Synthesis,characterization, and electroluminescence of fluorene and carbazole‐based blue light‐emitting polymers with different noncoplanar molecular architectures

In order to investigate the explicit optoelectronic variations of the photoluminescent polymer with sterically hindered side chains, three novel alternate polymers (P0, P1, and P2) based on fluorene and carbazole moieties were successfully synthesized through Suzuki coupling reaction. The molecular structures of the polymers were fully characterized by ¹H‐NMR, ¹³C‐NMR, elemental analysis, and gel permeation chromatograph, respectively. The photophysical properties, thermal stability, and energy band gaps of polymers P0, P1, and P2 were further examined through UV–vis absorption, photoluminescent spectra, differential scanning calorimetry, thermogravimetric analysis, and cyclic voltammetry. The experimental results indicated that the polymers took on wide band gaps of about 3.50 eV with deep blue emission in thin solid films. These polymers were found to show a high thermal stability with decomposition temperatures at 5% weight loss of the compounds in the range of 353–416 °C. Blue light‐emitting electroluminescent devices of the most branched polymer P2 with highest light‐emitting efficiency as emitting layers were characterized, which showed obviously improved spectral stabilities with respect to the parent polyfluorene materials. In conclusion, we have established an effective method to improve the spectral stabilities of polyfluorene material by synthesizing the zigzag‐shaped copolymer of fluorene and carbazole with sterically hindered pendant moieties of different molecular sizes. Copyright © 2014 John Wiley & Sons, Ltd.     

Rapid screening and determination of nerve agent metabolites in human urine by LC-MS/MS

Qualitative screening procedures have been developed for the rapid detection and identification of the metabolites of nerve agents in the urine samples and extracts using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The combination of negative electrospray ionization (ESI) using a C₁₈ column and water-methanol mobile phase modified with ammonium formate provides a rapid screening procedure for nerve agent degradation products with limit of detection of 1 ng/mL in the precursor-ion analysis. Also, determination of the alkyl methylphosphonic acids was carried out by the SRM scan mode with the limit of detection of 0.1 ng/mL. These procedures will be applicable to the trace analysis of metabolites of nerve agents in human urine matrices in the Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency test.     

Microcalorimetric investigation on antibacterial activity of the peptide from Plutella xylostella

The antibacterial activities of a kind of novel peptide from Plutella xylostella (pxCECA1) on methicillin-resistant staphylococcus aureus (MRSA) and Escherichia coli (E. coli) growth were investigated by microcalorimetry. The heat flow power–time curves of MRSA and E. coli growth in the presence of pxCECA1 were recorded using the 3114/3115 Thermal Activity Monitor Air Isothermal Calorimeter based on ampoule mode at 37 °C. Some parameters including growth rate constant k, maximum power output P _max, total heat output Q_t, generation time t _g, growth inhibitory ratio I, and half-inhibitory concentration of the drugs IC₅₀ were obtained to elucidate the antibacterial activity of pxCECA1. The results showed that k, P _max, and Q _t decreased, but I and t _g increased or delayed with the increase in pxCECA1 concentration. The IC₅₀ of pxCECA1 on E. coli was 6.122 μg mL^?1 and MRSA was 7.809 μg mL^?1. It could be concluded that pxCECA1 had stronger inhibitory effect on E. coli than MRSA. In vivo test was simultaneously performed using an E. coli and MRSA infection model to validate the antibacterial activity of pxCECA1. The results revealed that pxCECA1 with broad spectrum antimicrobial activities hopefully represented a class of promising substitute of antimicrobial agents.     

Electrospinning synthesis and photocatalytic property of CaFe2O4/MgFe2O4 heterostructure for degradation of tetracycline

CaFe₂O₄/MgFe₂O₄ nanowires with heterostructure had been successfully synthesized by electrospinning method. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X‐Ray diffraction (XRD), UV–Vis diffuse reflectance spectra (UV‐Vis DR) and Environment scanning electron microscopy (ESEM). The novel CaFe₂O₄/MgFe₂O₄ nanowires exhibit an enhanced photocatalytic activity for degrading of tetracycline (TC) under visible light. Compared with bare CaFe₂O₄ or MgFe₂O₄ samples, the prepared CaFe₂O₄/MgFe₂O₄ (Ca:Mg:Fe = 3:2:10) composited nanowires show the best photocatalytic performance with a degradation efficiency of 40% after 150 min reaction time. This enhancement is attributed to the heterostructure of CaFe₂O₄/MgFe₂O₄ nanowires, which effectively repress the recombination of photo‐generated electrons and holes. Based on heterostructure and energy band positions, the enhancement of mechanism under visible‐light enhances the photocatalytic activity.     

