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.     

Convenient Synthesis of Various Substituted Homotaurines from Alk‐2‐enamides

Various substituted homotaurines (=3‐aminopropane‐1‐sulfonic acids) 6 were readily synthesized in satisfactory to good yields via the Michael addition of thioacetic acid to alk‐2‐enamides 3 (→ 4 ), followed by LiAlH₄ reduction (→ 5 ) and performic acid oxidation (Scheme 1). The configuration of ‘anti’‐disubstituted homotaurine ‘anti’‐ 6h was deduced from the 3‐(acetylthio)alkanamide (=S‐(3‐amino‐1,2‐dimethyl‐3‐oxopropyl) ethanethioate)‘anti’‐ 4h formed in the Michael addition, which was identified via the Karplus equation analysis, and confirmed by X‐ray diffraction analysis. The current route is an efficient method to synthesize diverse substituted homotaurines, including 1‐, 2‐, and N‐monosubstituted, as well as 1,2‐, 1,N‐, 2,N‐, and N,N‐disubstituted homotaurines (Table).     

Structure‐Dependent Electrocatalysis of Ni(OH)2 Hourglass‐like Nanostructures Towards L‐Histidine

As the properties of nanomaterials are strongly dependent on their size, shape and nanostructures, probing the relations between macro‐properties and nanostructures is challenging for nanoscientists. Herein, we deliberately chose three types of Ni(OH)₂ with hexagonal, truncated trigonal, and trigonal hourglass‐like nanostructures, respectively, as the electrode modifier to demonstrate the correlation between the nanostructures and their electrocatalytic performance towards L ‐histidine. It was found that the hexagonal hourglass‐like Ni(OH)₂ sample had the best electrocatalytic activity, which can be understood by a cooperative mechanism: on one hand, the hexagonal sample possesses the largest specific surface area and the tidiest nanostructure, resulting in the most orderly packing on the electrode surface; on the other hand, its internal structure with the most stacking faults would generate a lot of unstable protons, leading to an enhanced electronic conductivity. The findings are important because they provide a clue for materials design and engineering to meet a specific requirement for electrocatalysis of L ‐histidine, possibly even for other biomolecules. In addition, the hexagonal Ni(OH)₂‐based biosensor shows excellent sensitivity and selectivity in the determination of L ‐histidine and offers a promising feature for the analytical application in real biological samples.     

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.     

Enhanced Electron Transfer for Hemoglobin in 2C_(12)N~ PVS-Composite Films Modified on Pyrolytic Graphite Electrodes

Some water-insoluble surfactants can be introduced onto surface of electrodes and formordered bilayer structure by self-assembling* The films provide a biomembrane-likemicroenvironment which is favorable to electron transfer for some redox proteins onelectrodesl. Surfactant-polymer multibilayer composite films show similarbiomembrane-mimetic bilayer structure to surfactant films alone, but demonstrateadvantages over the latter for their physically stronger solidity and stability because ofintr…     

信息经济时代的客户知识模型

客户知识由客户界定，沟通渠道，客户需求，客户行为以及客户赢利价值五个层次组成。其中每个知识层次都是包含该层次具体内容的客户知识子集。客户知识的掌握是一个过程，它从了解客户的基本信息以实现对客户进行界定开始，到识别客户对企业的赢利价值这一客户知识的核心。客户知识是制定“以客户为中心”的整合营销行动计划的基础。     

Purification,Characterization and ~1H NMR Resonance Assignment of an α-Like Neurotoxin BmK 16 from the Venom of Chinese Scorpion Buthus martensii Karsch

IntroductionThescorpionvenomsarerichsourceoffascinatingpeptides,whichusuallycomposedof 2 8— 70aminoacidresidues.TheyinteractspecificallywiththeNa+,K+,Ca2 +orCl- ionchannelsandarewidelyservedasusefultoolsinprobingtheproteinmappingofionchannelsandclarifyingthemolecularmechanisminvolvedinthesignaltransmissionandchannelgating .Thelong chainneurotox inpolypeptides (6 2— 6 7aminoacidresidues)isolatedfromscorpionscanbedividedintotwoclasses ,α andβ toxins ,onthebasisoftheireffectsonthesodiumchan…     

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.     

在新型光解反应体系中降解乙酰丙酸

介绍一种新型的光解反应体系. 该体系用空气(氧)电极作负载型TiO2 光催化膜的对电极. 空气(氧)电极是以空气中的氧作反应物,在电催化剂的作用下合成H2O2,为光化学氧化反应提供廉价的原料. 将空气(氧)电极应用于光催化反应体系,使光化学氧化反应和光催化氧反应同时发生于同一体系. 实验结果表明,在相同的光照条件下,乙酰丙酸在新型光解反应体系中的降解速度比在单一的光催化体系中或在光化学反应体系中明显增大. 文中对实验结果进行了初步分析     

电磁场统一性质的三维描述

论述了电场与磁场本质上的统一性质,构造了三维空间中电磁场的统一场量,给出它的方程、场量的模方与能量和动量的关系,发现三维空间中的统一场量自身的标积竟然是相对论变换下的不变量．