Electrochemical myoglobin biosensor based on carbon ionic liquid electrode modified with Fe3O4@SiO2 microsphere

In this paper, a Fe₃O₄@SiO₂ core-shell structure microsphere was synthesized and used to investigate the direct electron transfer of myoglobin (Mb) with a 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the substrate electrode. The mixture of Mb and Fe₃O₄@SiO₂ microsphere could form an organic–inorganic composite, which was immobilized on the surface of CILE with a chitosan (CS) film. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared on CS/Mb-Fe₃O₄@SiO₂/CILE with the formal peak potential (E ^0′) located at ?0.31 V (vs. saturated calomel electrode), which was corresponded to the electroactive center of Mb heme Fe(III)/Fe(II) redox couples. Direct electrochemical behaviors of Mb in CS-Fe₃O₄@SiO₂ composite film were carefully investigated with the electrochemical parameters calculated. The CS/Mb-Fe₃O₄@SiO₂/CILE showed good electrocatalytic behaviors to the reduction of trichloroacetic acid in the concentration range from 0.2 to 11.0 mmol L^?1 with the detection limit of 0.18 mmol L^?1 (3σ). Based on CS/Mb-Fe₃O₄@SiO₂/CILE, a new third-generation reagentless electrochemical biosensor was constructed with higher sensitivity and reproducibility.     

Effect of temperature on the morphologies and electrochemical properties of polyaniline-gold fibrillar nanocomposites

The polyaniline-gold (PANI-AuNPs) fibrillar nanocomposites were prepared via a simple one-pot synthesis route in ethylene glycol (EG) medium. The morphology of PANI-AuNPs was characterized by transmission electron microscopy (TEM), and their electrochemical properties were studied by CV, TAF and EIS measurement using an electrochemical workstation. The results show that the morphology of nanocomposites can be controlled by changing the temperature. The diameter of PANI-AuNPs composite nanofiber reduce from about 80 to 30 nm, and the size of AuNP also reduce from about 20 to 4 nm, with the rise of synthesized temperature. When the synthesized temperature is 10°C, the distribution of AuNPs is the best, and the amount of AuNPs dispersed in PANI is the most, as well as the electrochemical performance of PANI-AuNPs is the most excellent.     

没食子酸修饰树脂对对氯苯胺和对硝基苯胺的吸附行为

通过Friedel-Crafts后交联及化学修饰反应,制备了没食子酸修饰的超高交联吸附树脂(GAMR),并通过傅里叶变换红外光谱仪、元素分析仪和比表面及孔径分析仪对其理化性质进行了表征。通过等温吸附实验和吸附动力学实验,研究了GAMR树脂对不同温度下水溶液中的对氯苯胺和对硝基苯胺的吸附行为。结果表明,GAMR树脂具有较高的比表面积(1227.1m2/g)和较丰富的微孔(888.5m2/g),树脂表面修饰了较丰富的羟基和羰基。GAMR树脂对对氯苯胺和对硝基苯胺均具有良好的吸附性能,吸附量随着温度的升高而下降。Freundlich等温吸附方程能够更好地拟合吸附等温线数据,GAMR树脂对对氯苯胺和对硝基苯胺的吸附机理较复杂。吸附焓变ΔH0,表示吸附过程为放热反应,且以物理吸附为主;吸附自由能变ΔG0,说明吸附过程可自发进行;吸附熵变ΔS0,表明吸附质分子在树脂表面上的运动受到了限制。动力学实验结果表明,吸附过程符合一级动力学方程,颗粒内扩散是吸附过程的主要控制步骤。     

3D amorphous carbon and graphene co-modified LiFePO4 composite derived from polyol process as electrode for high power lithium-ion batteries

Amorphous carbon and graphene co-modified LiFePO_4 nanocomposite has been synthesized via a facile polyol process in connection with a following thermal treatment.Various characterization techniques,including XRD.Mossbauer spectra,Raman spectra,SEM,TEM,BET,O_2-TPO,galvano charge-discharge,CV and EIS were applied to investigate the phase composition,carbon content,morphological structure and electrochemical performance of the synthesized samples.The effect of introducing way of carbon sources on the properties and performance of LiFePO_4/C/graphene composite was paid special attention.Under optimized synthetic conditions,highly crystalized olivine-type LiFePO_4was successfully obtained with electron conductive Fe_2P and FeP as the main impurity phases.SEM and TEM analyses demonstrated the graphene sheets were randomly distributed inside the sample to create an open structured LiFePO_4 with respect to graphene,while the glucosederived carbon mainly coated over LiFeP04 particles which effectively connected the graphene sheets and LiFePO_4 particles to result in a more efficient charge transfer process.As a result,favorable electrochemical performance was achieved.The performance of the amorphous carbon-graphene co-modified LiFePO_4 was further progressively improved upon cycling in the first 200 cycles to reach a reversible specificcapacity as high as 97 mAh·g~(-1) at 10 C rate.     

