电化学阻抗法测定金属氢化物电极中氢的扩散系数

应用电化学阻抗法测定了不同荷电状态 (SOC)和不同温度下MlNi3.75Co0 .65Mn0 .4 Al0 .2 金属氢化物电极中氢的扩散系数 .结果表明 :室温下该电极中氢的扩散系数随其荷电量的增大而减小 ,SOC为 5 0 %时氢的扩散系数随温度的升高而增大 ,相应的氢扩散活化能为 35kJ/mo     

Facile and Versatile Chemoenzymatic Synthesis of Enterobactin Analogues and Applications in Bacterial Detection

Siderophores, such as enterobactin (Ent), are small molecules that can be selectively imported into bacteria along with iron by cognate transporters. Siderophore conjugates are thus a promising strategy for delivering functional reagents into bacteria. In this work, we present an easy‐to‐perform, one‐pot chemoenzymatic synthesis of functionalized monoglucosylated enterobactin (MGE). When functionalized MGE is conjugated to a rhodamine fluorophore, which affords RhB‐Glc‐Ent, it can selectively label Gram‐negative bacteria that utilize Ent, including some E. coli strains and P. aeruginosa. V. cholerae, a bacterium that utilizes linearized Ent, can also be weakly targeted. Moreover, the targeting is effective under iron‐limiting but not iron‐rich conditions. Our results suggest that the RhB‐Glc‐Ent probe is sensitive not only to the bacterial strain but also to the iron condition in the environment.     

Oligomeric Tectonics: Supramolecular Assembly of Double‐Stranded Oligobisnorbornene through π–π Stacking

Self‐assembly at the molecular level in solutions or on a surface is a subject of current interest. Herein we describe the tailoring of oligobisnorbornene 1 , which represents an innovative concept of a preorganized building block on the tens of nanometer scale. The rodlike 1 has vinyl and styrenyl end groups. Scanning tunneling microscopy (STM) reveals that the oligomers aggregate anisotropically along the long axis and form a one‐dimensional assembly in which, remarkably, no interstitial gap appears between neighboring oligomers. Dynamic light‐scattering (DLS) measurements indicate that the assembly develops in solution. With a shear treatment for dropcast films, a unidirectionally ordered domain with a defect density less than 0.5 % can be prepared. Simulation results by molecular dynamics suggest that there may be multiple interactions such as π–π stacking and dipolar attractions taking place between the termini of the oligomers. To demonstrate the importance of double bonds in the oligomeric backbones and termini towards the tectonic assembly, a hydrogenated analogue was synthesized; π–π interactions are thus less significant and the film morphology is completely different from that of 1 . This work extends the concept of molecular tectonics to preorganized oligomers and opens up a new avenue of nanopatterning toward nanodevices.     

On the Discreteness and Convergence in n-Dimensional Mobius Groups

Throughout this paper, we adopt the same notations as in [1,6, 8] such as the Möbius group M(Rⁿ), the Clifford algebraC_n–1, the Clifford matrix group SL(2, _n), the Cliffordnorm of ||A||=(|a|²+|b|²+|c|²+|d|²) (1) and the Clifford metric of SL(2, _n) or of the Möbius groupM(Rⁿ) d(A₁,A₂)=||A₁–A₂||(|a₁–a₂|²+|b₁–b₂|²+|c₁–c₂|²+|d₁–d₂|²)(2) where |·| is the norm of a Clifford number and represents f_i M(), i = 1,2, and so on. In addition, we adopt some notions in [6, 12]:the elementary group, the uniformly bounded torsion, and soon. For example, the definition of the uniformly bounded torsionis as follows.     

恒电位阶跃法研究贮氢合金MlNi_(3.75)Co_(0.65)Mn_(0.4)Al_(0.2)中氢的扩散行为

本文用恒电位阶跃法研究了不同放电深度 (DOD)和不同温度下贮氢合金MlNi3.75Co0 .6 5Mn0 .4 Al0 .2 中氢的扩散行为 .结果表明 :室温下该合金中氢的扩散系数随DOD的增大而增大 ,在5 0 %DOD的该合金中 ,氢的扩散系数随温度的升高而增大 ,扩散活化能为 19.87kJ/mol     

Hierarchical Self‐Assembly of Supramolecular Hydrophobic Metallacycles into Ordered Nanostructures

We describe herein the hierarchical self‐assembly of discrete supramolecular metallacycles into ordered fibers or spherical particles through multiple noncovalent interactions. A new series of well‐defined metallacycles decorated with long alkyl chains were obtained through metal–ligand interactions, which were capable of aggregating into ordered fibroid or spherical nanostructures on the surface, mostly driven by hydrophobic interactions. In‐depth studies indicated that the morphology diversity was originated from the structural information encoded in the metallacycles, including the number of alkyl chains and their spatial orientation. Interestingly, the morphology of the metallacycle aggregates could be tuned by changing the solvent polarity. These findings are of special significance since they provide a simple yet highly controllable approach to prepare ordered and tunable nanostructures from small building blocks by means of hierarchical self‐assembly.     

