Summary
PRIVATE-ATLANTIC (P2Y12 Receptor Inhibition with VASP Testing using Elisa kit during the ATLANTIC study) is a pre-specified substudy of the randomised, double-blind ATLANTIC trial in patients ...with ST-segment elevation myocardial infarction, designed to help interpret the main trial results. The primary objective of ATLANTIC was to assess coronary reperfusion prior to percutaneous coronary intervention (PCI) with pre- vs in-hospital ticagrelor 180 mg loading dose (LD). PRIVATE-ATLANTIC assessed platelet inhibition in 37 patients by measurement of vasodilator-associated stimulated phosphoprotein (VASP) platelet reactivity index (PRI) and VerifyNow platelet reactivity units (PRU) before angiogram (T1), immediately after PCI (T2), 1 (T3), and 6 (T4) hours (h) after PCI, and before next study drug administration (T5). The median time difference between the two ticagrelor LD was 41 minutes. Platelet reactivity was unaffected at T1 when measured by VASP-PRI (89.8 vs 93.9% for pre- and in-hospital ticagrelor, respectively; p = 0.18) or PRU (239 vs 241; p = 0.82). Numerical differences were apparent at T2 and maximal at T3. Morphine administration significantly delayed onset of platelet inhibition at T3 (VASP-PRI 78.2 vs 23.4% without morphine; p = 0.0116) and T4 (33.1 vs 11.0%; p = 0.0057). In conclusion, platelet inhibition in ATLANTIC was unaffected by pre-hospital ticagrelor administration at the time of initial angiogram due to the short transfer delay. The maximum difference in platelet inhibition was detected 1 h after PCI (T3). Morphine administration was associated with delayed onset of action of ticagrelor and appeared more important than timing of ticagrelor administration.
We construct here a highly active and stable Co9S8@CdIn2S4 heterostructure for photocatalytic H2 evolution under visible light. In a hierarchical hollow construction with closely connected ...heterogeneous shells, two photoactive sulfide semiconductors are incorporated rationally. This unique architecture can efficiently allow photoinduced charges to be separated and transferred and provide a broad surface area and exposure of rich sites for photocatalytic redox reactions. The Co9S8@CdIn2S4 hierarchical hollow heterostructure shows enhanced light-harvesting ability and remarkable catalytic activity because of its distinctive structural and compositional advantages. The photocatalyst shows a high hydrogen evolution rate of 4604 μmol h–1 g–1 without any noble metal as a cocatalyst under 1.5 AM simulated light irradiation. In this work, using the two-dimensional ultrathin subunits with distinct structural and compositional benefits, we show how this material can be interfaced successfully to give intriguing photophysical properties.
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IJS, KILJ, NUK, PNG, UL, UM
Surface atomic arrangement and coordination of photocatalysts highly exposed to different crystal facets significantly affect the photoreactivity. However, controversies on the true photoreactivity ...of a specific facet in heterogeneous photocatalysis still exits. Herein, we exemplified well‐defined BiOBr nanosheets dominating with respective facets, (001) and (010), to track the reactivity of crystal facets for photocatalytic water splitting. The real photoreactivity of BiOBr‐(001) were evidenced to be significantly higher than BiOBr‐(010) for both hydrogen production and oxygen evolution reactions. Further in situ photochemical probing studies verified the distinct reactivity is not only owing to the highly exposed facets, but dominated by the co‐exposing facets, leading to an efficient spatial separation of photogenerated charges and further making the oxidation and reduction reactions separately occur with different reaction rates, which ordains the fate of the true photoreactivity.
Intrinsic facet‐dependent photoreactivity: It is demonstrated that the spatial separation of photogenerated charges between top and lateral facets of BiOBr nanosheets dominates the intrinsic facet‐dependent photoreactivity, and not the commonly recognized highly exposed active facets.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for ...the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>>Ar-OMe>ArCH₂-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons.
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BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
The electrophilic/nucleophilic character of a series of captodative (CD) ethylenes involved in polar cycloaddition reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. ...The transition state structures for the electrophilic/nucleophilic interactions of two CD ethylenes toward a nucleophilically activated ethylene, 2-methylene-1,3-dioxolane, and an electrophilically activated ethylene, 1,1-dicyanoethyelene, have been studied, and their electronic structures have been characterized using both NBO and ELF methods. Analysis of the reactivity indexes of the CD ethylenes explains the reactivity of these species. While the electrophilicity of the molecules accounts for the reactivity toward nucleophiles, it is shown that a simple index chosen for the nucleophilicity, Ν, based on the HOMO energy is useful explaining the reactivity of these CD ethylenes toward electrophiles.
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IJS, KILJ, NUK, PNG, UL, UM
This essay tells the story of the conception of the Two‐State Reactivity (TSR) notion. Since scientific career is part of life's flow, the story blends sub‐stories of scientific colleagues and ...events. This is also a story of a beguiling paradigm, which has started from a puzzling reactivity of the diatomic oxidant FeO+, has continued to larger oxidants, like the active species of Cytochrome P450 and of nonheme enzymes, and its extension to reductive processes. Finally, the essay discusses prospects of experimental probing of the reactive spin‐state, and of the transition state constitution for these reactions by means of tunneling‐augmented kinetic isotope effects.
