Optical properties of flower‐like CdS prepared by a hydrothermal method with SDBS as surfactant

In this article, flower‐like CdS structures have been prepared by a hydrothermal method with SDBS as surfactant. The influences of different experimental conditions on the morphologies, UV‐Vis and fluorescence properties of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet‐visible (UV–Vis) and room‐temperature photoluminescence (PL). The XRD result indicates that the flower‐like CdS structures are of hexagonal phase. The FESEM results indicate that the main role of SDBS is to make the CdS crystals assemble together to form the flower‐like structures. The UV–Vis results show CdS has a strong absorption in the ultraviolet region and visible‐light region. The PL results show CdS has two emission peaks, respectively at 461 nm and 553 nm. The growth mechanism for the formation of flower‐like CdS structures is also described.     

Highly Enantioselective Ring‐Opening Reactions of Aziridines with Indole and Its Application in the Building of C3‐Halogenated Pyrroloindolines

A magnesium‐catalyzed asymmetric ring‐opening reaction of aziridine with indole has been realized by employing commercially available chiral ligands. Both of the enantiomers of the ring‐opening product could be obtained with good yields and a high level of enantioselectivity. The corresponding ring‐opening product could be further transformed to various types of enantioenriched C₃‐halogenated‐pyrroloindolines.     

Arylphosphonylation and Arylazidation of Activated Alkenes

Two radical‐mediated processes of activated alkenes, namely arylphosphonylation and arylazidation, are described. The difunctionalization of alkenes by a tandem process that involves radical addition, 1,4‐aryl migration, and desulfonylation generates α‐aryl‐β‐heterofunctionalized amides bearing a quaternary stereocenter when the substituent on the nitrogen atom is an aryl group. Alternatively, heterooxindoles or spirobicycles can be obtained with excellent regioselectivity in the presence of an alkyl substituent on the nitrogen atom.     

Tailoring A Poly(ether sulfone) Bipolar Membrane: Osmotic-Energy Generator with High Power Density

Osmotic energy, obtained through different concentrations of salt solutions, is recognized as a form of a sustainable energy source. In the past years, membranes derived from asymmetric aromatic compounds have attracted attention because of their low cost and high performance in osmotic energy conversion. The membrane formation process, charging state, functional groups, membrane thickness, and the ion-exchange capacity of the membrane could affect the power generation performance. Among asymmetric membranes, a bipolar membrane could largely promote the ion transport. Here, two polymers with the same poly(ether sulfone) main chain but opposite charges were synthesized to prepare bipolar membranes by a nonsolvent-induced phase separation (NIPS) and spin-coating (SC) method. The maximum power density of the bipolar membrane reaches about 6.2 W m⁻² under a 50-fold salinity gradient, and this result can serve as a reference for the design of bipolar membranes for osmotic energy conversion systems.     

Metal-reinforced sulfonic-acid-modified zirconia for the removal of trace olefins from aromatics

Metal-reinforced sulfonic-acid-modified zirconia catalysts were successfully prepared and used to remove trace olefins from aromatics in a fixed-bed reactor. Catalysts were characterized by ICP-OES, N₂ adsorption–desorption, X-ray diffraction, thermogravimetric analysis (TGA), and pyridine-FTIR spectroscopy. Different metals and calcination temperatures had great influence on the catalytic activity. Alumina-reinforced sulfated zirconia exhibited outstanding catalytic performance, stable regeneration activity, and giant surface area, and are promising in industrial catalysis. TGA showed that the decomposition of methyl could be attributed to Brønsted acid sites, and pyridine-FTIR spectroscopy proved the weak Brønsted sites on these synthesized metal-reinforced sulfated zirconia. Also, a relation between the reaction rate and weak Brønsted acid density is proposed.     

Dicyclohepta[ijkl,uvwx]rubicene with Two Pentagons and Two Heptagons as a Stable and Planar Non-benzenoid Nanographene

Polycyclic aromatic hydrocarbons with hexagons/pentagons or hexagons/heptagons have been intensively investigated in recent years, but those with simultaneous presence of hexagons, pentagons and heptagons remain rare. In this paper, we report dicyclohepta[ijkl,uvwx]rubicene ( DHR ), a non-benzenoid isomer of dibenzo[bc,kl]coronene with two pentagons and two heptagons. We developed an efficient and scalable synthetic method for DHR by using Scholl reaction and dehydrogenation. Crystal structure of DHR shows that the benzenoid rings, two pentagons and two heptagons are coplanar. The bond lengths analysis and the ICSS(1)zz and LOL-π calculations indicate that the incorporation of two formal azulene moieties has an effect on the conjugated structure. The π-electrons of benzenoid and pentagon rings are more delocalized. Cyclic voltammetry studies indicate that DHR shows multiple oxidation and reduction potentials. Interestingly, DHR exhibits unusual S₀ to S₂ absorption and abnormal anti-Kasha S₂ to S₀ emission. Moreover, crystals of DHR exhibit semiconducting behaviour with hole mobility up to 0.082 cm² V⁻¹ s⁻¹.     

通过赝反伽伐尼反应实现金纳米粒子模块替换

通过可控的方式精确调控纳米粒子的结构仍是一个富有挑战性和鼓舞人心的课题.尽管单原子或两、三个金属原子的精细调控已经在金纳米粒子中实现,涉及三个以上金属原子的取代（模块取代）还没有报道.本工作报道了环己硫醇配体保护的Au₄₈（CHT）₂₆的合成及其通过赝反伽伐尼过程的模块取代.单晶结构揭示模块取代的产物与母体团簇共用一个相似的Au₃₁（CHT）₁₂主体,但剩余部分不同（Au₆（CHT）₁₁ vs.Au₁₆（CHT）₁₄）.一个有趣的发现是模块取代抑制了Au₄₈（CHT）₂₆的光热过程,却增强了它的发射,赋予了所合成团簇更好的双（多）功能应用潜力.光热效应的减弱和发射的增强也暗示了这两种作用能够彼此至少部分转化,对于研究这两种效应之间的相互影响也具有重要的启示.     

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.     

Catalytic Enantioselective Synthesis of anti‐Vicinal Silylboronates by Conjunctive Cross‐Coupling

Chiral 1,2‐bimetallic reagents are useful motifs in synthetic chemistry. Although syn‐1,2‐bimetallic compounds can be prepared by alkene dimetallation, anti‐1,2‐bimetallics are still rare. The stereospecific 1,2‐metallate shift that occurs during conjunctive cross‐coupling is shown to enable a practical and modular approach to the catalytic synthesis of enantioenriched anti‐1,2‐borosilanes. In addition to reaction development, the synthetic utility of anti‐1,2‐borosilanes was investigated, including applications to the synthesis of anti‐1,2‐diols and anti‐1,2‐amino alcohols     

Influence of the molding angle on tensile properties of FDM parts with orthogonal layering

Fused deposition molding (FDM) is one of the most widely used three‐dimensional (3D) printing technologies. This paper explores the influence of the forming angle on the tensile properties of FDM specimens. Orthogonal layering details were studied through experiments, theory, and finite element simulations. The stiffness and strength of the specimens were analyzed using the classical laminated plate theory and the Tsai–Wu failure criterion. The experimental process was simulated using finite element simulations. Results show that it is feasible to predict the stiffness and strength of FDM specimens using classical laminated plate theory and the Tsai–Wu failure criterion. A molding angle of 45° leads to specimens with maximized tensile properties. Numerical simulations show that changing the molding angle changes the internal stress and deformation fields inside samples, leading to FDM samples with different mechanical properties due to the orthogonal layers at different molding angles.