Assembly,Structures, and Properties of a Series of Metal‐Organic Coordination Polymers Derived from a Semi‐rigid Bis‐pyridyl‐bis‐amide Ligand

Four metal‐organic coordination polymers [Cd(4‐bpcb)_1.5Cl₂(H₂O)] ( 1 ), [Cd(4‐bpcb)_0.5(mip)(H₂O)₂] · 3H₂O ( 2 ), [Co(4‐bpcb)(oba)(H₂O)₂] ( 3 ), and [Ni(4‐bpcb)(oba)(H₂O)₂] ( 4 ) [4‐bpcb = N,N′‐bis(4‐pyridinecarboxamide)‐1, 4‐benzene, H₂mip = 5‐methylisophthalic acid, and H₂oba = 4, 4′‐oxybis(benzoic acid)] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, elemental analyses, IR spectroscopy, powder X‐ray diffraction, and TG analysis. In complex 1 , two Cl^– anions serve as bridges to connect two Cd‐(μ₁‐4‐bpcb) subunits forming a dinuclear unit, which are further linked by μ₂‐bridging 4‐bpcb to generate 1D zigzag chain. Complex 2 shows a 2D 6³ network constructed by [Cd‐mip]_n zigzag chains and μ₂‐bridging 4‐bpcb ligands. Complexes 3 and 4 are isostructural 2D (4, 4) grid networks derived from [M‐oba]_n (M = Co, Ni) zigzag chains and [M‐(4‐bpcb)]_n linear chains. The 1D chains for 1 and the 2D networks for 2 – 4 are finally extended into 3D supramolecular architectures by hydrogen bonding interactions. The roles of dicarboxylates and central metal ions on the assembly and structures of the target compounds were discussed. Moreover, the thermal stabilities, photoluminescent properties, and photocatalytic activities of complexes 1 – 4 and the electrochemical properties of complexes 3 and 4 were investigated.     

Efficient separation of tocopherol homologues in vegetable oil by ionic‐liquid‐based countercurrent chromatography using a non‐aqueous biphasic system

Tocopherol homologues are important fat‐soluble bioactive compounds with high nutritional value. However, it is of great challenge to separate these homologues because of their high structural similarities. In this work, ionic‐liquid‐based countercurrent chromatography was used for the separation and purification of tocopherol homologues. Conventional countercurrent chromatography and ionic‐liquid‐based countercurrent chromatography solvent systems were evaluated in respect of partition coefficient, separation factor, and stationary phase retention factor to separate these targets. Kind of ionic liquids, amount of ionic liquid, and sample amount were systematically optimized. A novel countercurrent chromatography non‐aqueous biphasic system composed of n‐hexane‐methanol‐1‐butyl‐3‐methylimidazolium chloride was established. The baseline separation of tocopherol mixtures was obtained in one cycle process. The ionic liquid played a key role in the countercurrent chromatography separation, which resulted in difference of partition behavior of individual tocopherol in the whole system through different hydrogen‐bonding affinity. Finally, n‐hexane‐methanol‐1‐butyl‐3‐methylimidazolium chloride (5:5:3, v/v) water‐free biphasic system was successfully applied to separate tocopherol homologues from vegetable oil that was not achieved beforehand. This method can be widely employed to separate many similar molecules such as tocotrienols, tocomonoenols, and marine‐derived tocopherol in food samples.     

Preparation of nano‐chitosan Schiff‐base copper complexes and their anticancer activity

A new kind of nano‐chitosan Schiff‐base Cu complexes with particle sizes of 350 nm were prepared by combination of nano‐chitosan, Cu and Schiff‐base, and characterized by FT‐IR spectra, TEM, DLS and elemental analysis. The modes and mechanism of interaction of the copper complexes with DNA were studied by the fluorescent probe method and electrophoresis analysis. The results suggest that the Cu complexes bound to DNA by electrostatic and intercalation modes. The anticancer activity of the Cu complexes was evaluated by Sulforhodamine B (SRB) assay in vitro. Nano‐chitosan and their Schiff‐base Cu complexes inhibited the growth of the liver cancer cell lines SMMC‐7721 in vitro. The inhibition rate of Schiff‐base Cu complexes was higher than that of nano‐chitosan. Nano‐chitosan combining with Schiff‐base and Cu improved their anticancer activity, which ascribed to the synergistic effect between the chitosan matrix and the planar construction of the Cu complexes. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation of Ag nanocrystals embedded silicate glass by field-assisted diffusion and its properties of optical absorption

Ag nanocrystals embedded silicate glass was successfully prepared by solid-state field-assisted diffusion, combined with post-annealing process. The changes of glass structure, the chemical states of Ag and O species, the microstructures of Ag nanocrystals, as well as the properties of optical absorption were studied for the as-diffused and post-annealed samples. The result showed that after the field-assisted diffusion process, some Ag⁺ ions replaced the alkaline ions in the glass matrix. Meanwhile, other Ag⁺ ions were reduced to Ag⁰ atoms occupying the interspaces of the network and Ag⁰ atoms clusters with small size were formed. This caused the relaxation of the glass network and the deceasing of force constant for Si–O linkage. After post-annealing process, bigger size of Ag nanoparticles were formed, which caused the peak corresponding to the surface plasmon resonance (SPR) observed.