Preparation of Ag nanoparticle-decorated poly(m-phenylenediamine) microparticles and their application for hydrogen peroxide detection

The chemical oxidation polymerization of m-phenylenediamine (MPD) by ammonium persulfate (APS) at room temperature results in the formation of poly(m-phenylenediamine) (PMPD) microparticles. The subsequent treatment of such microparticles with an aqueous AgNO(3) solution produces Ag nanoparticle (AgNP)-decorated PMPD microparticles. It was found that as-formed AgNPs exhibited remarkable catalytic performance toward the reduction of hydrogen peroxide (H(2)O(2)). The enzymeless H(2)O(2) sensor constructed with such composites showed a fast amperometric response time of less than 5 s, and the corresponding linear range and detection limit were estimated to be from 0.1 to 30 mM and 4.7 μM, respectively, at a signal-to-noise ratio of 3.     

Highly sensitive and selective colorimetric sensors for uranyl (UO2(2+)): development and comparison of labeled and label-free DNAzyme-gold nanoparticle systems

Colorimetric uranium sensors based on uranyl (UO2(2+)) specific DNAzyme and gold nanoparticles (AuNP) have been developed and demonstrated using both labeled and label-free methods. In the labeled method, a uranyl-specific DNAzyme was attached to AuNP, forming purple aggregates. The presence of uranyl induced disassembly of the DNAzyme functionalized AuNP aggregates, resulting in red individual AuNPs. Once assembled, such a "turn-on" sensor is highly stable, works in a single step at room temperature, and has a detection limit of 50 nM after 30 min of reaction time. The label-free method, on the other hand, utilizes the different adsorption properties of single-stranded and double-stranded DNA on AuNPs, which affects the stability of AuNPs in the presence of NaCl. The presence of uranyl resulted in cleavage of substrate by DNAzyme, releasing a single stranded DNA that can be adsorbed on AuNPs and protect them from aggregation. Taking advantage of this phenomenon, a "turn-off" sensor was developed, which is easy to control through reaction quenching and has 1 nM detection limit after 6 min of reaction at room temperature. Both sensors have excellent selectivity over other metal ions and have detection limits below the maximum contamination level of 130 nM for UO2(2+) in drinking water defined by the U.S. Environmental Protection Agency (EPA). This study represents the first direct systematic comparison of these two types of sensor methods using the same DNAzyme and AuNPs, making it possible to reveal advantages, disadvantages, versatility, limitations, and potential applications of each method. The results obtained not only allow practical sensing application for uranyl but also serve as a guide for choosing different methods for designing colorimetric sensors for other targets.     

化学反应的选择性和金属有机化学

本文是对旨在提高合成效率的化学反应选择性和金属有机化学关系的综述,按金属有机化合物的基元反应进行讨论。     

Selective Determination of Dopamine in the Presence of Ascorbic Acid at Porous‐Carbon‐Modified Glassy Carbon Electrodes

Selective dopamine (DA) determinations using porous‐carbon‐modified glassy carbon electrodes (GCE) in the presence of ascorbic acid (AA) were studied. The effects of structure textures and surface functional groups of the porous carbons on the electrochemical behavior of DA was analyzed based on both cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements. The differential pulse voltammetry of DA on the modified GCE was determined in the presence of 400‐fold excess of AA, and the linear determination ranges of 0.05–0.99, 0.20–1.96, and 0.6–12.60 μM with the lowest detected concentrations of 4.5×10^?3, 4.4×10^?2, and 0.33 μM were obtained on the mesoporous carbon, mesoporous carbon with carboxylic and amino groups modified electrodes, respectively.     

The Effects of the Modified Starches on the Melting Flow and Biodegradation of the Starch/Glycerol Blend

Summary: The purpose of this study was to improve the melting flow of starch/glycerol(GA) blends by modified starches. A variety of modified starches, which was treated by hydrolysis and acid hydrolysis, with and without ultrasonic treatment were used. The MFI (melt flow index) of blends increased from 0.5g/10min to 300g/10min when the addition of acid hydrolysis starch (0.3M CA-starch) was 70wt%. Their crystalline behaviors were analyzed by XRD results. The ultrasonic treatment has been proved to have the effect of hydrolysis without acids and synergistic effect on recrystalline. The SEM micrographs of the blend with the ultrasonic treatment starch gave the cleaving surface with comparison to the other blends. The weight loss of the blends with acid hydrolysis starches reached to 60∼80% after one week biodegradation as the ultrasonic treatment was used.     

Spectral Properties and Solubilization Location of 2'-Ethylhexyl 4-(N,N-Dimethylamino)benzoate in Micelles

Dual fluorescence and UV absorption of 2'-ethylhexyl 4-(N,N-dimethylamino)benzoate (EHDMAB) were investigated in cationic, non-ionic and anionic micelles. When EHDMAB was solubilized in different micelles, the UV absorption of EHDMAB was enhanced. Twisted intramolecular charge transfer (TICT) emission with longer wavelength was observed in ionic micelles, whereas TICT emission with shorter wavelength was obtained in non-ionic micelles. In particular, dual fluorescence of EHDMAB was significantly quenched by the positively charged pyridinium ions arranged in the Stern layer of cationic micelles. UV radiation absorbed mainly decays via TICT emission and radiationless deactivation. The dimethylamino group of EHDMAB experiences different polar environments in ionic and non-ionic micelles according to the polarity dependence of TICT emission of EHDMAB in organic solvents. In terms of the molecular structures and sizes of EHDMAB and surfactants, each individual EHDMAB molecule should be buried in micelles with its dimethylamino group toward the polar head groups of different micelles and with its 2'-ethylhexyl chain toward the hydrophobic micellar core. Dynamic fluorescence quenching measurements of EHDMAB provide further support for the location of EHDMAB in different micelles.     

Angular-shaped naphthalene tetracarboxylic diimides for n-channel organic transistor semiconductors

A series of compounds based on the angular-shaped naphthalene tetracarboxylic diimide core have been synthesized, characterized and used as active layers of organic field-effect transistors (OFETs). The fabricated OFET devices exhibit n-type semiconducting characteristics, demonstrating the first examples of semiconductors based on angular-shaped naphthalene tetracarboxylic diimides.     

Soluble and Green‐light‐emitting Oligo(9‐fluorenylideneacetic acid): Electrosynthesis and Characterization

A novel semiconducting oligo(9‐fluorenylideneacetic acid) (OFYA) with good redox activity and stability was successfully electrosynthesized by direct anodic oxidation of 9‐fluorenylideneacetic acid (FYA) in CH₂Cl₂ containing boron trifluoride diethyl etherate (BFEE) as the supporting electrolyte. The as‐formed OFYA film was readily soluble in dimethyl sulfoxide and tetrahydrofuran, and partly soluble in water, alcohol, acetonitrile and acetone. FT‐IR and ¹H NMR spectra, together with computational results proved that FYA was probably polymerized through the coupling at C(2) and C(7) positions. Further, OFYA was a typical green light‐emitter with maximal emission at 555 nm and its fluorescence quantum yield was distinctly improved in comparison with that of the monomer. The oligomer was also studied by UV‐vis spectroscopy, MALDL‐TOF mass spectrometry, and thermal analysis, respectively.