Development of [3]ferrocenophane-derived N/B frustrated Lewis pairs for the metal-free catalytic hydrogenation of imines

A series of novel [3]ferrocenophane-derived N/B frustrated Lewis pairs (FLPs) were synthesized and successfully applied to the catalytic hydrogenation of imines in 71–93% yields. This approach could be easily conducted on gram scale and provided versatile synthetic route for the key intermediate of sertraline hydrochloride without heavy metal residues.     

Facile synthesis of 1-(arylimino)naphthalen-2(1H)-ones from anilines and 2-naphthols promoted by NaBr/K2S2O8/CAN

An efficient method has been developed for the synthesis of 1-(arylimino)naphthalen-2(1H)-ones through the cascade reaction of anilines and 2-naphthols promoted by NaBr/K₂S₂O₈/Ce(NH₄)₂(NO₃)₆. Using this protocol, a series of 1-(arylimino)naphthalen-2(1H)-ones was obtained in good to excellent yields (17 examples, 70–92% yields). The reactions may proceed through the following steps: bromination of 2-naphthols by in-situ-generated bromine from NaBr and K₂S₂O₈ to afford 1-bromonaphthalen-2-ols, coupling of 1-bromonaphthalen-2-ols with anilines to afford the corresponding amines, and subsequent oxidation of the amines into the products by Ce(NH₄)₂(NO₃)_6. These newly obtained α-imine ketones have great potentials for synthesis of special optical materials bearing naphthalene moiety.     

A series of fluorenone-carbazole based regioisomers as bipolar host materials for efficient organic light emitting diodes

A series of fluorenone-carbazole based regioisomers (1–4) have been synthesized and applied as host materials for red OLEDs to investigate the effect of different connection configuration on the optoelectronic properties, charge transport capability and device performance. The optoelectronic properties, thermal stability, redox behaviors and charge transport characteristics of these four compounds were fully characterized. These four hosts demonstrated high thermal stability, bipolar charge transport properties and good EL performance. Although these four compounds demonstrated similar HOMO and LUMO energy levels, the twisted structure of 1 led to the smallest singlet-triplet energy gap, which could account in part for the observation of its better EL performance.     

Organic base-promoted efficient dehydrogenative/decarboxylative aromatization of tetrahydro-β-carbolines into β-carbolines under air

Organic base DBN has been identified as an efficient reagent for promoting the dehydrogenative/decarboxylative aromatization of tetrahydro-β-carbolines under air atmosphere, to access the corresponding β-carbolines in moderate to good yields. The utility of this protocol for the gram-scale synthesis of β-carboline alkaloids eudistomin U (7) and harmane (10) has also been demonstrated.     

Synthesis,Crystal Structures,and Anti‐cervical Cancer Activity Evaluation of Three Trinuclear Transition Metal(II) Complexes with N,O‐Donor Schiff Base Ligand

A new bi‐nucleating Schiff base ligand, 2‐(((3‐(dimethylamino)propyl)imino)methyl)‐6‐methoxyphenol (HL₁) was prepared by a one‐pot condensation reaction, which was further used in the construction of three trinuclear Schiff base transition metal(II) complexes [Cu₃(L1)₂(OH)₂(H₂O)₂](NO₃)₂ ( 1 ), [Co₃(L1)₂(OH)₂(H₂O)₂](NO₃)₂ ( 2 ), and [Cu₃(L1)₂(N₃)₄] ( 3 ). Furthermore, a green hand grinding technique was implemented to reduce the particle size of the coordination complexes to generate the nanoscale compounds. The SEM studies reveal the formation of square and spherical particles for nano 1 and 2 , and nanorod for nano 3 . In addition, the anti‐proliferation activity of nano 1 – 3 was detected on the human cervical cancer Hela cells with CCK‐8 assay. The cell viability curves and IC₅₀ values indicated that only nano 1 has anti‐proliferation activity on Hela cells. To further investigate the mechanism of nano 1 induced Hela cell death, the Annexin V‐FITC/PI double staining assay, western blot assay, and ROS level detection was conducted.     

