Electro-oxidative intermolecular CSP2-H amination of heteroarenes via proton-coupled electron transfer.

A new electrochemical proton-coupled electron transfer method for the intermolecular CSP2-H amination of heteroarenes without oxidants, metal catalysts and external electrolytes has been developed. Various new N-containing heteroarenes were prepared in medium to high yields, and the indole-containing product could be converted into practical 2-oxindole by simple basic hydrolysis. Mechanistic investigation indicated that ester sulfonyl-substituted N-radicals could be formed by the combination of 2,6-lutidine and electrochemical oxidation, which is the key to achieve the desired chemoselectivity.

Radical cascade silylation/cyclization of 1,7-dienes to access silyl-substituted benzo[b]azepin-2-ones.

A novel silyl radical-induced cascade silylation/cyclization of 1,7-dienes has been realized employing readily available hydrosilanes as a silicon source and Cu(I) salt as a catalyst. This protocol introduces diverse silicon fragments into a challenging 7-membered ring structure and provides an efficient approach to a wide array of biologically important silyl-substituted benzo[b]azepin-2-ones. Several control experiments suggest that the reaction undergoes a free radical process. The gram-scale synthesis and late-stage transformations further demonstrate the scalability and applicability of the reaction in organic synthesis.

Geminal-atom catalysis for cross-coupling.

Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis1-4. However, the architecture of these mononuclear metal species stabilized on solid supports may not be optimal for catalysing complex molecular transformations owing to restricted spatial environment and electronic quantum states5,6. Here we report a class of heterogeneous geminal-atom catalysts (GACs), which pair single-atom sites in specific coordination and spatial proximity. Regularly separated nitrogen anchoring groups with delocalized π-bonding nature in a polymeric carbon nitride (PCN) host7 permit the coordination of Cu geminal sites with a ground-state separation of about 4 Å at high metal density8. The adaptable coordination of individual Cu sites in GACs enables a cooperative bridge-coupling pathway through dynamic Cu-Cu bonding for diverse C-X (X = C, N, O, S) cross-couplings with a low activation barrier. In situ characterization and quantum-theoretical studies show that such a dynamic process for cross-coupling is triggered by the adsorption of two different reactants at geminal metal sites, rendering homo-coupling unfeasible. These intrinsic advantages of GACs enable the assembly of heterocycles with several coordination sites, sterically congested scaffolds and pharmaceuticals with highly specific and stable activity. Scale-up experiments and translation to continuous flow suggest broad applicability for the manufacturing of fine chemicals.

Gate-Tunable Renormalization of Spin-Correlated Flat-Band States and Bandgap in a 2D Magnetic Insulator.

Emergent quantum phenomena in two-dimensional van der Waal (vdW) magnets are largely governed by the interplay between exchange and Coulomb interactions. The ability to precisely tune the Coulomb interaction enables the control of spin-correlated flat-band states, band gap, and unconventional magnetism in such strongly correlated materials. Here, we demonstrate a gate-tunable renormalization of spin-correlated flat-band states and bandgap in magnetic chromium tribromide (CrBr3) monolayers grown on graphene. Our gate-dependent scanning tunneling spectroscopy (STS) studies reveal that the interflat-band spacing and bandgap of CrBr3 can be continuously tuned by 120 and 240 meV, respectively, via electrostatic injection of carriers into the hybrid CrBr3/graphene system. This can be attributed to the self-screening of CrBr3 arising from the gate-induced carriers injected into CrBr3, which dominates over the weakened remote screening of the graphene substrate due to the decreased carrier density in graphene. Precise tuning of the spin-correlated flat-band states and bandgap in 2D magnets via electrostatic modulation of Coulomb interactions not only provides effective strategies for optimizing the spin transport channels but also may exert a crucial influence on the exchange energy and spin-wave gap, which could raise the critical temperature for magnetic order.

Phase-Controlled Cobalt Catalyst Boosting Hydrogenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran.

