Alloyed Crystalline CdSe1-xSx Semiconductive Nanomaterials – A Solid State 113Cd NMR Study

Solid-state NMR analysis on wurtzite alloyed CdSe_1−xS_x crystalline nanoparticles and nanobelts provides evidence that the ¹¹³Cd NMR chemical shift is not affected by the varying sizes of nanoparticles, but is sensitive to the S/Se anion molar ratios. A linear correlation is observed between ¹¹³Cd NMR chemical shifts and the sulfur component for the alloyed CdSe_1−xS_x (0<x<1) system both in nanoparticles and nanobelts (δ_Cd=169.71⋅X_S+529.21). Based on this correlation, a rapid and applied approach has been developed to determine the composition of the alloyed nanoscalar materials utilizing ¹¹³Cd NMR spectroscopy. The observed results from this system confirm that one can use ¹¹³Cd NMR spectroscopy not only to determine the composition but also the phase separation of nanomaterial semiconductors without destruction of the sample structures. In addition, some observed correlations are discussed in detail.     

Stabilities,Electronic Structures,and Bonding Properties of Iron Complexes (E1E2)Fe(CO)2(CNArTripp2)2 (E1E2=BF,CO, N2, CN−, or NO+)**

The coordination of 10-electron diatomic ligands (BF, CO N₂) to iron complexes Fe(CO)₂(CNAr^Tripp2)₂ [Ar^Tripp2=2,6-(2,4,6-(iso-propyl)₃C₆H₂)₂C₆H₃] have been realized in experiments very recently (Science, 2019 , 363, 1203–1205). Herein, the stability, electronic structures, and bonding properties of (E₁E₂)Fe-(CO)₂(CNAr^Tripp2)₂ (E₁E₂=BF, CO, N₂, CN⁻, NO⁺) were studied using density functional (DFT) calculations. The ground state of all those molecules is singlet and the calculated geometries are in excellent agreement with the experimental values. The natural bond orbital analysis revealed that Fe is negatively charged while E₁ possesses positive charges. By employing the energy decomposition analysis, the bonding nature of the E₂E₁–Fe(CO)₂(CNAr^Tripp2)₂ bond was disclosed to be the classic dative bond E₂E₁→Fe(CO)₂(CNAr^Tripp2)₂ rather than the electron-sharing double bond. More interestingly, the bonding strength between BF and Fe(CO)₂(CNAr^Tripp2)₂ is much stronger than that between CO (or N₂) and Fe(CO)₂(CNAr^Tripp2)₂, which is ascribed to the better σ-donation and π back-donations. However, the orbital interactions in CN⁻→Fe(CO)₂(CNAr^Tripp2)₂ and NO⁺→Fe(CO)₂(CNAr^Tripp2)₂ mainly come from σ-donation and π back-donation, respectively. The different contributions from σ donation and π donation for different ligands can be well explained by using the energy levels of E₁E₂ and Fe(CO)₂(CNAr^Tripp2)₂ fragments.     

Gastroprotective Effects of Inulae Flos on HCl/Ethanol-Induced Gastric Ulcers in Rats

Inulae Flos, the flower of Inula britannica L., is used as a dietary supplement, beverage, and medicine in East Asia. In this study, we evaluated the gastroprotective effects of Inulae Flos extract (IFE) against gastric mucosal lesions induced by hydrochloric acid (HCl)/ethanol in rats and explored its potential mechanisms by measuring antioxidant enzyme activity, mucus secretion, and prostaglandin E₂ (PGE₂) levels. Pretreatment with IFE at doses of 100 and 300 mg/kg significantly inhibited gastric lesions in HCl/ethanol-treated rats. IFE increased the activities of superoxide dismutase and catalase and the levels of glutathione and PGE₂ in gastric tissues. The administration of IFE also significantly increased the gastric wall mucus contents in HCl/ethanol-induced gastric lesions. These findings suggest that IFE has gastroprotective effects against HCl/ethanol-induced gastric lesions and exerts these effects through increased antioxidant levels and gastric mucus secretion. Inulae Flos may be a promising agent for the prevention and treatment of gastritis and gastric ulcers.     

Sorbents for the Direct Capture of CO2 from Ambient Air

The urgency to address global climate change induced by greenhouse gas emissions is increasing. In particular, the rise in atmospheric CO₂ levels is generating alarm. Technologies to remove CO₂ from ambient air, or “direct air capture” (DAC), have recently demonstrated that they can contribute to “negative carbon emission.” Recent advances in surface chemistry and material synthesis have resulted in new generations of CO₂ sorbents, which may drive the future of DAC and its large‐scale deployment. This Review describes major types of sorbents designed to capture CO₂ from ambient air and they are categorized by the sorption mechanism: physisorption, chemisorption, and moisture‐swing sorption.     