Syntheses,Structures, and Magnetic Properties of Two DMTCNQ and DETCNQ Gadolinium Complexes

Two DMTCNQ (DMTCNQ = 2,5‐dimethyl‐7,7,8,8‐tetracyano‐p‐quinodimethane) and DETCNQ (DETCNQ = 2,5‐diethyl‐7,7,8,8‐tetracyano‐p‐quinodimethane) gadolinium complexes [Gd(DMTCNQ)₂(CH₃OH)(H₂O)₆][DMTCNQ] · 4H₂O ( 1 ) and [Gd(DETCNQ)(H₂O)₇][2DETCNQ] ( 2 ) were synthesized by reactions of GdCl₃ · 6H₂O with Li(DMTCNQ) or Li(DETCNQ). X‐ray diffraction analysis reveals that complexes 1 and 2 are discrete complexes. The central metal atom in 1 is coordinated by two DMTCNQ ligand radicals whereas that in 2 is coordinated by just one DETCNQ ligand radical. The adjacent molecules are connected by the intermolecular hydrogen bonds to form the two‐dimensional (2D) supramolecular layer structures, which are further packed into a three‐dimensional (3D) supramolecular architecture through the π–π interactions between ligand radicals in 1 and 2 . Magnetic investigation indicates that the antiferromagnetic interactions between spin carriers exists in 1 and 2 .     

A New Planar Hexanuclear Dysprosium Cluster Exhibiting Slow Magnetic Relaxation Features

Reaction of the Schiff base ligand H₂L and dysprosium acetate result in a new planar Dy₆ cluster [Dy₆(μ₃‐OH)L₆(Ac)₆] · MeOH ( 1 ) [H₂L = N'‐(2‐hydroxybenzylidene)‐2‐(hydroxyimino)propanohydrazide, HAc = acetic acid], which was successfully structurally and magnetically characterized. Single‐crystal X‐ray diffraction analysis revealed that 1 contained a hexanuclear dysprosium cluster [Dy₆], which is composed of four Dy₃ triangular units. Magnetic measurements suggest that 1 displays single‐molecule magnet (SMM) behavior which is enhanced by applying a 4000 Oe direct‐current field. The effective anisotropic barrier U_eff/k_B = 14.9 K and the pre‐exponential factor τ₀ = 1.31 × 10^–6 s are also obtained. This work may provide more insights for the design and investigation of lanthanide‐based SMMs.     

Chemo‐ and Regioselective Dihydroxylation of Benzene to Hydroquinone Enabled by Engineered Cytochrome P450 Monooxygenase

Hydroquinone (HQ) is produced commercially from benzene by multi‐step Hock‐type processes with equivalent amounts of acetone as side‐product. We describe an efficient biocatalytic alternative using the cytochrome P450‐BM3 monooxygenase. Since the wildtype enzyme does not accept benzene, a semi‐rational protein engineering strategy was developed. Highly active mutants were obtained which transform benzene in a one‐pot sequence first into phenol and then regioselectively into HQ without any overoxidation. A computational study shows that the chemoselective oxidation of phenol by the P450‐BM3 variant A82F/A328F leads to the regioselective formation of an epoxide intermediate at the C3=C4 double bond, which departs from the binding pocket and then undergoes fragmentation in aqueous medium with exclusive formation of HQ. As a practical application, an E. coli designer cell system was constructed, which enables the cascade transformation of benzene into the natural product arbutin, which has anti‐inflammatory and anti‐bacterial activities.     

Guiding Uniform Li Plating/Stripping through Lithium–Aluminum Alloying Medium for Long‐Life Li Metal Batteries

The uncontrolled growth of Li dendrites upon cycling might result in low coulombic efficiency and severe safety hazards. Herein, a lithiophilic binary lithium–aluminum alloy layer, which was generated through an in situ electrochemical process, was utilized to guide the uniform metallic Li nucleation and growth, free from the formation of dendrites. Moreover, the formed LiAl alloy layer can function as a Li reservoir to compensate the irreversible Li loss, enabling long‐term stability. The protected Li electrode shows superior cycling over 1700 h in a Li|Li symmetric cell.     

Nanozyme‐Catalyzed Cascade Reactions for Mitochondria‐Mimicking Oxidative Phosphorylation

Multiple‐enzyme‐involving cascade reactions that yield bioenergy are necessary in natural oxidative phosphorylation. However, in vitro applications are hampered by the sensitivity of catalytic activity to environmental adaptation. Herein, we explore nanozyme‐catalyzed cascade reactions in an assembled hybrid architecture for mitochondria‐mimicking oxidative phosphorylation. Hollow silica microspheres containing trapped gold nanoparticles were synthesized to promote two enzyme‐like catalytic reactions that transform glucose into gluconic acid in the presence of oxygen. The resulting transmembrane proton gradient drives natural ATP synthase reconstituted on the surface to convert ADP and inorganic phosphate into ATP. The assembled architecture possesses high activity for oxidative phosphorylation, comparable to that of natural mitochondria. This study provides a new natural–artificial hybrid prototype for exploring bioenergy supply systems and holds great promise for ATP‐powered bioapplications.