Nickel(0)-Catalyzed Denitrogenative Transannulation of Benzotriazinones with Alkynes: Mechanistic Insights of Chemical Reactivity and Regio- and Enantioselectivity from Density Functional Theory and Experiment

The mechanism of Ni(0)-catalyzed denitrogenative transannulation of 1,2,3-benzotriazin-4­(<i>3H</i>)-ones with alkynes to access isoquinolones has been comprehensively studied by a density functional theory (DFT) calculation and control experimental investigation. The results indicate that the transformations proceed via a sequential nitrogen extrusion, carbometalation, Ni–C bond insertion, and reductive elimination process. A frontier molecular orbital (FMO) theory and natural bond orbital (NBO) analysis reveals that the advantages of substituents on chemical reactivity and regioselectivity exist for multiple reasons: (1) Phenyl groups on the N atom of benzotriazinone and/or unsymmetrical alkynes mainly account for the high reactivity and regioselectivity via its electronic effect. (2) The π···π interaction between the phenyl substituent on the alkyne and triazole ring might partially contribute to the high regioselectivity when unsymmetrical alkynes were employed as the substrates. Furthermore, DFT calculations successfully explain the origin of enantioselectivity and discrepancy of reactivities between different <i>N</i>-substituted benzotriazinones for the asymmetric construction of axially chiral isoquinolones in an atroposelective manner. The calculated results indicate that high enantioselectivity is mainly determined by the structural difference between these two transition states of the key annulation step, which lies in the orientation of the naphthyl substituent relative to the chiral ligand

Additional file 1 of Potential causal associations between leisure sedentary behaviors, physical activity, sleep traits, and myopia: a Mendelian randomization study

Supplementary Material

Co₃O₄ Nanospheres Embedded in a Nitrogen-Doped Carbon Framework: An Electrode with Fast Surface-Controlled Redox Kinetics for Lithium Storage

Herein, we develop a Co₃O₄-based anode material with a hierarchical structure similar to that of a lotus pod, where single yolk–shell-structured Co₃O₄@Co₃O₄ nanospheres are well embedded in a nitrogen-doped carbon (N–C) conductive framework (Co₃O₄@Co₃O₄/N–C). This distinctive architecture contains multiple advantages of both the yolk–shell structure and conductive N–C framework to improve the Li ion storage performance. Especially, the doping of the N atom in N–C increases the interaction between the carbon and adsorbents, which is confirmed by the theoretical calculations in this work, making the carbon framework much more electrochemically active. As a result, the Co₃O₄@Co₃O₄/N–C exhibits fast surface-controlled kinetics, which corroborate the high counterion mobility and the ultrafast electron-transfer kinetics of the electrode. Due to these synergetic effects, desired capacity stability (1169.6 mAh g^–1 at 200 mA g^–1 after 100 cycles) and superior rate performance (633.4 mAh g^–1 at 10 A g^–1) have been realized in this Co₃O₄@Co₃O₄/N–C electrode

Dual-Porosity SiO₂/C Nanocomposite with Enhanced Lithium Storage Performance

Mesoporous SiO₂ nanospheres (MSNs) and carbon nanocomposite with dual-porosity structure (DMSNs/C) were synthesized via a straightforward approach. Both MSNs and DMSNs/C showed uniform pore size distribution, high specific surface area, and large pore volume. When evaluated as an anode material for lithium ion batteries (LIBs), the DMSNs/C nanocomposite not only delivered an impressive reversible capacity of 635.7 mAh g^–1 (based on the weight of MSNs in the electrode material) over 200 cycles at 100 mA g^–1 with Coulombic efficiency (CE) above 99% but also exhibited excellent rate capability. The significant improvement of the electrochemical performance was attributed to synergetic effects of the dual-mesoporous structure and carbon coating layer: (i) the dual-porosity structure could increase the contact area and facilitate Li⁺ diffusion at the interface between the electrolyte and active materials, as well as buffer the volume change of MSNs, and (ii) the homogeneous carbon coating represented an excellent conductive layer, thus significantly speeding the lithiation process of the MSNs significantly, while further restraining the volume expansion. Considering the facile preparation and good lithium storage abilities, the DMSNs/C nanocomposite holds promise in applications in practical LIBs

Supplementary_1 – Supplemental material for Effects of Information Technology–Based Two-Way Referral on Diagnosis and Management of Cervical Lesions: A Cluster-Controlled Trial in China

<p>Supplemental material, Supplementary_1 for Effects of Information Technology–Based Two-Way Referral on Diagnosis and Management of Cervical Lesions: A Cluster-Controlled Trial in China by Long-Mei Jin, Ling Xu, Jun Xu, Xiao-Hua Zhang, Lin-Lin Zhang, Li-Hong Zhu, Hui-Bin Yang, Lei Zhang, Yan Yao and Hua Feng in Asia Pacific Journal of Public Health</p

