Hemin-histamine-montmorillonite clay conjugate as a model biocatalyst to mimic natural peroxidase

We successfully synthesized the first hemin-montmorillonite bio-conjugate with an amino acid residue to mimic natural peroxidase enzyme. Histamine was intercalated in montmorillonite by cation exchange, then a hemin molecule was loaded onto the histamine-montmorillonite with an adsorption capacity of 7.0 mg g-1. The hemin-histamine-montmorillonite conjugate shows high peroxidase activity as indicated by the oxidation of guaiacol, which is attributed to the activation of hemin by Fe–N complex formation between the imidazole group in histamine and the iron ion in the hemin molecule. Temperature- dependent peroxidase activity for this synthesized biomimetic material indicates that raising the reaction temperature could significantly enhance the activity of the conjugate. The biomimetic catalyst has good reusability; nearly 100% activity can be retained after three cycles. Because montmorillonite clay is widely distributed in the environment, this material offers great potential for in situ and ex situ remediation of many organic contaminants in surface/subsurface soils.     

Selective adsorption of metronidazole on conjugated microporous polymers

Conjugated microporous polymers (CMPs) have recently received extensive attention in oil/organic solvent-water separation field as a kind of ideal porous absorbents with tunable porosity, large surface areas, and super-hydrophobicity. However, reports on the application of CMPs in adsorption of hydrophilic contaminants from water are very few. In this work, we studied the adsorption of metronidazole (MNZ), a polar antibiotic, by two kinds of CMPs. The adsorption characteristics of MNZ by the CMPs, including adsorption kinetics, mechanism, and isotherm parameters were calculated. The adsorption kinetics of MNZ was well expressed by the pseudo-second-order model, and the adsorption process was found to be mainly controlled by film diffusion. The adsorption isotherm data agreed well with the Langmuir isotherm model, and the values of free energy E indicated that the adsorption nature of MNZ on the CMPs was physisorption. Increasing dispersion degree of the CMPs in MNZ solution resulted in greater adsorption. This work may provide fundamental guidance for the removal of antibiotics by CMPs.     

Monodispersed AuPd nanoalloy: composition control synthesis and catalytic properties in the oxidative dehydrogenative coupling of aniline

A series of AuPd@C nanoalloy catalysts with tunable compositions were successfully prepared by a co-reduction method. The use of borane-tert-butylamine complex as reductant and oleylamine as both solvent and reductant was very effective for the preparation of the monodispersed nanoalloy. We evaluated the catalytic activity of these AuPd@C nanoalloys for oxidative dehydrogenative coupling of aniline, which showed better catalytic activity than equal amounts of sole Au@C or Pd@C catalyst. The Au₁Pd₃@C catalyst exhibited the best performance, indicating that the conversion and selectivity were improved along with the increase of Pd composition. However if the Pd composition was too high in the AuPd alloy, Au₁Pd₇@C achieved only 81% conversion in this reaction.     

Ferrocenylethynyl‐Terminated Azobenzenes: Synthesis,Electrochemical, and Photoisomerization Studies

Ferrocenylethynyl‐terminated derivatives 8 – 12 have been synthesized and characterized by electrochemistry and UV/Vis spectroscopy. The electrochemical and photophysical studies indicate that the electronic communication in ferrocenylethynyl‐substituted derivatives is strongly influenced by the substituted position of the ferrocenylethynyl moiety. In situ electrochemical oxidation or chemical oxidation caused a characteristically weak ligand‐to‐metal charge‐transfer (LMCT) band to appear at 700–1000 nm. Subsequent electrochemical reduction or chemical reduction recovered the most of the original curve and the color of the solution as well. Among the derivatives, compound 8 exhibits the highest cis/trans molar ratio (64:36) in the photostationary state (PSS) upon light irradiation at 365 nm. Compound 8 exhibits excellent fatigue resistance and reversibility under several repeated reversible isomerization cycles.     