The search for non-noble metal catalysts for chemical transformations is of paramount importance. In this study, an efficient non-noble metal catalyst for hydrogenation, hexagonal close-packed cobalt (HCP-Co), was synthesized through a simple one-step reduction of ß-Co(OH)2 nanosheets via a temperature-induced phase transition. The obtained HCP-Co exhibited several-times-higher catalytic efficiency than its face-centered cubic cobalt (FCC-Co) counterpart in the hydrogenation of the C=C/C=O group, especially for the 5-hydroxymethylfurfural (HMF) hydrogenation (8.5-fold enhancement). Density functional theory calculations demonstrated that HMF molecules were adsorbed more firmly on the (112_0) facet of HCP-Co than that on the (111) facet of FCC-Co, favoring the activation of the C=O group in the HMF molecule. The stronger adsorption on the (112_0) facet of HCP-Co also led to lower activation energy than that on the (111) facet of FCC-Co, thereby resulting in high activity and selectivity. Moreover, HCP-Co exhibited outstanding catalytic stability during the hydrogenation of HMF. These results highlight the possibility of fabricating hydrogenation catalysts with satisfactory catalytic properties by precisely tuning their active crystal phase.

Ferromagnetic single-atom spin catalyst for boosting water splitting.

Heterogeneous single-atom spin catalysts combined with magnetic fields provide a powerful means for accelerating chemical reactions with enhanced metal utilization and reaction efficiency. However, designing these catalysts remains challenging due to the need for a high density of atomically dispersed active sites with a short-range quantum spin exchange interaction and long-range ferromagnetic ordering. Here, we devised a scalable hydrothermal approach involving an operando acidic environment for synthesizing various single-atom spin catalysts with widely tunable substitutional magnetic atoms (M1) in a MoS2 host. Among all the M1/MoS2 species, Ni1/MoS2 adopts a distorted tetragonal structure that prompts both ferromagnetic coupling to nearby S atoms as well as adjacent Ni1 sites, resulting in global room-temperature ferromagnetism. Such coupling benefits spin-selective charge transfer in oxygen evolution reactions to produce triplet O2. Furthermore, a mild magnetic field of ~0.5 T enhances the oxygen evolution reaction magnetocurrent by ~2,880% over Ni1/MoS2, leading to excellent activity and stability in both seawater and pure water splitting cells. As supported by operando characterizations and theoretical calculations, a great magnetic-field-enhanced oxygen evolution reaction performance over Ni1/MoS2 is attributed to a field-induced spin alignment and spin density optimization over S active sites arising from field-regulated S(p)-Ni(d) hybridization, which in turn optimizes the adsorption energies for radical intermediates to reduce overall reaction barriers.

Removal of Polystyrene Microplastics from Aqueous Solution Using the Metal-Organic Framework Material of ZIF-67.

Due to the continuous and adverse effects of microplastics on the environment, an increasing number of studies have begun to focus on their migration patterns and removal from aquatic environments. Herein, our study innovatively evaluated the ability of the capacity of ZIF-67, a novel metal-organic framework (MOF) material, to adsorb polystyrene (PS) microplastics (MPs) from aqueous solutions, aiming to explore the potential of MOF materials to remove MPs from wastewater. The adsorption ratio of PSMPs (5 mg/L, 30 mL) by ZIF-67 reached up to 92.1%, and the PSMP adsorption equilibrium was achieved within 20 min at 298 K. The adsorption of PSMPs would be favored at a pH of 8, a PSMPs solution concentration of 5 mg/L, and a temperature of 298 K. Further analyses demonstrated that hydrogen bond interactions, π-π stacking, and electrostatic interactions played a crucial role in the adsorption of PSMPs by ZIF-67 in aqueous solutions. Our findings thus provide insight into novel methods to remove MPs from acidic and weakly alkaline aquatic environments and wastewater.

A feasible biochar derived from biogas residue and its application in the efficient adsorption of tetracycline from an aqueous solution.

The recovery of carbon materials from biogas residue (BR) could efficiently promote the efficient utilization of waste and the preparation of novel materials. In this study, a green and feasible reagent of citric acid was introduced and applied in the modification of biogas residue biochar (BRC). The modified biogas residue biochar (CABRC) showed a superior adsorption ability due to its higher specific surface area (approximately 6 times that of the BRC). Additionally, the adsorption capacities of CABRC and BRC for TC were 58.25 mg/g and 20.77 mg/g, respectively, while the TC adsorption performance of CABRC was 2.8 times that of BRC. The adsorption of TC by both BRC and CABRC was primarily controlled by physical adsorption and chemical adsorption (including pore filling, hydrogen bonding, π-π DEA interaction, and electrostatic interaction). Therefore, CABRC should be considered an environmentally friendly material due to its higher adsorption performance, which could expand its application in wastewater treatment.

The Potential for PE Microplastics to Affect the Removal of Carbamazepine Medical Pollutants from Aqueous Environments by Multiwalled Carbon Nanotubes.

