Three‐Dimensional Metal–Fullerene Frameworks

Hexakis‐substituted [60]fullerene adducts with icosahedral symmetry provide an unprecedented scaffold for the spatial arrangement of twelve functional groups with high geometric precision. This unique molecular symmetry identifies such polyfunctional organic building blocks as potential highly connective linkers for coordination polymer and metal–organic framework synthesis. Hereby, the linker exhibits a higher connectivity than the metal ions and with the main connectivity based on the ligand, this can create a new type of inversely cross‐linked framework. Two hexakis adducts bearing either twelve glycolic acid or 3‐hydroxypropionic acid side chains attached to its malonate units were incorporated as organic connectivity centers in the first fullerene‐containing three‐dimensional frameworks by coordination with Zn²⁺.     

Zn or O? An Atomic Level Comparison on Antibacterial Activities of Zinc Oxides

For the first time, the influence of different types of atoms (Zn and O) on the antibacterial activities of nanosized ZnO was quantitatively evaluated with the aid of a 3D‐printing‐manufactured evaluation system. Two different outermost atomic layers were manufactured separately by using an ALD (atomic layer deposition) method. Interestingly, we found that each outermost atomic layer exhibited certain differences against gram‐positive or gram‐negative bacterial species. Zinc atoms as outermost layer (ZnO?Zn) showed a more pronounced antibacterial effect towards gram‐negative E. coli (Escherichia coli), whereas oxygen atoms (ZnO?O) showed a stronger antibacterial activity against gram‐positive S. aureus (Staphylococcus aureus). A possible antibacterial mechanism has been comprehensively discussed from different perspectives, including Zn²⁺ concentrations, oxygen vacancies, photocatalytic activities and the DNA structural characteristics of different bacterial species.     

Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N‐Heterocyclic Carbene–Copper Complex

The alkylative carboxylation of allenamide catalyzed by an N‐heterocyclic carbene (NHC)–copper(I) complex [(IPr)CuCl] with CO₂ and dialkylzinc reagents was investigated. The reaction of allenamides with dialkylzinc reagents (1.5 equiv) and CO₂ (1 atm.) proceeded smoothly in the presence of a catalytic quantity of [(IPr)CuCl] to afford (Z)‐α,β‐dehydro‐β‐amino acid esters in good yields. The reaction is regioselective, with the alkyl group introduced onto the less hindered γ‐carbon, and the carboxyl group introduced onto the β‐carbon atom of the allenamides. The first step of the reaction was alkylative zincation of the allenamides to give an alkenylzinc intermediate followed by nucleophilic addition to CO₂. A variety of cyclic and acyclic allenamides were found to be applicable to this transformation. Dialkylzinc reagents bearing β‐hydrogen atoms, such as Et₂Zn or Bu₂Zn, also gave the corresponding alkylative carboxylation products without β‐hydride elimination. The present methodology provides an easy route to alkyl‐substituted α,β‐dehydro‐β‐amino acid ester derivatives under mild reaction conditions with high regio‐ and stereoselectivtiy.     

Metal Oxide Assisted Preparation of Core–Shell Beads with Dense Metal–Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants

Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L^?1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings.     

Aspartate‐Based CXCR4 Chemokine Receptor Binding of Cross‐Bridged Tetraazamacrocyclic Copper(II) and Zinc(II) Complexes

The CXCR4 chemokine receptor is implicated in a number of diseases including HIV infection and cancer development and metastasis. Previous studies have demonstrated that configurationally restricted bis‐tetraazamacrocyclic metal complexes are high‐affinity CXCR4 antagonists. Here, we present the synthesis of Cu²⁺ and Zn²⁺ acetate complexes of six cross‐bridged tetraazamacrocycles to mimic their coordination interaction with the aspartate side chains known to bind them to CXCR4. X‐ray crystal structures for three new Cu²⁺ acetate complexes and two new Zn²⁺ acetate complexes demonstrate metal‐ion‐dependent differences in the mode of binding the acetate ligand concomitantly with the requisite cis‐V‐configured cross‐bridged tetraazamacrocyle. Concurrent density functional theory molecular modelling studies produced an energetic rationale for the unexpected [Zn(OAc)(H₂O)]⁺ coordination motif present in all of the Zn²⁺ cross‐bridged tetraazamacrocycle crystal structures, which differs from the chelating acetate [Zn(OAc)]⁺ structures of known unbridged and side‐bridged tetraazamacrocyclic Zn²⁺‐containing CXCR4 antagonists.     

Efficient Synthesis of Diaryl Ketones by Nickel‐Catalyzed Negishi Cross‐Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect

The first Negishi cross‐coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross‐coupling was accomplished with bench‐stable, inexpensive precatalyst [Ni(PPh₃)₂Cl₂] that shows high functional‐group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, <10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional‐group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross‐coupling under mild conditions.     

基于闪锌矿晶体中受激电磁耦子散射产生可调谐太赫兹波的理论研究

基于受激电磁耦子散射原理,采用已报道的利用非线性光学参量振荡方法产生可调谐太赫兹波的实验条件作为理论分析的实验模型,以GaAs,GaP, InP,ZnTe晶体为代表,计算分析了在闪锌矿晶体中参量振荡产生太赫兹波的吸收、增益特性,对输出THz波的调谐特性给出了详尽分析.分析太赫兹波高效耦合输出的腔型结构,并与掺氧化镁铌酸锂晶体组成的太赫兹波参量振荡器做对比. 关键词： 太赫兹波 太赫兹波参量振荡 电磁耦子 闪锌矿晶体     

纳米级ZnO/MgO固体的合成及其对CO的氧化活性

The ZnO/MgO solid samples containing the ZnO nanoparticles of controllable size were prepared using colloidal technique. The catalytic performance of the ZnO/MgO samples for the CO oxidation was measured. It was revealed that the rate of the CO oxidation reaction on the ZnO nanoparticles with variable average radius (2.01-2.29 nm) shows nonmonotonic dependence caused by the quantum-confinement effect.     

Gold(I)-catalyzed intramolecular cyclopropanation of dienynes

Gold(I) complexes are the most active catalysts for the biscyclopropanation of dienynes to form tetracyclic compounds. PtII and ZnII are also able to promote the biscyclopropanation, although less efficiently. The configurations obtained in all cases with the use of gold(I) catalysts can be explained by the pathway proceeding through anti cyclopropyl gold carbenes. Similar intermediates are most probably involved in reactions catalyzed by RuII and PtII. Two different cyclopropanation pathways have been found; they depend on the structures of the cyclopropyl gold carbenes (anti or syn) and the relative arrangements of the metal carbenes and the alkenes.     

Synthesis and Crystal Structure of a New One-dimensional Zn(II) Nitronyl Nitroxide Complex Bridged by Pyridine-2,4-dicarboxylate Anion

1 INTRODUCTION The synthesis and study of transition metal com- pounds incorporating organic free radicals directly bound to their coordination sphere are a major re- search aim in the field of molecular magnetism[1]. Exceptional stability, ease of chemical modification and versatility in their coordination properties have made nitroxide free radicals one of the most attrac- tive spin carriers for the design of molecular magne- tic materials[2, 3]. The structures and magnetic prope- rties …