[{Cu(phen)2}(μ‐malato){Cu(phen)(NO3)}](NO3)·4H2O: malate acting as a tetra­dentate and dibridging ligand in a dinuclear copper complex

The crystal structure of the title compound, μ‐2‐hydroxy­butane­dioato‐1κ²O⁴,O^4′:2κ³O¹,O²,O⁴‐nitrato‐2κO‐tris­(1,10‐phen­anthroline)‐1κ⁴N,N′;2κ²N,N′‐dicopper(II) nitrate tetra­hydrate, [Cu₂(C₄H₃O₅)(NO₃)(C₁₂H₈N₂)₃](NO₃)·4H₂O, contains an unsymmetrical dinuclear copper complex with Cu(phen)₂ and Cu(phen)(NO₃) moieties (phen is 1,10‐phenanthroline) bridged by a malate (2‐hydroxy­butane­dioate) ligand, which acts as a double‐bridging and tetra­dentate ligand. As a result of this double‐bridging action, especially the direct coordination of the O atom of one carboxyl­ate group of malate to the two Cu atoms, the Cu⋯Cu distance is only 4.199 (1) Å and the two phen planes are roughly parallel [the shortest inter­planar distance is 3.28 (1) Å], exhibiting an obvious intra­molecular π–π stacking inter­action.     

Tolerance factor and phase stability of the garnet structure. Corrigendum

An error in an equation in the paper by Song et al. [ Acta Cryst. (2019), C 75 , 1353–1358 ] is corrected.     

Asymmetric Synthesis of a Fused Tricyclic Hydronaphthofuran Scaffold by Desymmetric [2+2+2] Cycloaddition

A rhodium(I)‐BINAP‐catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily available materials with excellent chemo‐, regio‐, diastereo‐, and enantioselectivity. Notable features of these reactions include 100 % atom economy, very broad scope, and mild reaction conditions.     

Topochemical Synthesis of Two‐Dimensional Transition‐Metal Phosphides Using Phosphorene Templates

Transition‐metal phosphides (TMPs) have emerged as a fascinating class of narrow‐gap semiconductors and electrocatalysts. However, they are intrinsic nonlayered materials that cannot be delaminated into two‐dimensional (2D) sheets. Here, we demonstrate a general bottom‐up topochemical strategy to synthesize a series of 2D TMPs (e.g. Co₂P, Ni₁₂P₅, and Co_xFe_2?xP) by using phosphorene sheets as the phosphorus precursors and 2D templates. Notably, 2D Co₂P is a p‐type semiconductor, with a hole mobility of 20.8 cm² V^?1 s^?1 at 300 K in field‐effect transistors. It also behaves as a promising electrocatalyst for the oxygen evolution reaction (OER), thanks to the charge‐transport modulation and improved surface exposure. In particular, iron‐doped Co₂P (i.e. Co_1.5Fe_0.5P) delivers a low overpotential of only 278 mV at a current density of 10 mA cm^?2 that outperforms the commercial Ir/C benchmark (304 mV).     

Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode

Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na_0.44Co_0.1Mn_0.9O₂ cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.     

Conjugated Copper–Catecholate Framework Electrodes for Efficient Energy Storage

A conjugated copper(II) catecholate based metal–organic framework (namely Cu‐DBC) was prepared using a D₂‐symmetric redox‐active ligand in a copper bis(dihydroxy) coordination geometry. The π‐d conjugated framework exhibits typical semiconducting behavior with a high electrical conductivity of ca. 1.0 S m^?1 at room temperature. Benefiting from the good electrical conductivity and the excellent redox reversibility of both ligand and copper centers, Cu‐DBC electrode features superior capacitor performances with gravimetric capacitance up to 479 F g^?1 at a discharge rate of 0.2 A g^?1. Moreover, the symmetric solid‐state supercapacitor of Cu‐DBC exhibits high areal (879 mF cm^?2) and volumetric (22 F cm^?3) capacitances, as well as good rate capability. These metrics are superior to most reported MOF‐based supercapacitors, demonstrating promising applications in energy‐storage devices.     

含侧链苯炔基的热固性聚酰亚胺薄膜

聚酰亚胺;苯炔基;热稳定性;玻璃化转变温度;力学性能     

离子液体中Mn（Salen）催化仲醇的氧化反应研究

以PhI(OAc)2为氧化剂,考察了1,3-二烷基咪唑硫酸酯系列离子液体中Mn(Salen)催化仲醇氧化的反应. 结果表明, 在MMISM-CH2Cl2(1:4,v:v)混合溶剂中, 反应条件为n((-苯乙醇): n(醋酸碘苯): n(催化剂1c)=50: 70: 1时, (-苯乙醇的转化率可以达到97.8%, 产物苯乙酮的选择性为100%, 远高于在纯CH2Cl2中的结果, 也要好于[bmim]BF4和[bmim]PF6对该反应的促进作用. 此外, BMISM及BEISE对催化剂1c有较好的稳定作用,催化剂可以重复使用.     

Establishment of the Model CD40 Cell Membrane Chromatography and Its Chromatographic Characteristics

A new model of atherosclerosis cell membrane chromatography has been established by using a CD40 cell membrane stationary phase (CD40 CMSP) prepared by immobilizing the CD40 cell membrane onto the surface of a silica carrier. The surface and chromatographic characteristics of CD40 CMSP were studied. The retention characteristics of anti-CD40 antibody and statins (lovastatin, simvastatin and pravastatin) were also investigated using this model. Affinities of the anti-CD40 antibody and statins toward CD40 cell membrane and receptors were based on the determination of log k′ values (the logarithm of capacity factor of a solute). There was a significant correlation between the affinity in the CD40–CMC and the effect in vitro for the pharmacological effect.     

Purification of low-abundance lysozyme in egg white via free-flow electrophoresis with gel-filtration chromatography

As an effective separation tool, free-flow electrophoresis has not been used for purification of low-abundance protein in complex sample matrix. Herein, lysozyme in complex egg white matrix was chosen as the model protein for demonstrating the purification of low-content peptide via an FFE coupled with gel fitration chromatography (GFC). The crude lysozyme in egg while was first separated via free-flow zone electrophoresis (FFZE). After that, the fractions with lysozyme activity were condensed via lyophilization. Thereafter, the condensed fractions were further purified via a GFC of Sephadex G50. In all of the experiments, a special poly(acrylamide- co-acrylic acid) (P(AM-co-AA)) gel electrophoresis and a mass spectrometry were used for identification of lysozyme. The conditions of FFZE were optimized as follows: 130 μL/min sample flow rate, 4.9 mL/min background buffer of 20 mM pH 5.5 Tris-Acetic acid, 350 V, and 14 °C as well as 2 mg/mL protein content of crude sample. It was found that the purified lysozyme had the purity of 80% and high activity as compared with its crude sample with only 1.4% content and undetectable activity. The recoveries in the first and second separative steps were 65% and 82%, respectively, and the total recovery was about 53.3%. The reasons of low recovery might be induced by diffusion of lysozyme out off P(AM-co-AA) gel and co-removing of high-abundance egg ovalbumin. All these results indicated FFE could be used as alternative tool for purification of target solute with low abundance.