A Novel Layered Sedimentary Rocks Structure of the Oxygen-Enriched Carbon for Ultrahigh-Rate-Performance Supercapacitors

In this paper, gelatin as a natural biomass was selected to successfully prepare an oxygen-enriched carbon with layered sedimentary rocks structure, which exhibited ultrahigh-rate performance and excellent cycling stability as supercapacitors. The specific capacitance reached 272.6 F g^–1 at 1 A g^–1 and still retained 197.0 F g^–1 even at 100 A g^–1 (with high capacitance retention of 72.3%). The outstanding electrochemical performance resulted from the special layered structure with large surface area (827.8 m² g^–1) and high content of oxygen (16.215 wt %), which effectively realized the synergistic effects of the electrical double-layer capacitance and pseudocapacitance. Moreover, it delivered an energy density of 25.3 Wh kg^–1 even with a high power density of 34.7 kW kg^–1 and ultralong cycling stability (with no capacitance decay even over 10 000 cycles at 2 A g^–1) in a symmetric supercapacitor, which are highly desirable for their practical application in energy storage devices and conversion

Supplement_2-CONSORT_checklist – Supplemental material for Effects of Information Technology–Based Two-Way Referral on Diagnosis and Management of Cervical Lesions: A Cluster-Controlled Trial in China

<p>Supplemental material, Supplement_2-CONSORT_checklist for Effects of Information Technology–Based Two-Way Referral on Diagnosis and Management of Cervical Lesions: A Cluster-Controlled Trial in China by Long-Mei Jin, Ling Xu, Jun Xu, Xiao-Hua Zhang, Lin-Lin Zhang, Li-Hong Zhu, Hui-Bin Yang, Lei Zhang, Yan Yao and Hua Feng in Asia Pacific Journal of Public Health</p

Carbon-Free Porous Zn₂GeO₄ Nanofibers as Advanced Anode Materials for High-Performance Lithium Ion Batteries

In this work, carbon-free, porous, and micro/nanostructural Zn₂GeO₄ nanofibers (p-ZGONFs) have been prepared via a dissolution-recrystallization-assisted electrospinning technology. The successful electrospinning to fabricate the uniform p-ZGONFs mainly benefits from the preparation of completely dissolved solution, which avoids the sedimentation of common Ge-containing solid-state precursors. Electrochemical tests demonstrate that the as-prepared p-ZGONFs exhibit superior Li-storage properties in terms of high initial reversible capacity of 1075.6 mA h g^–1, outstanding cycling stability (no capacity decay after 130 cycles at 0.2 A g^–1), and excellent high-rate capabilities (e.g., still delivering a capacity of 384.7 mA h g^–1 at a very high current density of 10 A g^–1) when used as anode materials for lithium ion batteries (LIBs). All these Li-storage properties are much better than those of Zn₂GeO₄ nanorods prepared by a hydrothermal process. The much enhanced Li-storage properties should be attributed to its distinctive structural characteristics including the carbon-free composition, plentiful pores, and macro/nanostructures. Carbon-free composition promises its high theoretical Li-storage capacity, and plentiful pores cannot only accommodate the volumetric variations during the successive lithiation/delithiation but can also serve as the electrolyte reservoirs to facilitate Li interaction with electrode materials

Nanoscale Polysulfides Reactors Achieved by Chemical Au–S Interaction: Improving the Performance of Li–S Batteries on the Electrode Level

In this work, the chemical interaction of cathode and lithium polysulfides (LiPSs), which is a more targeted approach for completely preventing the shuttle of LiPSs in lithium–sulfur (Li–S) batteries, has been established on the electrode level. Through simply posttreating the ordinary sulfur cathode in atmospheric environment just for several minutes, the Au nanoparticles (Au NPs) were well-decorated on/in the surface and pores of the electrode composed of commercial acetylene black (CB) and sulfur powder. The Au NPs can covalently stabilize the sulfur/LiPSs, which is advantageous for restricting the shuttle effect. Moreover, the LiPSs reservoirs of Au NPs with high conductivity can significantly control the deposition of the trapped LiPSs, contributing to the uniform distribution of sulfur species upon charging/discharging. The slight modification of the cathode with <3 wt % Au NPs has favorably prospered the cycle capacity and stability of Li–S batteries. Moreover, this cathode exhibited an excellent anti-self-discharge ability. The slight decoration for the ordinary electrode, which can be easily accessed in the industrial process, provides a facile strategy for improving the performance of commercial carbon-based Li–S batteries toward practical application