Partial Oxidation of Methane to Synthesis Gas over Hexaaluminates LaMAl11O19-δ catalysts

A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu)were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11O19-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.     

L—组氨酸和色氨酸三元体系中稀土（Ⅲ）,钙（Ⅱ）的化学形态

在模拟生理条件下（３７℃,Ｉ＝０．１５ｍｏｌ／ＬＮａＣｌ）,用ｐＨ电位滴定与计算机模拟计算相结合的方法研究了镨（Ⅲ）、钆（Ⅲ）、铽（Ⅲ）、镱（Ⅲ）４ｔｋｈ ｔｑｄ ｆｆｆｆｙｂ ｂｂ ｔ ｑｇｈ （Ⅱ）、锌（Ⅱ）离子在Ｌ－组氨酸、色氨酸三元体系中的化学形态。讨论了稀土（Ⅲ）、钙（Ⅱ）和锌（Ⅱ）的物种分布特点。     

Large scale synthesis of red emissive carbon dots powder by solid state reaction for fingerprint identification

Red emissive carbon dots(CDs) powder was synthesized on a large scale from phloroglucinol and boric acid by a novel solid state reaction with yield up to 75%. This method is safe and convenient, for it needs neither high pressure reactors nor complicated post-treatment procedures. The as-prepared carbon dots powder exhibited strong red fluorescence with excitation-independent behavior. XPS measurement and PL spectra suggest that such red fluorescence arise from boron-doped structures in CDs, which increases along with the boron concentration on CDs surface but decreases when the concentration quenching effect takes place. To overcome the aggregation induced fluorescence quenching of the solid CDs powder,the conventional methods are dispersing CDs into a large amount of inert substrates. But our present work provides a new strategy to realize strong red fluorescence of CDs in solid state. As a result, such carbon dots powder works well for latent fingerprint identification on various material surfaces.     

Synthesis of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-one derivatives via a TBAI-catalyzed radical cascade cyclization

We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-one derivatives. With the TBAI–TBHP catalytic system, a broad series of structurally diverse indolo[2,1-a]isoquinolin-6(5H)-one derivatives were obtained in moderate to excellent yields. The reaction features mild reaction conditions, operationally easiness, scaled-up feasibility, and high functional-group-tolerance.     

Electrochemical aptamer sensor for highly sensitive detection of mercury ion with Au/Pt@carbon nanofiber‐modified electrode

In this paper, an electrochemical aptamer sensor was proposed for the highly sensitive detection of mercury ion (Hg²⁺). Carbon nanofiber (CNF) was prepared by electrospinning and high‐temperature carbonization, which was used for the loading of platinum nanoparticles (PtNPs) by the hydrothermal method. The Pt@CNF nanocomposite was modified on the surface of carbon ionic liquid electrode (CILE) to obtain Pt@CNF/CILE, which was further decorated by gold nanoparticles (AuNPs) through electrodeposition to get Au/Pt@CNF/CILE. Self‐assembling of the thiol‐based aptamer was further realized by the formation of Au‐S bond to get an electrochemical aptamer sensor (Aptamer/Au/Pt@CNF/CILE). Due to the specific binding of aptamer probe to Hg²⁺ with the formation of T‐Hg²⁺‐T structure, a highly sensitive quantitative detection of Hg²⁺ could be achieved by recording the changes of current signal after reacting with Hg²⁺ within the concentration range from 1.0 × 10^?15 mol/L to 1.0 × 10^?6 mol/L and the detection limit of 3.33 × 10^?16 mol/L (3σ). Real water samples were successfully analyzed by this method.     

