Na-W-Mn/SiO2催化剂体系中W和Mn对甲烷氧化偶联反应的作用

制备了一系列不同W,Mn含量的Na-W-Mn/SiO2催化剂,并进行了其催化甲烷氧化偶联反应性能评价和XPS,XRD表征.研究结果表明,W和Mn的含量分别为2.2%≤W≤8.9%和0.5%≤Mn≤3%时,催化剂具有较好的甲烷氧化偶联反应性能.Mn的表面浓度与甲烷的转化率和乙烯的选择性有较好的对应关系,W的表面浓度与乙烷的选择性有一定的关联,据此提出Na-O-Mn和Na-O-W都是甲烷氧化偶联反应的活性中心.反应的活性相是Na2WO4,Na2W2O7和Mn2O3.     

基质辅助激光解吸电离-飞行时间质谱表征6氟双酚A芳香环状聚醚酮(砜)

应用基质辅助激光解吸电离飞行时间质谱,在不同阳离子剂的存在下,对6氟双酚A聚芳醚酮(砜)环状低聚物的结构进行了确认,研究了环状化合物对金属离子的选择性及激光质谱表征含氟环状低聚物的适宜条件.     

Dinuclear Ruthenium(II) Complexes That Induce and Stabilise G‐Quadruplex DNA

A series of dinuclear ruthenium(II) complexes were synthesised, and the complexes were determined to be new highly selective compounds for binding to telomeric G‐quadruplex DNA. The interactions of these complexes with telomeric G‐quadruplex DNA were studied by using circular dichroism (CD) spectroscopy, fluorescence resonance energy transfer (FRET) melting assays, isothermal titration calorimetry (ITC) and molecular modelling. The results showed that the complexes 1 , 2 and 4 induced and stabilised the formation of antiparallel G‐quadruplexes of telomeric DNA in the absence of salt or in the presence of 100 mM K⁺‐containing buffer. Furthermore, complexes 1 and 2 strongly bind to and effectively stabilise the telomeric G‐quadruplex structure and have significant selectivity for G‐quadruplex over duplex DNA. In comparison, complex 3 had a much lesser effect on the G‐quadruplex, suggesting that possession of a suitably sized plane for good π–π stacking with the G‐quadruplets is essential for the interaction of the dinuclear ruthenium(II) complexes with the G‐quadruplex. Moreover, telomerase inhibition by the four complexes and their cellular effects were studied, and complex 1 was determined to be the most promising inhibitor of both telomerase and HeLa cell proliferation.     

Oxidized Carbon Nitrides: Water‐Dispersible,Atomically Thin Carbon Nitride‐Based Nanodots and Their Performances as Bioimaging Probes

Three‐dimensional (3D) carbon nitride (C₃N₄)‐based materials show excellent performance in a wide range of applications because of their suitable band structures. To realize the great promise of two‐dimensional (2D) allotropes of various 3D materials, it is highly important to develop routes for the production of 2D C₃N₄ materials, which are one‐atom thick, in order to understand their intrinsic properties and identify their possible applications. In this work, water‐dispersible, atomically thin, and small carbon nitride nanodots were produced using the chemical oxidation of graphitic C₃N₄. Various analyses, including X‐ray diffraction, X‐ray photoelectron, Fourier‐transform infrared spectroscopy, and combustion‐based elemental analysis, and thermogravimetric analysis, confirmed the production of 3D oxidized C₃N₄ materials. The 2D C₃N₄ nanodots were successfully exfoliated as individual single layers; their lateral dimension was several tens of nanometers. They showed strong photoluminescence in the visible region as well as excellent performances as cell‐imaging probes in an in vitro study using confocal fluorescence microscopy.     

Ionic Conductivity of β‐Cyclodextrin–Polyethylene‐Oxide/Alkali‐Metal‐Salt Complex

Highly conductive, crystalline, polymer electrolytes, β‐cyclodextrin (β‐CD)–polyethylene oxide (PEO)/LiAsF₆ and β‐CD–PEO/NaAsF₆, were prepared through supramolecular self‐assembly of PEO, β‐CD, and LiAsF₆/NaAsF₆. The assembled β‐CDs form nanochannels in which the PEO/X⁺ (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion.     

Polyoxometalate‐Mediated One‐Pot Synthesis of Pd Nanocrystals with Controlled Morphologies for Efficient Chemical and Electrochemical Catalysis

Polyoxometalates (POMs), as inorganic ligands, can endow metal nanocrystals (NCs) with unique reactivities on account of their characteristic redox properties. In the present work, we present a facile POM‐mediated one‐pot aqueous synthesis method for the production of single‐crystalline Pd NCs with controlled shapes and sizes. The POMs could function as both reducing and stabilizing agents in the formation of NCs, and thus gave a fine control over the nucleation and growth kinetics of NCs. The prepared POM‐stabilized Pd NCs exhibited excellent catalytic activity and stability for electrocatalytic (formic acid oxidation) and catalytic (Suzuki coupling) reactions compared to Pd NCs prepared without the POMs. This shows that the POMs play a pivotal role in determining the catalytic performance, as well as the growth, of NCs. We envision that the present approach can offer a convenient way to develop efficient NC‐based catalyst systems.     

Tuning the Upconversion Luminescence Lifetimes of KYb2F7:Ho3+ Nanocrystals for Optical Multiplexing

Conventional luminescent color coding is limited by spectral overlap and the interference of background fluorescence, thus restricting the number of distinguishable identities that can be used in practice. Here, we demonstrate the possibility of generating diverse time‐domain codes, specially designed for a single emission band, using lanthanide‐doped upconversion nanocrystals. Based on the knowledge of concentration quenching, the upconversion luminescence kinetics of KYb₂F₇: Ho³⁺ nanocrystals can be precisely controlled by modifying the dopant concentration of Ho³⁺ ions, resulting in a tunable emission lifetime from 75.8 to 1944.5 μs, which suggests the practicality of these time‐domain codes for optical multiplexing.     

1,2,1′,2′-双蒽醌-3,12-二羧酸的还原反应

1,2,1＇,2＇-双蒽醌-3,12-二羧酸(1)是一个π-共轭体系芳环化合物,内环酮基由于受空间效应和共振效应的影响,不能被还原成相应的醇或相应的碳氢基团,却成了不常见的内“双氧桥”化合物(4)。化合物2,3,4的结构已经确定,并对1的还原机理进行了初步讨论。     

Instantaneous Free Radical Scavenging by CeO2 Nanoparticles Adjacent to the Fe−N4 Active Sites for Durable Fuel Cells

To achieve the Fe−N−C materials with both high activity and durability in proton exchange membrane fuel cells, the attack of free radicals on Fe−N₄ sites must be overcome. Herein, we report a strategy to effectively eliminate radicals at the source to mitigate the degradation by anchoring CeO₂ nanoparticles as radicals scavengers adjacent (Sca^ad-CeO2) to the Fe−N₄ sites. Radicals such as ⋅OH and HO₂⋅ that form at Fe−N₄ sites can be instantaneously eliminated by adjacent CeO₂, which shortens the survival time of radicals and the regional space of their damage. As a result, the CeO₂ scavengers in Fe−NC/Sca^ad-CeO2 achieved ∼80 % elimination of the radicals generated at the Fe−N₄ sites. A fuel cell prepared with the Fe−NC/Sca^ad-CeO2 showed a smaller peak power density decay after 30,000 cycles determined with US DOE PGM-relevant AST, increasing the decay of Fe−NC_Phen from 69 % to 28 % decay.