Microplastics are ubiquitous in aquatic environments and interact with other kinds of pollutants, which affects the migration, transformation, and fate of those other pollutants. In this study, we employ carbamazepine (CBZ) as the contaminant to study the influence of polyethylene (PE) microplastics on the adsorption of CBZ pollutants by multiwalled carbon nanotubes (MCNTs) in aqueous solution. The adsorption capacity of CBZ by MCNTs in the presence of PE microplastics was obviously lower than that by MCNTs alone. The influencing factors, including the dose of microplastics, pH, and CBZ solution concentration, on the adsorption of CBZ by MCNTs and MCNTs-PE were thoroughly investigated. The adsorption rate of CBZ by MCNTs decreased from 97.4% to 90.6% as the PE microplastics dose increased from 2 g/L to 20 g/L. This decrease occurred because the MCNTs were coated on the surface of the PE microplastics, which further decreased the effective adsorption area of the MCNTs. This research provides a framework for revealing the effect of microplastics on the adsorption of pollutants by carbon materials in aqueous environments.

Empowerment programs for parental mental health of preterm infants: A meta-analysis.

OBJECTIVE: To assess the effectiveness of empowerment programs on mental health in parents of preterm infants. METHODS: Ten databases were searched for randomised controlled trials and quasi-experimental studies published from inception to March 2020, and two reviewers independently and critically assessed trial quality and extracted data. RESULTS: Eight studies with a total of 1029 participants met the inclusion criteria. Empowerment programs significantly improved parental mental health, particularly maternal stress and depression. This meta-analysis also indicated that Creating Opportunities for Parent Empowerment (COPE) had a medium effect on maternal mental health. Both empowerment-based health education and empowerment programs conducted during the infants' hospitalisation had large effects on maternal mental health, whereas those conducted from hospitalisation to one week after discharge showed no significant effect. CONCLUSION: Empowerment programs have positive effects on parental mental health, especially for mothers. PRACTICE IMPLICATIONS: Our study provides objective evidence for the development of future empowerment programs.

[Effect of wenxin capsule on myocyte apoptosis and expression of Bcl-2, Fas gene protein in rats of experimental myocardial ischemia].

OBJECTIVE: To explore the molecular mechanism of Wenxin Capsule (WXC, an effective Chinese composite drug) in preventing and treating myocardial ischemia of coronary heart disease. METHODS: Rat model of myocardial ischemia was established by subcutaneous multi-point injecting isoproterenol. Effect of WXC on cell apoptosis was observed by transmission electron microscopy and TUNEL method, and its effect on apoptotic related gene Bcl-2 and Fas gene protein expression was observed by immunohistochemical method. RESULTS: Isoproterenol induced myocardial ischemic injury could cause evident cardial cell apoptosis, obvious enhance Fas gene protein expression and mild enhance Bcl-2 gene protein expression. WXC could significantly down-regulate Fas, up-regulate Bcl-2 gene protein expression, significantly inhibit and block the myocardial cell apoptosis. CONCLUSIONS: To inhibit and block the event of cell apoptosis through regulating Bcl-2 and Fas gene protein expression in ischemic myocardium might be one of the mechanisms of WXT in preventing and treating myocardial ischemic injury of coronary heart disease.

Expression, Purification, Crystallization and Preliminary X-ray Diffraction Analysis of the Mutant Pro(229)Ser of Thermostable Catechol 2,3-dioxygenase.

The mutant Pro(229)Ser of thermostable catechol 2,3-dioxygenase (TC23O) was expressed and purified. Enzymatic analysis revealed that its thermostability was decreased, the temperature corresponding to 50% enzyme activity being about 10.2 degrees lower than that of the wild type TC23O. Its kinetic parameter k(cat)/K(m) value (4.89x 10(6) mol(-1).s(-1)) was lower than that of the wild type TC23O(6.97x10(6) mol(-1).s(-1)). By the hanging-drop vapor-diffusion method using polyethylene glycol 400 as a precipitant, the mutant Pro(229)Ser of TC23O crystallizedat 4 degrees. X-ray diffraction analysis revealed that the crystals belong to the orthorhombic space group I(222) with unit-cell parameters a 7.059 nm, b 7.415 nm, c 13.311 nm, and they diffracted to at least 0.24 nm resolution. Assuming the presence of 2 molecules of the mutant Pro(229)Ser in the asymmetric unit, the Matthews parameter (Vm) was calculated to be 2.49x10( 3) nm(3).D(-1), and the solventcontent was about 51%. The crystal structure determination is now in progress.