Micro‐/Nanostructured Multicomponent Molecular Materials: Design,Assembly, and Functionality

Molecule‐based micro‐/nanomaterials have attracted considerable attention because their properties can vary greatly from the corresponding macro‐sized bulk systems. Recently, the construction of multicomponent molecular solids based on crystal engineering principles has emerged as a promising alternative way to develop micro‐/nanomaterials. Unlike single‐component materials, the resulting multicomponent systems offer the advantages of tunable composition, and adjustable molecular arrangement, and intermolecular interactions within their solid states. The study of these materials also supplies insight into how the crystal structure, molecular components, and micro‐/nanoscale effects can influence the performance of molecular materials. In this review, we describe recent advances and current directions in the assembly and applications of crystalline multicomponent micro‐/nanostructures. Firstly, the design strategies for multicomponent systems based on molecular recognition and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low‐dimensional multicomponent micro‐/nanostructures. Their new applications are also outlined. Finally, we briefly discuss perspectives for the further development of these molecular crystalline micro‐/nanomaterials.     

Determination of triapine,a ribonucleotide reductase inhibitor,in human plasma by liquid chromatography tandem mass spectrometry

Triapine is an inhibitor of ribonucleotide reductase (RNR). Studies have shown that triapine significantly decreases the activity of RNR and enhanced the radiation‐mediated cytotoxicity in cervical and colon cancer. In this work, we have developed and validated a selective and sensitive LC‐MS/MS method for the determination of triapine in human plasma. In this method, 2‐[(3‐fluoro‐2‐pyridinyl)methylene] hydrazinecarbothioamide (NSC 266749) was used as the internal standard (IS); plasma samples were prepared by deproteinization with acetonitrile; tripaine and the IS were separated on a Waters Xbridge Shield RP₁₈ column (3.5 µm; 2.1 × 50 mm) using a mobile phase containing 25.0% methanol and 75.0% ammonium bicarbonate buffer (10.0 mm , pH 8.50; v/v); column eluate was monitored by positive turbo‐ionspray tandem mass spectrometry; and quantitation of triapine was carried out in multiple‐reaction‐monitoring mode. The method developed had a linear calibration range of 0.250–50.0 ng/mL with correlation coefficient of 0.999 for triapine in human plasma. The IS‐normalized recovery and the IS‐normalized matrix factor of triapine were 101–104% and 0.89–1.05, respectively. The accuracy expressed as percentage error and precision expressed as coefficient of variation were ≤±6 and ≤8%, respectively. The validated LC‐MS/MS method was applied to the measurement of triapine in patient samples from a phase I clinical trial. Copyright © 2015 John Wiley & Sons, Ltd.     

Mechanically strong and stiff supramolecular polymers enabled by fiber reinforced long-chain alkane matrix

Fiber-reinforced-concrete (FRC) mechanism refers short discrete fibers that are uniformly distributed and randomly oriented, which offers an effective way to improve the mechanical performance of concrete. In the design of supramolecular polymers, an analogous concept of FRC appears to have been considered very rarely-although fibrous structure has been frequently observed/generated during the supramolecular polymerization. In this work, we apply the alkane thermosets, octadecane (C₁₈H₃₈) and tetracosane (C₂₄H₅₀), taking the role of “concrete”, and the low-molecular-weight monomer with long alkyl chains as the essential “fiber” component, to fabricate the “fiber reinforced supramolecular polymer”. Very much like FRC mechanism in material science, the resulting fiber reinforced supramolecular polymer thus exhibit unusually high mechanical strength and stiffness, which is unprecedented in the conventional supramolecular strategy.     

利用静电场中光电离效率谱精确确定1,3-二乙氧基苯分子的电离能

电离能是原子和分子的重要的特性参数,在光物理和光化学过程中起着重要作用,精确电离能对相关研究具有重要意义.电离能是调试零动能光谱信号的重要参考数据,在判断异构物数量和分子构型方面也起着关键作用.1,3-二乙氧基苯是一种重要的苯的衍生物,实验证实在超声分子束中包含两种旋转异构物Ⅰ(downup)和Ⅲ(down-down).它们的精确电离能还未见文献报道.本文采用直线式飞行时间质谱仪测量了静电场中1,3-二乙氧基苯光电离效率曲线,通过不同电场强度下测量的电离能(Stark效应)对场强的平方根线性拟合给出了两种异构物Ⅰ和Ⅲ精确的电离能分别为(62419±2)cm^–1和(63378±2)cm^–1.相对于通常的脉冲电场加速机制和零动能光谱测量的电离能,精确度大约分别由(±10)cm^–1和(±5)cm^–1提高到(±2)cm^–1.分析和讨论了不同方法测量的物理机制和优缺点.     

