Z-selective, anti-Markovnikov addition of alkoxides to terminal alkynes: an electron transfer pathway?

Potassium alkoxides undergo anti-Markovnikov addition to aryl-substituted alkynes with Z selectivity in DMF as the solvent. The yields and efficiency of the reaction was also found to be enhanced by the addition of a secondary amine ligand such as N,N′-dimethylethylenediamine. Mechanistic investigations suggest that the products, reaction rates and selectivity can be explained via a single electron transfer from the alkoxide to the alkyne. This leads to a radical anion intermediate, which then rapidly combines with the alkoxide to yield a vinyl anion whose lifetime governs the E:Z selectivity observed in the products

Hydrodynamic performance of a dual-floater hybrid system combining a floating breakwater and an oscillating-buoy type wave energy converter

The high cost of power generation impedes commercial-scale wave power operations. The objective of this work is to provide a cost-sharing solution by combining wave energy extraction and coastal protection. A two-dimensional numerical wave tank was developed using Star-CCM+ Computational Fluid Dynamics software to investigate the hydrodynamic performance of a dual-floater hybrid system consisting of a floating breakwater and an oscillating-buoy type wave energy converter (WEC), and was compared with published experimental results. The differences between the hydrodynamic performance of the hybrid system, a single WEC and a single breakwater were compared. Wave resonance in the WEC-breakwater gap has a significant impact on system performance, with the hybrid system demonstrating both better wave attenuation and wave energy extraction capabilities at low wave frequencies, i.e., wider effective frequency. Forces on the breakwater were generally reduced due to the WEC. Wave resonance in the narrow gap has an adverse effect on the energy efficiency of the hybrid system with an asymmetric WEC, while a beneficial effect with a symmetric WEC. The wave energy conversion efficiency of hybrid system can be improved by increasing the draft and width of the WEC and decreasing the distance between the WEC and the breakwater. The findings of this paper make wave energy economically competitive and commercial-scale wave power operations possible

Gamma radiolytic stability of CyMe4BTBP and the effect of nitric acid

The highly selective nitrogen donor ligand CyMe4BTBP for An(III) separation by solvent extraction was irradiated in a 60Co γ-source under varying conditions. Organic solutions of 10 mmol/L ligand in 1-octanol were contacted with different concentrations of nitric acid to observe the influence of an aqueous phase during irradiation. In subsequent liquid-liquid extraction experiments, distribution ratios of 241Am and 152Eu were determined. Distribution ratios decreased with increasing absorbed dose when irradiation was performed in the absence of nitric acid. With addition of nitric acid, initial distribution ratios remained constant over the whole examined dose range up to 300 kGy. For qualitative determination of radiolysis products, HPLC-MS measurements were performed. The protective effect of nitric acid was confirmed, since in samples irradiated with acid contact, no degradation products were observed, but only addition products of the 1-octanol molecule to the CyMe4BTBP molecule

Gamma radiolytic stability of CyMe4BTBP and the effect of nitric acid

The highly selective nitrogen donor ligand CyMe4BTBP for An(III) separation by solvent extraction was irradiated in a 60Co γ-source under varying conditions. Organic solutions of 10 mmol/L ligand in 1-octanol were contacted with different concentrations of nitric acid to observe the influence of an aqueous phase during irradiation. In subsequent liquid-liquid extraction experiments, distribution ratios of 241Am and 152Eu were determined. Distribution ratios decreased with increasing absorbed dose when irradiation was performed in the absence of nitric acid. With addition of nitric acid, initial distribution ratios remained constant over the whole examined dose range up to 300 kGy. For qualitative determination of radiolysis products, HPLC-MS measurements were performed. The protective effect of nitric acid was confirmed, since in samples irradiated with acid contact, no degradation products were observed, but only addition products of the 1-octanol molecule to the CyMe4BTBP molecule

Hydrodynamic performance of a dual-floater hybrid system combining a floating breakwater and an oscillating-buoy type wave energy converter

The high cost of power generation impedes commercial-scale wave power operations. The objective of this work is to provide a cost-sharing solution by combining wave energy extraction and coastal protection. A two-dimensional numerical wave tank was developed using Star-CCM+ Computational Fluid Dynamics software to investigate the hydrodynamic performance of a dual-floater hybrid system consisting of a floating breakwater and an oscillating-buoy type wave energy converter (WEC), and was compared with published experimental results. The differences between the hydrodynamic performance of the hybrid system, a single WEC and a single breakwater were compared. Wave resonance in the WEC-breakwater gap has a significant impact on system performance, with the hybrid system demonstrating both better wave attenuation and wave energy extraction capabilities at low wave frequencies, i.e., wider effective frequency. Forces on the breakwater were generally reduced due to the WEC. Wave resonance in the narrow gap has an adverse effect on the energy efficiency of the hybrid system with an asymmetric WEC, while a beneficial effect with a symmetric WEC. The wave energy conversion efficiency of hybrid system can be improved by increasing the draft and width of the WEC and decreasing the distance between the WEC and the breakwater. The findings of this paper make wave energy economically competitive and commercial-scale wave power operations possible

Transition-metal-free synthesis of ynol ethers and thioynol ethers via displacement at sp centers: a revised mechanistic pathway

We present here valuable extensions to our previous work in preparing highly functionalized, heteroatom-substituted alkynes via displacement at an sp center. Our results show that a wide range of ynol ethers can be prepared by the same methodology and that the same protocol can be applied to the synthesis of synthetically useful thioynol ethers. We also present new observations that have led us to revise our original hypothesis in favor of a pathway involving radical intermediates

Acute Care Surgery Models Worldwide: A Systematic Review

Background: The Acute Care Surgery (ACS) model was developed as a dedicated service for the provision of 24/7 nontrauma emergency surgical care. This systematic review investigated which components are essential in an ACS model and the state of implementation of ACS models worldwide. Methods: A literature search was conducted using PubMed, MEDLINE, EMBASE, Cochrane library, and Web of Science databases. All relevant data of ACS models were extracted from included articles. Results: The search identified 62 articles describing ACS models in 13 countries. The majority consist of a dedicated nontrauma emergency surgical service, with daytime on-site attending coverage (cleared from elective duties), and 24/7 in-house resident coverage. Emergency department coverage and operating room access varied widely. Critical care is fully embedded in the original US model as part of the acute care chain (ACC), but is still a separate unit in most other countries. While in most European countries, ACS is not a recognized specialty yet, there is a tendency toward more structured acute care. Conclusions: Large national and international heterogeneity exists in the structure and components of the ACS model. Critical care is still a separate component in most systems, although it is an essential part of the ACC to provide the best pre-, intra- and postoperative care of the physiologically deranged patient. Universal acceptance of one global ACS model seems challenging; however, a global consensus on essential components would benefit any healthcare system

Observations on transition metal free biaryl coupling: potassium tert-butoxide alone promotes the reaction without diamine or phenanthroline catalysts

Biaryl coupling (often labelled 'C-H activation') of aromatic systems can be achieved by potassium tert-butoxide alone in the absence of any amine or bipyridine catalyst (1,10-phenanthroline or N,N'-dimethylethylenediamine being the most common), previously reported to be essential. Various mechanistic studies and observations are presented which suggest that when 1,10-phenanthroline is employed as the catalyst, the alkoxide is destroyed almost immediately