Co-POM@MOF-derivatives with trace cobalt content for highly efficient oxygen reduction

A simple and effective method for constructing highly efficient oxygen reduction catalysts with trace amount of isolated cobalt was firstly developed by the pyrolysis of Co-centered polyoxometalate@metalorganic framework （Co-POM@MOF）.The Co-centered polyoxometalate ([Co W₁₂O₄₀]^6-) was confined in the well-defined void space of ZIF-8 to achieve homogeneous dispersion of polyoxoanions,where the isolated Co centers were well surrounded by the W-O shell and ZIF-8 fra...     

SYNTHESIS,CRYSTAL STRUCTURE AND ELECTROCHEMISTRY PROPERTIES OF Cu-COMPOUND BY RIGID LIGAND

Journal of Structural Chemistry - A new novel Cu(II) compound formulated as Cu(C4N6H4)2Cl2 (1) (C4N6H4 = 1H-3,4′-bi-1,2,4-triazole) is successfully synthesized by a...     

等压法测定298.15K下LiCl-CaCl2-H2O体系的活度系数

The isopiestic method was used to determinate isopiestic molality and osmotic coefficients in single-salt solutions of LiCl-H2O(molality range from 0.5 to 9.0 mol· kg-1),CaCl2-H2O(molality range from 0.35 to 5.2 mol· kg-1) and multisalt solution LiCl-CaCl2-H2O(ionic strength range from 0.5 to 15.7 mol· kg-1) at 298.15K,from which Pitzer's interaction parameters of single salt ,mixed salts of the systems were obtained.The mean ionic activity coefficients of LiCl、 CaCl2 in pure and mixed solutions were reported.     

Double Michael addition of nitromethane to divinyl ketones: A remarkably positive effect of additive

An efficient double Michael addition of nitromethane to divinyl ketones was established in good to high yields (75–99%). A wide range of cyclohexanones were obtained with excellent diastereocontrol (up to >20:1 dr) and enantioinduction (91–99% ee) in a one-pot fashion. The involvement of basic additive significantly enhanced the reactivity of this cascade sequence.     

Tuning the morphology of amphiphilic copolymer aggregates by compound emulsifier via emulsion–solvent evaporation

A series of poly(4-vinylpyridine)-b-poly{6-[4-(4-butyloxyphenylazo)phenoxy]hexyl methacrylate} (P4VP-b-PAzoMA) were employed to fabricate aggregates via the emulsion–solvent evaporation method. The emulsion was stabilized by compound emulsifier composed of SDS and span60. By tuning the ratio of two emulsifiers, P4VP-b-PAzoMA could self-assemble into various morphologies including porous microspheres, tremella-like aggregates, bowl-like aggregates and wrinkled microspheres. The transformation of the morphologies could be ascribed to three major aspects: the stability of emulsified chloroform droplets, the permeation of water into chloroform and the dispersity of the interior water droplets with regard to different HLB values. Besides, the morphology could even be tuned by changing the block ratio and the concentration of P4VP-b-PAzoMA, and the HLB dependent morphology changing was also proved within other block ratio or different concentration. The study uncovers a convenient and effective technique to manipulate the morphology of amphiphilic copolymer aggregates.     

Magnetically-recoverable carbonaceous material: An efficient catalyst for the synthesis of 5-hydroxymethylfurfural and 5-ethoxymethylfurfural from carbohydrates

A novel, magnetically recoverable carbonaceous solid acid Fe₃O₄@C-SO₃H catalyst for the conversion of carbohydrates to 5-ethoxymethylfurfural (EMF) was developed. The effect of the DMSO fraction in the ethanol-DMSO binary solvent on the distribution of the reaction products was investigated. The catalyst showed an excellent activity in the synthesis of EMF from fructose and 5-hydroxymethylfurfural (HMF). 5- Ethoxymethylfurfural was also obtained with a high yield of 64.2% in an ethanol–DMSO solvent system via one-step conversion of fructose. After reaction, the catalyst could be recovered by exposure of the reaction mixture to external magnetic field and reused several times without a loss of catalytic activity.     

Phosphine‐mediated Highly Enantioselective Spirocyclization with Ketimines as Substrates

Phosphine‐catalyzed enantioselective annulation reactions involving ketimines are a daunting synthetic challenge owing to the intrinsic low reactivity of ketimine substrates. A highly enantioselective [3+2] cycloaddition reaction that makes use of isatin‐derived ketimines as reaction partners was developed. Notably, both simple and γ‐substituted allenoates could be utilized, and various 3,2′‐pyrrolidinyl spirooxindoles with a tetrasubstituted stereocenter were obtained in excellent yields and with nearly perfect enantioselectivity (>98 % ee in all cases).     

Direct Hydrogenation of Dinitrogen and Dioxygen via Eley–Rideal Reactions

Most Eley–Rideal abstraction reactions involve an energetic gas‐phase atom reacting directly with a surface adsorbate to form a molecular product. Molecular projectiles are generally less reactive, may dissociate upon collision with the surface, and thus more difficult to prove that they can participate intact in abstraction reactions. Here we provide experimental evidence for direct reactions occurring between molecular N₂⁺ and O₂⁺ projectiles and surface‐adsorbed D atoms in two steps: first, the two atoms of the diatomic molecule undergo consecutive collisions with a metal surface atom without bond rupture; and second, the rebounding molecule abstracts a surface D atom to form N₂D and O₂D intermediates, respectively, detected as ions. The kinematics of the collisional interaction confirms product formation by an Eley–Rideal reaction mechanism and accounts for inelastic energy losses commensurate with surface re‐ionization. Such energetic hydrogenation of dinitrogen may provide facile activation of its triple bond as a first step towards bond cleavage.     

Facile Assembly of Benzo[b]naphtho[2,3‐d]azocin‐6(5 H)‐ones by a Palladium‐Catalyzed Double Carbometalation

The palladium‐catalyzed reaction of 2‐alkynylanilines with 2‐(2‐bromobenzylidene)cyclobutanone as an efficient route to 7,8‐dihydrobenzo[b]naphtho[2,3‐d]azocin‐6(5 H)‐ones was developed. The fused eight‐membered ring was constructed conveniently. During the reaction process, double carbometalation was involved, which resulted in excellent selectivity with the formation of three new bonds. This transformation is highly efficient and leads to fused polycycles in good to excellent yields with good functional group tolerance.     

Standard molar enthalpy of formation of [(C12H8N2)2Bi(O2NO)3] and its biological activity on Schizosaccharomyces pombe

The title complex [(C₁₂H₈N₂)₂Bi(O₂NO)₃] was synthesized by reaction of 1,10-phenanthroline (phen) and Bi(NO₃)₃·5H₂O. The structure of the complex was characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. An advanced solution-reaction isoperibol microcalorimeter was applied to determine the standard molar enthalpies of formation at 298.15 K of the complex and Bi(NO₃)₃·5H₂O, giving –(798.92 ± 5.99) and –(1986.87 ± 0.20) kJ mol⁻¹, respectively. The biological effect of the complex was evaluated by microcalorimetry on the growth of Schizosaccharomyces pombe (S. pombe). According to thermogenic curves, the corresponding thermokinetics and thermodynamic parameters were derived. The complex had good bioactivity on the growth metabolism of S. pombe, with the value of IC₅₀ being 2.8 × 10⁻⁵ mol L⁻¹.