Synthesis and self-assembly behavior of thermoresponsive poly(oligo(ethylene glycol) methyl ether methacrylate)-POSS with tunable lower critical solution temperature

This article reports on the synthesis of a novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) end-capped poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-oligo(ethylene glycol) methacrylate) (POSS-P(MEO₂MA-co-OEGMA)). These thermoresponsive organic–inorganic hybrid polymers exhibit critical phase transition temperature in water, which can be finely tuned by changing the feed ratio of OEGMA and MEO₂MA. The lower critical solution temperature (LCST) of POSS-P(MEO₂MA-co-OEGMA) increases from 31 to 59 °C with the increasing of OEGMA content. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies show that these polymers can self-assemble into spherical micelles with the thermosensitive block into the corona and the POSS forming the core, and larger aggregates are formed when the temperature values are above their LCSTs. These thermoresponsive polymers POSS-P(MEO₂MA-co-OEGMA) with self-assembly behavior and tunable tempetature-responsive property have the potential applications in material science and biotechnology.     

Gene Cloning,Expression, and Characterization of an Exo-inulinase from Paenibacillus polymyxa ZJ-9

An inulinase-producing strain, Paenibacillus polymyxa ZJ-9, was isolated from natural sources to produce R,R-2,3-butanediol via one-step fermentation of raw inulin extracted from Jerusalem artichoke tubers. The inulinase gene from P. polymyxa ZJ-9 was cloned and overexpressed in Escherichia coli BL21 (DE3), and the purified recombinant inulinase was estimated to be approximately 56 kDa by both sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS–PAGE) and gel filtration chromatography. This result suggests that the active form of the inulinase is probably a monomer. Terminal hydrolysis fructose units from the inulin indicate that enzymes are exo-inulinase. The purified recombinant enzyme showed maximum activity at 25 °C and pH 6.0, which indicate its extreme suitability for industrial applications. Zn²⁺, Fe²⁺, and Mg²⁺ stimulated the activity of the purified enzyme, whereas Co²⁺, Cu²⁺, and Ni²⁺ inhibited enzyme activity. The K _m and V _max values for inulin hydrolysis were 1.72 mM and 21.69 μmol min^?1 mg^?1 protein, respectively. The same parameters toward sucrose were 41.09 mM and 78.7 μmol min^?1 mg^?1 protein, respectively. Considering its substrate specificity and other enzymatic characteristics, we believe that this inulinase gene from P. polymyxa ZJ-9 could be transformed into other special bacterial strains to allow inulin conversion to other biochemicals and bioenergy through one-step fermentation.     

Single-Molecule Magnetism in Dy2 Cluster Based on a Schiff Base Ligand

Two dinuclear Ln^III-based clusters, namely [Dy₂L₂(NO₃)₂(DME)₄] ( 1 ) and [Gd₂L₂(NO₃)₂(DME)₄] ( 2 ) [H₂L = (E)-2-((2-hydroxybenzylidene)amino)phenol] were obtained under hydrothermal condition. Two Ln^III ions are bridged by two phenolic hydroxyl oxygen atoms, and the distances of them are 3.829 Å (Dy1–Dy1A) and 3.860 Å (Gd1–Gd1A). Two Dy1–O–Dy1A and Gd1–O–Gd1A angles are 109.4° and 109.8°, respectively. Magnetic studies reveal a weak antiferromagnetic interaction between Gd ions in complex 2 , and single-molecule magnet behavior for 1 with U_eff = 49.9 K and τ₀ = 1.54 × 10^–6 s.     

N-Confused Phlorin-Prodigiosin Chimera: meso-Aryl Oxidation and π-Extension Triggered by Peripheral Coordination

An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring ( 1 ) was synthesized. Pd^II and B^III coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3 . Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the Pd^II-coordinating phenoxy group to afford 4 . Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5 . Furthermore, peripheral coordination of B^III in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of Ag^III at the inner cavity to afford 3-Ag and 5-Ag , respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.     

单层类水滑石纳米片的可控合成及规模生产展望

水滑石(LDHs)是一种阴离子黏土材料,由于其主体层板厚度的可调性,使其在光/电催化、电池、超级电容器、传感器以及生物医药等领域都具有广泛应用。降低层厚至单层可使材料的物理化学性质发生根本改变,从而优化催化性能。近期研究表明,利用自上而下,自下而上的方法,可以实现单层LDHs类材料的合成,但是受限于产量(g级)以及成本设备等问题,目前规模化制备高质量单层LDHs类材料还没有工业案例。成核晶化隔离法是目前唯一规模化合成纳米LDHs的工业化方法,具有成本低,产量可吨级放大等优点。本综述从合成方法、表征手段、应用三个角度讨论了单层及超薄LDHs的精准调控,详细论述了近期关于单层及超薄LDHs合成突破以及LDHs的规模化生产进展,并对其性能进行了总结,为后续设计高性能单层LDHs提供思路。     

磺酰脲类化合物在水稻田中的除草性能

水稻是我国重要的粮食作物,但杂草对水稻的产量和品质产生了严重影响。 化学防除是治理水稻田杂草最有效的途径。 文中设计合成了苯环2,6-取代和2,5-取代两个系列磺酰脲类化合物,并通过核磁共振波谱仪(NMR)和高分辨质谱仪(HRMS)等对其进行了结构表征。 通过水稻田除草活性和安全性测试发现化合物在水稻田中具有较好的除草活性,尤其是化合物10a对水稻田中的主要杂草稗草和醴肠除草活性(目测初筛防效大于90%)优于对照药醚苯磺隆和氯磺隆,安全性与之相当。