Single Atoms of Iron on MoS2 Nanosheets for N2 Electroreduction into Ammonia

Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH₃). Reported herein is a novel Fe-MoS₂ catalyst with Fe atomically dispersed onto MoS₂ nanosheets, imitating natural nitrogenase, to boost N₂ electroreduction into NH₃ at room temperature. The Fe-MoS₂ nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mg_cat.⁻¹ h⁻¹ for NH₃ at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N₂ was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS₂ with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N₂ into NH₃. This work provides new ideas for the design of catalysts for N₂ electroreduction and strengthens the understanding about N₂ activation over Mo-based catalysts.     

Three New Serratane Triterpenoids from Phlegmariurus squarrosus

Three new serratane triterpenoids, (3α,14α,15α,21α)‐3,14,15,21,29‐pentahydroxyserratan‐24‐oic acid ( 1 ), (3α,21β)‐serrat‐14‐ene‐3,21,24,30‐tetraol ( 2 ), and (3α,21α)‐serrat‐14‐ene‐3,21,24,29‐tetraol ( 3 ), were isolated from Phlegmariurus squarrosus, together with eight known compounds. Their chemical structures were elucidated on the basis of in‐depth spectroscopic analyses.     

Nitrophenol Derivatives Oxidized by Cerium(IV) Ammonium Nitrate (CAN) and Their Cytotoxicity

Oxidation of a series of phenols with cerium(IV) ammonium nitrate (CAN) in acetonitrile under mild conditions yields the mixture of corresponding nitrophenols. In the cases of methylphenols and hydroxy ‐carboxylic acids, the steric effect may reduce the nitration reaction. Compounds 3a and 4b showed selective activities to Hep 3B and Hep G2 cancer cell lines, respectively. Compound 2c showed selective activities to Hep G2 and MDA‐MB‐231 cancer cell lines. Furthermore, compound 10b showed selective activities to Hep G2, Hep 3B, MCF‐7 and MDA‐MB‐231 cancer cell lines.     

Complex Tellurium Salts with Supramolecular Bidimensional Lattices: Synthesis and X‐ray Characterization of (2‐Br‐C5NH5)2[TeX6] (X = Cl,Br)

The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H₃O)₂[TeX₆], which reacts subsequently with (2‐Br‐C₅NH₅)⁺X^‐ to afford (2‐Br‐C₅NH₅)₂[TeCl₆] ( 1 ) and (2‐Br‐C₅NH₅)₂[TeBr₆] ( 2 ). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P2₁/n (monoclinic, 1 ) and P1¯ (triclinic, 2 ). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX₆E‐system of the hexahalotellurates [TeX₆]^2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations.     

(C2H10N2)[BPO4F2] — Structural Relations between [BPO4F2]2— and [Si2O6]4—

(C₂H₁₀N₂)[BPO₄F₂] — Strukturbeziehungen zwischen [BPO₄F₂]^2— und [Si₂O₆]^4— Colourless crystals of (C₂H₁₀N₂)[BPO₄F₂] were prepared from mixture of ethylendiamine, H₃BO₃, BF₃ · C₂H₅NH₂, H₃PO₄ and HCl under mild hydrothermal conditions (220 °C). The crystal structure was determined by single crystal methods (triclinic, P1¯ (no. 2), a = 451.85(5) pm, b = 710.20(8) pm, c = 1210.2(2) pm, α = 86.08(1)°, β = 88.52(2)°, γ = 71.74(1)°, Z = 2) and contains infinite tetrahedral zweier‐single‐chains {[BPO₄F₂]^2—} which are isoelectronic (48e^—) with the polyanions {[Si₂O₆]^4—} of the pyroxene family.     

catena‐Poly­[[tetra­aqua­iron(II)]‐μ‐succinato‐κ2O:O′]

The title complex, {[Fe(C₄H₄O₄)(H₂O)₄]}_n, is an infinite poly­meric compound bridged by the succinate dianion. Two carboxyl­ate groups coordinate in a monodentate manner to the Fe^II atom, in a trans fashion, with an O—Fe—O bond angle of 175.72 (6)° and Fe—O distances of 2.0886 (14) and 2.1008 (15) Å. One of the uncoordinated carboxyl­ate O atom forms an intramolecular hydrogen bond with a coordinated water mol­ecule. Extensive hydrogen bonding between parallel poly­meric complex chains results in a three‐dimensional supramolecular structure.     