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DOBA, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, SIK, UILJ, UKNU, UL, UM, UPUK
The masked transition‐metal frustrated Lewis pairs Cp*M(κ3N,N’,N’’‐L)SbF6 (Cp*=η5‐C5Me5; M=Ir, 1, Rh, 2; HL=pyridinyl‐amidine ligand) reversibly activate H2 under mild conditions rendering the ...hydrido derivatives Cp*MH(κ2N,N’‐HL)SbF6 observed as a mixture of the E and Z isomers at the amidine C=N bond (M=Ir, 3Z, 3E; M=Rh, 4Z, 4E). DFT calculations indicate that the formation of the E isomers follows a Grotthuss type mechanism in the presence of water. A mixture of Rh(I) isomers of formula (Cp*H)Rh(κ2N,N’‐HL)SbF6 (5 a–d) is obtained by reductive elimination of Cp*H from 4. The formation of 5 a–d was elucidated by means of DFT calculations. Finally, when 2 reacts with D2, the Cp* and Cp*H ligands of the resulting rhodium complexes 4 and 5, respectively, are deuterated as a result of a reversible hydrogen ion from the Cp* ligand and D2 activation at rhodium.
Cooperate and you will get it: The masked FLPs depicted in the Scheme activate dihydrogen and the usually spectator Cp* ligand undergoes reductive elimination and H/D exchange processes.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Ammonia (NH3) is a valuable chemical for fertilizer production and for use as an effective hydrogen carrier. Electrocatalytic nitrate reduction has recently received great attention as an alternative ...for NH3 synthesis due to its kinetically favorable reaction. However, this promising strategy suffers from low Faradaic efficiency (FE) at large current density (>100 mA cm–2) and low nitrate concentrations because of the competing hydrogen evolution reaction. Herein, we report a catalyst consisting of earth-abundant cobalt–copper (Co1–x Cu x ) nanoparticles supported on a three-dimensional substrate for efficient and selective NH3 synthesis via electrocatalytic nitrate reduction. Typically, the optimized Co0.5Cu0.5 catalyst performs at a high NH3 Faradaic efficiency (FE) of over 95% at −0.03 V with NH3 partial current density of ∼176 mA cm–2 at 50 mM nitrate, which is 7.3- and 1.7-fold higher than that of pure Co and Cu counterparts. Importantly, replacing Co with Cu enables the tuning of onset potential on Co catalyst maintaining high selectivity toward NH3. A stability test over 12 cycles confirmed the long-term operation of this catalyst. This work offers a facile strategy for tuning the catalyst’s elemental composition to attain a desired electrocatalytic activity.
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The reactivity of metal surfaces is a cornerstone concept in chemistry, as metals have long been used as catalysts to accelerate chemical reactions. Although fundamentally important, ...the reactivity of metal surfaces has hitherto not been explicitly defined. For example, in order to compare the activity of two metal surfaces, a particular probe adsorbate, such as O, H, or CO, has to be specified, as comparisons may vary from probe to probe. Here we report that the metal surfaces actually have their own intrinsic/eigen reactivity, independent of any probe adsorbate. By employing unsupervised machine learning algorithms, specifically, principal component analysis (PCA), two dominant eigenvectors emerged from the binding strength dataset formed by 10 commonly used probes on 48 typical metal surfaces. According to their chemical characteristics revealed by vector decomposition, these two eigenvectors can be defined as the covalent reactivity and the ionic reactivity, respectively. Whereas the ionic reactivity turns out to be related to the work function of the metal surface, the covalent reactivity cannot be indexed by simple physical properties, but appears to be roughly connected with the valence-electron number normalized density of states at the Fermi level. Our findings expose that the metal surface reactivity is essentially a two-dimensional vector rather than a scalar, opening new horizons for understanding interactions at the metal surface.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The expected future demand for food and animal‐derived protein will require environment‐friendly novel food sources with high nutritional value. Insects may be one of such novel food sources. ...However, there needs to be an assessment of the risks associated with their consumption, including allergic risks. Therefore, we performed a systematic review aiming to analyse current data available regarding the allergic risks of consuming insects. We reviewed all reported cases of food allergy to insects, and studied the possibility of cross‐reactivity and co‐sensitisation between edible insects, crustaceans and house dust mites. We analysed a total of 25 articles – eight assessing the cross‐reactivity/co‐sensitisation between edible insects, crustaceans and house dust mites; three characterizing allergens in edible insects and 14 case reports, describing case series or prevalence studies of food allergy caused by insects. Cross‐reactivity/co‐sensitisation between edible insects and crustaceans seems to be clinically relevant, while it is still unknown if co‐sensitisation between house dust mites and edible insects can lead to a food allergy. Additionally, more information is also needed about the molecular mechanisms underlying food allergy to insects, although current data suggest that an important role is played by arthropod pan‐allergens such as tropomyosin or arginine kinase.
A systematic review aiming to analyse current data available regarding the allergic risks of consuming edible insects is performed. It is concluded that consumers allergic to crustaceans should avoid edible insects due to risk of allergic reaction. Additionally, workers at insect farms should be monitored for the development of both inhalant and food allergy caused by those edible insects reared at the farms.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