Boron group element doping of Li1.5Al0.5Ge1.5(PO4)3 based on microwave sintering

Journal of Solid State Electrochemistry - We report effectiveness of dopants selected from group 13, such as B, Ga, and In, on the conductivity of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) that is recognized as...     

Selective C-alkylation Between Alcohols Catalyzed by N-Heterocyclic Carbene Molybdenum

The first implementation of a molybdenum complex with an easily accessible bis-N-heterocyclic carbene ligand to catalyze β-alkylation of secondary alcohols via borrowing-hydrogen (BH) strategy using alcohols as alkylating agents is reported. Remarkably high activity, excellent selectivity, and broad substrate scope compatibility with advantages of catalyst usage low to 0.5 mol%, a catalytic amount of NaOH as the base, and H₂O as the by-product are demonstrated in this green and step-economical protocol. Mechanistic studies indicate a plausible outer-sphere mechanism in which the alcohol dehydrogenation is the rate-determining step.     

FeNi Alloy Nanoparticles Encapsulated in Carbon Shells Supported on N-Doped Graphene-Like Carbon as Efficient and Stable Bifunctional Oxygen Electrocatalysts

The development of cost-effective and durable oxygen electrocatalysts remains highly critical but challenging for energy conversion and storage devices. Herein, a novel FeNi alloy nanoparticle core encapsulated in carbon shells supported on a N-enriched graphene-like carbon matrix (denoted as FeNi@C/NG) was constructed by facile pyrolyzing the mixture of metal salts, glucose, and dicyandiamide. The in situ pyrolysis of dicyandiamide in the presence of glucose plays a significant effect on the fabrication of the porous FeNi@C/NG with a high content of doped N and large specific surface area. The optimized FeNi@C/NG catalyst displays not only a superior catalytic performance for the oxygen reduction reaction (ORR, with an onset potential of 1.0 V and half-wave potential of 0.84 V) and oxygen evolution reaction (OER, the potential at 10 mA cm⁻² is 1.66 V) simultaneously in alkaline, but also outstanding long-term cycling durability. The excellent bifunctional ORR/OER electrocatalytic performance is ascribed to the synergism of the carbon shell and FeNi alloy core together with the high-content of nitrogen doped on the large specific surface area graphene-like carbon.     

Enzymatic Extraction of Bioactive and Self‐Assembling Wool Keratin for Biomedical Applications

Keratin is widely recognized as a high‐quality renewable protein resource for biomedical applications. Despite their extensive existence, keratin resources such as feathers, wool, and hair exhibit high stability and mechanical properties because of their high disulfide bond content. Consequently, keratin extraction is challenging and its application is greatly hindered. In this work, a biological extraction strategy is proposed for the preparation of bioactive keratin and the fabrication of self‐assembled keratin hydrogels (KHs). Based on moderate and controlled hydrolysis by keratinase, keratin with a high molecular weight of approximately 45 and 28 kDa that retain its intrinsic bioactivities is obtained. The keratin products show excellent ability to promote cell growth and migration and are conferred with significant antioxidant ability because of their intrinsically high cysteine content. In addition, without the presence of any cross‐linking agent, the extracted keratin can self‐assemble into injectable hydrogels. The KHs exhibit a porous network structure and 3D culture ability, showing potential in promoting wound healing. This enzyme‐driven keratin extraction strategy opens up a new approach for the preparation of keratin that can self‐assemble into injectable hydrogels for biomedical engineering.     

Selectivity switch in transformation of CO2 from ethanol to methanol on Cu embedded in the defect carbon

The copper-based catalysts have been generally regarded as high-performance catalysts for CO_2 hydrogenation toward methanol,while the production of ethanol via C–C coupling on the copper-based catalysts is still challenging. Herein, we report a new catalyst where Cu nanoparticles are embedded in the carbon support with abundant defect sites, achieving a high selectivity for ethanol in the CO_2 hydrogenation. The experiments coupled with the theoretical studies show a clear map where carbon defects serve as anchor sites that can stabilize interfacial copper species, and interfacial Cu sites with low coordination numbers can adsorb two C_1 species and later convert them to a C_2 species via a hydrogenation-induced coupling reaction. Further adjacent Cu atoms of interfacial Cu sites can facilitate OH reduction reactions via the Cu–Cu bridge adsorption to assist the formation of ethanol. Especially, those specific active sites easily disappear in the reducing conditions and during the reaction, the major product can transform from ethanol to methanol.