation has been devised, employing oxindoles and pyrazolones as prototypical platforms. Insights into these regioselective tandem Michael-anti-Michael processes have been gleaned through DFT calculations.High chlorine doses (50-200 mg/L) are used in postharvest washing facilities to control foodborne pathogen outbreaks. However, chlorine can react with biopolymers (e.g., lipids) within the produce to form chlorinated byproducts that remain in the food. During chlorination of micelles of oleic acid, an 18-carbon alkene fatty acid, chlorine added rapidly across the double bond to form the two 9,10-chlorohydrin isomers at a 100% yield. The molar conversion of lipid-bound oleic acid to 9,10-chlorohydrins in chlorine-treated glyceryl trioleate and produce was much lower, reflecting the restricted access of chlorine to lipids. Yields from spinach treated with 100 mg/L chlorine at 7.5 °C for 2 min increased from 0.05% (0.9 nmol/g-spinach) for whole leaf spinach to 0.11% (2 nmol/g) when shredding increased chlorine access. Increasing temperature (21 °C) and chlorine contact time (15 min) increased yields from shredded spinach to 0.83% (22 nmol/g) at 100 mg/L chlorine and to 1.8% (53 nmol/g) for 200 mg/L chlorine. Oleic acid 9,10-chlorohydrin concentrations were 2.4-2.7 nmol/g for chlorine-treated (100 mg/L chlorine at 7.5 °C for 2 min) broccoli, carrots, and butterhead lettuce, but 0.5-1 nmol/g for cabbage, kale, and red leaf lettuce. Protein-bound chlorotyrosine formation was higher in the same vegetables (5-32 nmol/g). The Chinese hamster ovary cell chronic cytotoxicity LC50 value for oleic acid 9,10-chlorohydrins was 0.106 mM. The cytotoxicity associated with the chlorohydrins and chlorotyrosines in low masses (9-52 g) of chlorine-washed vegetables would be comparable to that associated with trihalomethanes and haloacetic acids at levels of regulatory concern in drinking water.It is vital to search for highly efficient bifunctional oxygen evolution/reduction reaction (OER/ORR) electrocatalysts for sustainable and renewable clean energy. Herein, we propose a single transition-metal (TM)-based defective AlP system to validate bifunctional oxygen electrocatalysis by using the density functional theory (DFT) method. We found that the catalytic activity is enhanced by substituting two P atoms with two N atoms in the Al vacancy of the TM-anchored AlP monolayer. Specifically, the overpotential of OER(ORR) in Co- and Ni-based defective AlP systems is found to be 0.38 (0.25 V) and 0.23 V (0.39 V), respectively, showing excellent bifunctional catalytic performance. The results are further presented by establishing the volcano plots and contour maps according to the scaling relation of the Gibbs free-energy change of *OH, *O, and *OOH intermediates. The d-band center and the product of the number of d-orbital electrons and electronegativity of the TM atom are the ideal descriptors for this system. To investigate the activity origin of the OER/ORR process, we performed the machine learning (ML) algorithm. The result indicates that the number of TM-d electrons (Ne), the radius of TM atoms (rd), and the charge transfer of TM atoms (Qe) are the three primary descriptors characterizing the adsorption behavior. Our results can provide a theoretical guidance for designing highly efficient bifunctional electrocatalysts and pave a way for the DFT-ML hybrid method in catalysis research.Acyclic quaternary carbon stereocenters exist widely in natural products and bioactive molecules, but their enantioselective construction remains a prominent challenge. In particular, multicomponent enantioselective couplings of simple precursors to acyclic all-carbon quaternary stereocenters are very rare. We describe herein an N-heterocyclic carbene (NHC)-Ni catalyzed redox-economical three-component reaction of aldehydes, alkynes, and enones that proceeds in a highly chemo-, regio-, and enantioselective manner. A wide variety of valuable acyclic α-quaternary chiral ketones were synthesized in a single step with 100% atom economy. This reaction proceeds through the formation of a transient cyclic enolate followed by an aldol reaction/ring-opening sequence. The strategy is expected to inspire new and efficient approaches to generate other acyclic quaternary stereocenters.Resolution of the XIII Congress of Surgeons of Russia.The authors report a rare disease at the junction of urology and cardiovascular surgery (arteriovenous malformation (AVM) of the scrotum). The options for correction of this disease are discussed. The authors describe the complications of natural course of disease and their treatment. Treatment strategy with AVM embolization is substantiated. Postoperative regression of symptoms is emphasized. The authors concluded safety and effectiveness of interventional correction of this disease.The authors describe successful treatment of a patient with consequences of a mine-explosive wound of the right thigh and abdomen, including damage to the duodenum. Staged surgical treatment made it possible to identify and eliminate defects in primary surgical treatment in time. Thus, favorable treatment results were obtained.Incidence of postoperative sternomediastinitis depends on various risk factors and makes up 8%. Surgical debridement with local management of the wound are used to achieve wound sterility. In some cases, sternectomy or subtotal sternal resection are performed for total sternal osteomyelitis with osteoporotic bone and multiple fractures. This procedure results an extensive bone defect. The final stage is anterior chest wall reconstruction. The most popular method is wound closure with autologous muscle or omental flaps. The authors describe a patient with sternomediastinitis who underwent staged treatment. At the final stage, subtotal sternectomy with simultaneous omentoplasty were performed. Additionally, mammary-gastroepiploic bypass grafting with right internal mammary artery and right gastroepiploic artery was carried out for additional vascularization of the omental flap. We found no similar surgery for sternomediastinitis in the literature. Long-term treatment outcome was followed-up (>50 months of relapse-free period and good quality of life).Hypertrophic cardiomyopathy (HCM) is a hereditary myocardial disease characterized by ventricular wall and interventricular septum thickening not associated with heart valve disease or any other external cause. Considering different localization of left ventricular obstruction, surgeons should be aware of various surgical approaches to various segments of interventricular septum. A personalized approach to each patient is essential to achieve favorable postoperative effect with minimal incidence of complications. This review is devoted to various surgical approaches to interventricular septum for different phenotypic variants of HCM.