Regiodivergent Intramolecular Nucleophilic Addition of Ketimines for the Diverse Synthesis of Azacycles

Azacycles such as indoles and tetrahydroquinolines are privileged structures in drug development. Reported here is an unprecedented regiodivergent intramolecular nucleophilic addition reaction of imines as a flexible approach to access N‐functionalized indoles and tetrahydroquinolines, by the control of reaction at the N‐terminus and C‐terminus, respectively. Using ketimines derived from 2‐(2‐nitroethyl)anilines with isatins or α‐ketoesters, the regioselective N‐attack reaction gives N‐functionalized indoles, while the catalytic enantioselective C‐attack reaction affords chiral tetrahydroquinolines featuring an α‐tetrasubstituted stereocenter. Mechanistic studies reveal that hydrogen‐bonding interactions may greatly facilitate such unusual N‐attack reactions of imines. The utility of this protocol is highlighted by the catalytic enantioselective formal synthesis of (?)‐psychotrimine, and the construction of various fused aza‐heterocycles.     

Unpaired 3d Electrons on Atomically Dispersed Cobalt Centres in Coordination Polymers Regulate both Oxygen Reduction Reaction (ORR) Activity and Selectivity for Use in Zinc–Air Batteries

Reversible oxygen conversion is important for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP=2,3,6,7,10,11‐hexaiminotriphenylene) as the ligand, to interrogate the role of metal centres in modulating the activity of the oxygen reduction reaction (ORR). Co₃HITP₂ and Ni₃HITP₂ are compared. Unpaired 3d electrons in Co₃HITP₂ result in less coplanarity but more radical character. Thus, despite of a reduced crystallinity and conductivity, the best ORR activity, comparable to 20 % Pt/C, is obtained for Co₃HITP₂, showing the 3d orbital configuration of the metal centre promotes ORR. Experimental and DFT studies show a transition of ORR pathway from four‐electron for Co₃HITP₂ to two‐electron for Ni₃HITP₂. Rechargeable zinc–air batteries using Co₃HITP₂ as the air cathode catalyst demonstrate excellent energy efficiency and stability.     

Gold and Carbene Relay Catalytic Enantioselective Cycloisomerization/Cyclization Reactions of Ynamides and Enals

The combined use of gold as transition metal catalyst and N‐heterocyclic carbene (NHC) as organic catalyst in the same solution for relay catalytic reactions was disclosed. The ynamide substrate was activated by gold catalyst to form unsaturated ketimine intermediate that subsequently reacted with the enals (via azolium enolate intermediate generated with NHC) effectively to form bicyclic lactam products with excellent diastereo‐ and enantio‐selectivities. The gold and NHC coordination and dissociation can be dynamic and tunable events, and thus allow the co‐existence of both active metal and carbene organic catalysts in appreciable concentrations, for the dual catalytic reaction to proceed.     

Conversion of Mg‐Li Bimetallic Alloys to Magnesium Alkoxide and Magnesium Oxide Ceramic Nanowires

Technologically important composites with enhanced thermal and mechanical properties rely on the reinforcement by the high specific strength ceramic nanofibers or nanowires (NWs) with high aspect ratios. However, conventional synthesis routes to produce such ceramic NWs have prohibitively high cost. Now, direct transformation of bulk Mg‐Li alloys into Mg alkoxide NWs is demonstrated without the use of catalysts, templates, expensive or toxic chemicals, or any external stimuli. This mechanism proceeds through the minimization of strain energy at the boundary of phase transformation front leading to the formation of ultra‐long NWs with tunable dimensions. Such alkoxide NWs can be easily converted in air into ceramic MgO NWs with similar dimensions. The impact of the alloy grain size and Li content, synthesis temperature, inductive and steric effects of alkoxide groups on the diameter, length, composition, ductility, and oxidation of the produced NWs is discussed.     

Visible‐Light‐Enabled Stereodivergent Synthesis of E‐ and Z‐Configured 1,4‐Dienes by Photoredox/Nickel Dual Catalysis

A stereodivergent reductive coupling reaction between allylic carbonates and vinyl triflates to furnish both E‐ and Z‐configured 1,4‐dienes has been achieved by visible‐light‐induced photoredox/nickel dual catalysis. The mild reaction conditions allow good compatibility of both vinyl triflates and allylic carbonates. Notably, the stereoselectivity of this synergistic cross‐electrophile coupling can be tuned by an appropriate photocatalyst with a suitable triplet‐state energy, providing a practical and stereodivergent means to alkene synthesis. Preliminary mechanistic studies shed some light on the coupling step as well as the control of the stereoselectivity step.     

A Low‐Cost and Environmentally Friendly Mixed Polyanionic Cathode for Sodium‐Ion Storage

Sodium‐ion batteries (NIBs) are the most promising alternatives to lithium‐ion batteries in the development of renewable energy sources. The advancement of NIBs depends on the exploration of new electrode materials and fundamental understanding of working mechanisms. Herein, via experimental and simulation methods, we develop a mixed polyanionic compound, Na₂Fe(C₂O₄)SO₄?H₂O, as a cathode for NIBs. Thanks to its rigid three dimensional framework and the combined inductive effects from oxalate and sulfate, it delivered reversible Na insertion/desertion at average discharging voltages of 3.5 and 3.1 V for 500 cycles with Coulombic efficiencies of ca. 99 %. In situ synchrotron X‐ray measurements and DFT calculations demonstrate the Fe²⁺/Fe³⁺ redox reactions contribute to electron compensation during Na⁺ desertion/insertion. The study suggests mixed polyanionic frameworks may provide promising materials for Na ion storage with the merits of low cost and environmental friendliness.