Highly porous magnetite/graphene nanocomposites for a solid-state electrochemiluminescence sensor on paper-based chips

Graphene-nanosheet-based highly porous magnetite nanocomposites (GN-HPMNs) have been prepared using a simple solvothermal method and used as an immobilization matrix for the fabrication of a solid-state electrochemiluminescence (ECL) sensor on paper-based chips. Highly porous Fe₃O₄ nanocrystal clusters were coated with acrylate and wrapped tightly on the skeleton of graphene nanosheets. The structures and sizes of the GN-HPMNs could be tuned by varying the proportions of the solvents ethylene glycol and diethylene glycol. Then, the relatively highly porous ones with an average diameter of about 65 nm were combined with Nafion to form composite films on an electrode surface for immobilization of Ru(bpy)₃ ²⁺ (bpy is 2,2′-bipyridine). Because of their porosity, negatively charged surface, and cooperative characteristics of magnetic nanomaterials and graphene, under an external magnetic field, the GN-HPMNs ensured effective immobilization, excellent electron transfer, and long-term stability of Ru(bpy)₃ ²⁺ in the composite film. The sensor developed exhibited excellent reproducibility with a relative standard deviation of 0.65 % for 30 continuous cycles. It was found to be much more favorable for detecting compounds containing tertiary amino groups and DNAs with guanine and adenine. A detection limit (signal-to-noise ratio of 3) of 5.0 nM was obtained for tripropylamine. As an application example, 0.5 nM single-nucleotide mismatch could be detected. This was the first attempt to introduce magnetic nanomaterials and an external magnetic field into paper-based chips. The sensor developed has the advantages of high sensitivity, good stability, and wide potential applicability as well as simplicity, low cost, and good disposability.

Determination of 48 fragrance allergens in toys using GC with ion trap MS/MS

This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single‐stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005–5.0 and from 0.02–20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5–109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7–10.5% and from 3.1–13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components.     

Facile synthesis of a porous network-like silver film for electrocatalytic detection of nitrate

We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of −0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N = 3) and a repeatability of 3.4 % (n = 5).

A facile method was developed for in situ construction of a porous network-like Ag film on a glassy carbon electrode by a galvanic replacement reaction, where a layer of Cu nanoparticles previously electrodeposited as a sacrificial template. Thus-formed Ag film displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward nitrate reduction.

     

Regular arrays of triangular‐microstructure formed on silicon (111) surface via ultrafast laser irradiation in KOH solution

The regular micrometer‐scale triangular arrays were formed using ultrafast femtosecond laser irradiation on (111) surface of silicon wafer immersed in KOH solution (0.1 g/ml). At low laser fluence, the resulting surface is covered by triangular pits microstructures, whereas at high laser fluence, the structures are transformed to multilayer‐triangular stacks‐microstructures. The number of triangular stacks layer increased as the laser fluence increased. The formation of triangle microstructure arrays depends on both silicon surface crystallographic orientation and the concentration of KOH solution. Either for lower KOH solution concentration (0.02 g/ml) or other silicon crystallographic orientation, triangle arrays cannot be obtained. We attribute the formation of triangular microstructure arrays to the laser‐assisted chemical etching process. Copyright © 2013 John Wiley & Sons, Ltd.     

纳米孔分析化学

源于自然界,服务于人类社会的纳米尺度装置包括生物及人工制备的纳米孔与纳米通道等。基于这些纳米尺度装置的分析化学简称纳米孔分析化学。本文对纳米孔分析化学的发展,特别是近年来在DNA测序、蛋白质分析的进展进行了综述,对于纳米孔分析化学发展的历史、基本分类、原理和应用作了介绍与展望。     

The effect of mesogenic and non-mesogenic crosslinking units on the phase behaviour of side-chain smectic and cholesteric elastomers

Chiral monomer (M₁ ), mesogenic and non-mesogenic crosslinking agents (C₁ and C₂ ), and the corresponding liquid crystalline elastomers (P₁ and P₂ series), have been synthesised. Their chemical structures have been characterised by Fourier transform infrared or ¹H nuclear magnetic resonance and their phase behaviour investigated by differential scanning calorimetry, polarising optical miscoscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction. The effect of the crosslinking unit on the phase behaviour of the elastomers has been studied. M₁ showed a cholesteric oily streak and focal conic texture. C₂ exhibited a nematic enantiotropic thread-like and schlieren texture, and a monotropic fan-shaped texture in the S_A phase. Due to the introduction of the mesogenic crosslinking unit, elastomers, P_2-1 ?P_2-5 , exhibited a cholesteric phase, while elastomers, P_1-1 ?P_1-4 , derived from a non-mesogenic crosslinking unit, exhibit a S_A phase. As the content of the crosslinking unit increased, the T _g of the P₁ series initially decreased and then increased, and the T _i of the series decreased. In the P₂ series the T _g increased, but the T _i initially increased and then decreased. TGA confirmed that all the elastomers had improved thermal stability.     

Cloning, Expression, and Characterization of β-mannanase from Bacillus subtilis MAFIC-S11 in Pichia pastoris

The β-mannanase gene (1,029 nucleotide) from Bacillus subtilis MAFIC-S11, encoding a polypeptide of 342 amino acids, was cloned and expressed in Pichia pastoris. To increase its expression, the β-mannanase gene was optimized for codon usage (mannS) and fused downstream to a sequence-encoding modified α-factor signal peptide. The expression level was improved by 2-fold. This recombinant enzyme (mannS) showed its highest activity of 24,600 U/mL after 144-h fermentation. The optimal temperature and pH of mannS were 50 °C and 6.0, respectively, and its specific activity was 3,706 U/mg. The kinetic parameters V _max and K _m were determined as 20,000 U/mg and 8 mg/mL, respectively, representing the highest ever expression level of β-mannanase reported in P. pastoris. In addition, the enzyme exhibited much higher binding activity to chitin, chitosan, Avicel, and mannan. The superior catalytic properties of mannS suggested great potential as an effective additive in animal feed industry.     

A facile one-pot, three-component synthesis of 3,3′-(4-arylpyridine-2,6-diyl)bis(2H-chromen-2-one) derivatives under microwave irradiation

A series of 3,3′-(4-arylpyridine-2,6-diyl)bis(2H-chromen-2-one) derivatives have been synthesized by the one-pot, three-component reaction of 3-acetylcoumarin, an aromatic aldehyde, and ammonium acetate in acetic acid under microwave irradiation. This procedure has the major advantages of short reaction time, good yields, low energy consumption, easy operation, and environmental friendliness. All of the products were characterized by IR and NMR spectroscopy, MS, and elemental analysis.