拟静态法测定混合溶剂的汽化热和汽化熵

讨论了沸点升高法测定混和溶剂化热和汽化熵的原理，并用拟静态法测定了乙醇－丙酮，并－四氯化碳和苯，甲苯三组混和溶剂在不同组成下的正常沸点，根据沸点数据求得了混和泶微分汽化热和汽化熵，实验结果表明，二元混和溶剂与理想溶液偏离不大时，其正常汽化熵符合Ｔｒｏｕｔｏｎ规则。     

Ring‐Opening Reactions of 3‐Aryl‐1‐benzylaziridine‐2‐carboxylates and Application to the Asymmetric Synthesis of an Amphetamine‐Type Compound

Nucleophilic ring‐opening reactions of 3‐aryl‐1‐benzylaziridine‐2‐carboxylates were examined by using O‐nucleophiles and aromatic C‐nucleophiles. The stereospecificity was found to depend on substrates and conditions used. Configuration inversion at C(3) was observed with O‐nucleophiles as a major reaction path in the ring‐opening reactions of aziridines carrying an electron‐poor aromatic moiety, whereas mixtures containing preferentially the syn‐diastereoisomer were generally obtained when electron‐rich aziridines were used (Tables 1–3). In the reactions of electron‐rich aziridines with C‐nucleophiles, S_N2 reactions yielding anti‐type products were observed (Table 4). Reductive ring‐opening reaction by catalytic hydrogenation of (+)‐trans‐(2S,3R)‐3‐(1,3‐benzodioxol‐5‐yl)aziridine‐2‐carboxylate (+)‐trans‐ 3c afforded the corresponding α‐amino acid derivative, which was smoothly transformed into (+)‐tert‐butyl [(1R)‐2‐(1,3‐benzodioxol‐5‐yl)‐1‐methylethyl]carbamate((+)‐ 14 ) with high retention of optical purity (Scheme 6).     

Four New Lariciresinol‐Based Lignan Glycosides from the Roots of Rhus javanica var. roxburghiana

The four new lariciresinol‐based lignan glycosides, (?)‐lariciresinol 4′‐(6″‐O‐feruloyl‐β‐D ‐glucopyranoside) ( 1 ), (?)‐lariciresinol 4′‐(4″,6″‐di‐O‐feruloyl‐β‐D ‐glucopyranoside) ( 2 ), 5,5′‐dimethoxylariciresinol 4′‐(4″,6″‐di‐O‐feruloyl)‐β‐D ‐glucopyranoside) ( 3 ), and 4‐O‐[α‐(1,2‐dihydroxyethyl)syringyl]‐5,5′‐dimethoxylariciresinol 4′‐(4″,6″‐di‐O‐feruloyl‐β‐D ‐glucopyranoside) ( 4 ), together with two known ones, lariciresinol 4′‐β‐D ‐glucopyranoside) ( 5 ) and tortoside B ( 6 ), were isolated from the BuOH extract of Rhus javanica var. roxburghiana roots, and their structures were established by means of various spectroscopic techniques.     

New Diterpene Alkaloids from Aconitum sungpanense var. leucanthum

Five new C₁₉ diterpene alkaloids, leucanthumsines A ( 1 ), B ( 2 ), C ( 3 ), D ( 4 ), and E ( 5 ), were isolated from the Chinese medicinal herb Aconitum sungpanense var. leucanthum, together with the known C₁₉ diterpene alkaloids pseudaconine, neoline, 1‐O‐methyldelphisine, crassicaudine, chasmanine, talatisamine, indaconitine, ezochansmanine, and leueantine D. The structures of these new alkaloids were elucidated by HR‐MS and advanced NMR methods, including ¹H‐ and ¹³C‐NMR (DEPT), ¹H,¹H‐COSY, HMQC, and HMBC experiments.