BODIPY‐Bridged Push–Pull Chromophores for Nonlinear Optical Applications

A set of linear and dissymmetric BODIPY‐bridged push–pull dyes are synthesized. The electron‐donating substituents are anisole and dialkylanilino groups. The strongly electron‐accepting moiety, a 1,1,4,4‐tetracyanobuta‐1,3‐diene (TCBD) group, is obtained by insertion of an electron‐rich ethyne into tetracyanoethylene. A nonlinear push–pull system is developed with a donor at the 5‐position of the BODIPY core and the acceptor at the 2‐position. All dyes are fully characterized and their electrochemical, linear and nonlinear optical properties are discussed. The linear optical properties of dialkylamino compounds show strong solvatochromic behavior and undergo drastic changes upon protonation. The strong push–pull systems are non‐fluorescent and the TCBD‐BODIPY dyes show diverse photochemistry and electrochemistry, with several reversible reduction waves for the tetracyanobutadiene moiety. The hyperpolarizability μβ of selected compounds is evaluated using the electric‐field‐induced second‐harmonic generation technique. Two of the TCBD‐BODIPY dyes show particularly high μβ (1.907 μm) values of 2050×10^?48 and 5900×10^?48 esu. In addition, one of these dyes shows a high NLO contrast upon protonation–deprotonation of the donor residue.     

Ultra‐performance liquid chromatography coupled with electrospray ionization/quadrupole time‐of‐flight mass spectrometry for the rapid analysis of constituents in the traditional Chinese medical formula Danggui San

In this work, ultra‐performance LC with ESI quadrupole TOF‐MS (UPLC–ESI‐Q‐TOF‐MS) and automated MetaboLynx analysis was used to rapidly separate and identify the chemical constituents of Danggui San, a traditional Chinese medical formula. The analysis was performed on a Waters UPLC BEH C₁₈ column using a gradient elution system. A hyphenated ESI and Q‐TOF analyzer was used for the determination of the accurate mass of the protonated or deprotonated molecule and fragment ions in both positive and negative modes. Based on retention times, accurate mass, and the mass spectrometric fragmentation characteristics, a total of 47 compounds distributed over the chemical groups of phthalides, flavonoids, monoterpene glycosides, sesquiterpenoids, phenolics, and alkaloids, were simultaneously separated within 18 min and identified or tentatively elucidated in Danggui San for the first time. UPLC–ESI‐Q‐TOF‐MS analysis revealed the complexity of the chemical composition of this formula. The method developed is rapid, accurate, reliable, and highly sensitive to characterize the chemical constituents of Danggui San.     

质子交换膜燃料电池梯度化膜电极

为实现质子交换膜燃料电池的高性能(高功率密度或大电流密度)、低成本(低铂载量)、长寿命发电,人们尝试在燃料电池的核心部件膜电极结构中引入梯度化设计的概念。梯度化膜电极包括膜电极中各组件的梯度化:气体扩散层的PTFE含量与孔隙率的梯度化,催化层的催化剂与Nafion用量的梯度化以及微孔层的疏水性与孔隙率的梯度化。梯度化膜电极中催化剂分布、孔隙率分布、亲/疏水性分布合理,具有良好的三相反应界面以及质子、电子、反应气体、水等多相物质高效传输通道,从而能满足在低铂载量、低加湿以及高电流密度条件下高性能稳定工作。本文整理了近几年来有关燃料电池梯度化膜电极研究的相关文献,梳理了梯度化膜电极研究发展脉络,归纳总结了各种梯度化膜电极的制备方法、性能以及构效关系,并展望了梯度化膜电极下一步研究方向,对高性能、低成本、长寿命的燃料电池开发具有指导意义。     

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5? as building blocks

A two-dimensional network compound [Ce(DMF)₄(H₂O)][α-BW₁₂O₄₀]·H₂O·(HDMA)₂ (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H₅BW₁₂O₄₀·nH₂O, Ce(NO₃)₃·6H₂O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P2₁/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R ₁ = 0.07710, wR ₂ = 0.1416. Structural analysis indicates that every [Ce(DMF)₄(H₂O)]³⁺ building block is surrounded by three adjacent [α-BW₁₂O₄₀]⁵⁻ polyanions, meanwhile, every [α-BW₁₂O₄₀]⁵⁻ polyanion interconnects with three neighboring [Ce(DMF)₄(H₂O)]³⁺ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560°C. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4–7 media.