Bifunctional Polyacrylonitrile Fiber‐Mediated Conversion of Sucrose to 5‐Hydroxymethylfurfural in Mixed‐Aqueous Systems

A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF‐PA[BnBr]) and a metal chloride was employed to produce 5‐hydroxymethylfurfural (HMF) from sucrose in mixed‐aqueous systems. The promoter of PANF‐PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8 %) of HMF, superior recyclability (6 cycles) of the process, and effective scale‐up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix‐bed reactor.     

Rational Design of Selenadiazole Derivatives to Antagonize Hyperglycemia‐Induced Drug Resistance in Cancer Cells

Hyperglycemia is an important factor for chemoresistance of hepatocellular carcinoma patients with diabetes to therapeutics. In the present study, a series of selenadiazole derivatives have been rationally designed, synthesized, and found be able to antagonize drug resistance in HepG2 cells to doxorubicin (DOX) under simulated diabetes conditions. Hyperglycemia could promote the cell proliferation through upregulation of ERK and AKT phosphorylation. However, the synthetic selenadiazole derivatives effectively potentiated the cellular uptake of DOX and enhanced the antiproliferative activity of DOX on HepG2 cells by induction of apoptosis, via regulation of ROS‐mediated AMPK activation, inhibition of mTORC1, and an increase in DNA damage. The selenadiazole derivatives that possess an increased lipophilicity could enhance the cellular uptake and anticancer efficacy of DOX. Taken together, this study provides a rational design strategy of selenadiazole derivatives to overcome hyperglycemia‐induced drug resistance.     

银(I)配位聚合物修饰Preyssler型多金属氧酸盐的高维、高连接结构的组装及性质

以AgNO3、K12.5Na1.5[Na P5W30O110]·15H2O及柔性配体1,1′-双(3,5-二甲基-1H-吡唑)甲烷(H2bdpm)为原料,利用水热合成方法合成了1个新的基于单核银为中心的Preyssler多酸阴离子的有机-无机杂化化合物:[Ag13(H2bdpm)8(H2O)5(HAg P5W30O110)]·2H2O(1),并通过元素分析、红外光谱、热重分析和X-射线单晶衍射等分析手段对化合物1进行了表征.X-射线单晶结构分析表明,该化合物属于三斜晶系,P1空间群,晶胞参数:a=19.135(5),b=20.313(5),c=28.400(5),Z=2,R1=0.0550,w R2=0.1542.化合物1包含罕见的以单核银为中心的Preyssler型多酸阴离子,该阴离子通过金属银连接形成二维无机层.相连的二维层之间通过多种Ag-H2bdpm金属有机亚单元进一步连接形成三维框架.该化合物最大的结构特点在于Preyssler型多酸阴离子的高连接(十八连接)以及Ag(I)离子多样的配位模式.     

Construction of Nitronyl Nitroxide‐Based 3d–4f Clusters: Structure and Magnetism

Three unprecedented nitronyl nitroxide radical‐bridged 3d–4f clusters, [Ln₂Cu₂(hfac)₁₀(NIT‐3py)₂(H₂O)₂](Ln^III=Y, Gd, Dy), have been obtained from the self‐assembly of Ln(hfac)₃, Cu(hfac)₂, and the radical ligand. The Dy complex shows a slow relaxation of magnetization, representing the first nitronyl nitroxide radical‐based 3d–4f cluster with single‐molecule magnet behavior.     

Iron(III)‐Selective Chelation‐Enhanced Fluorescence Sensing for In Vivo Imaging Applications

A “turn‐on” pattern Fe³⁺‐selective fluorescent sensor was synthesized and characterized that showed high fluorescence discrimination of Fe³⁺ over Fe²⁺ and other tested ions. With a 62‐fold fluorescence enhancement towards Fe³⁺, the probe was employed to detect Fe³⁺ in vivo in HeLa cells and Caenorhabditis elegans, and it was also successfully used to elucidate Fe³⁺ enrichment and exchange infected by innexin3 (Inx3) in hemichannel‐closed Sf9 cells.     

Preface

<正>Organic photovoltaics(OPVs),especially the solutionprocessable organic photovoltaic materials and devices,have attracted great attention in recent years because of the advantages of simple device structure,low cost,light weight and flexibility of the organic solar cells(OSCs).The highest power conversion efficiency of the OSCs has been im-