Effect of formation factors on light crude oil oxidation via TG-FTIR

This research aimed at the investigation of the effect of formation factors on the light crude oil during the high temperature air injection process. For this purpose, thermogravimetric and Fourier Transform Infrared Spectroscopy techniques were combined to investigate the light crude oil and oil mixed with formation water and sand at 58, 250, and 450 °C, respectively. The results showed that at different temperature range, the mass drop rate presented different trend and the formation water and sand increased the activation energy of the oxidation reaction. The formation sand exhibited the excellent catalytic effect at relative low temperature. The oxygen addition reaction massively was trigged at 250 °C, and the bond scission reaction dominated at 450 °C. With different additives at different temperature range, the type, concentration, and produced timing of the products presented different tendency.     

Biosynthesis of Streptolidine Involved Two Unexpected Intermediates Produced by a Dihydroxylase and a Cyclase through Unusual Mechanisms

Streptothricin‐F (STT‐F), one of the early‐discovered antibiotics, consists of three components, a β‐lysine homopolymer, an aminosugar D ‐gulosamine, and an unusual bicyclic streptolidine. The biosynthesis of streptolidine is a long‐lasting but unresolved puzzle. Herein, a combination of genetic/biochemical/structural approaches was used to unravel this problem. The STT gene cluster was first sequenced from a Streptomyces variant BCRC 12163, wherein two gene products OrfP and OrfR were characterized in vitro to be a dihydroxylase and a cyclase, respectively. Thirteen high‐resolution crystal structures for both enzymes in different reaction intermediate states were snapshotted to help elucidate their catalytic mechanisms. OrfP catalyzes an Fe^II‐dependent double hydroxylation reaction converting L ‐Arg into (3R,4R)‐(OH)₂‐L ‐Arg via (3S)‐OH‐L ‐Arg, while OrfR catalyzes an unusual PLP‐dependent elimination/addition reaction cyclizing (3R,4R)‐(OH)₂‐L ‐Arg to the six‐membered (4R)‐OH‐capreomycidine. The biosynthetic mystery finally comes to light as the latter product was incorporation into STT‐F by a feeding experiment.     

Pumping through Porous Hydrophobic/Oleophilic Materials: An Alternative Technology for Oil Spill Remediation

Recently, porous hydrophobic/oleophilic materials (PHOMs) have been shown to be the most promising candidates for cleaning up oil spills; however, due to their limited absorption capacity, a large quantity of PHOMs would be consumed in oil spill remediation, causing serious economic problems. In addition, the complicated and time‐consuming process of oil recovery from these sorbents is also an obstacle to their practical application. To solve the above problems, we apply external pumping on PHOMs to realize the continuous collection of oil spills in situ from the water surface with high speed and efficiency. Based on this novel design, oil/water separation and oil collection can be simultaneously achieved in the remediation of oil spills, and the oil sorption capacity is no longer limited to the volume and weight of the sorption material. This novel external pumping technique may bring PHOMs a step closer to practical application in oil spill remediation.     

Hexafluoroantimonic Acid Catalysis: Formal [3+2+2] Cycloaddition of Aziridines with Two Alkynes

A practical method for the synthesis of azepine derivatives, a typical seven‐membered heterocyclic ring system, was developed and involves the use of hexafluoroantimonic acid to catalyze a formal [3+2+2] cycloaddition of aziridines with two alkynes. This method was applicable to two of the same or different terminal alkynes for the [3+2+2] cycloaddition with unactivated aziridines, and furnished the corresponding azepine derivatives in good yields with good levels of chemo‐ and regioselectivity. The mechanism was also discussed according to the results of the in situ HRMS and ¹H NMR analysis.     

Physical and electrochemical properties of (La0.3Sr0.7)0.93TiO3–δ synthesized by Pechini method as an anode material for solid oxide fuel cells

The lanthanum strontium titanate (LST) has to be calcined at significantly high temperature (above 1,300 °C) to obtain its pure perovskite structure when synthesized by conventional solid-state method, which is main reason for reducing active surface area. In this study, A-site deficient (La_0.3Sr_0.7)_0.93TiO₃ was synthesized by Pechini method. Although the prepared powders were calcined at 600 °C, the pure perovskite structure can be obtained without any secondary phase such as TiO₂. Moreover, the porosity and surface area are 6 times and one order of magnitude higher in the LST powders synthesized by Pechini method than in the powders synthesized by solid-state method. Based on these results, the LST electrode (Pechini) leads to two times lower electrode resistance than the LST electrode (solid-state). Thus, the LST powders synthesized by Pechini can contributes to saving the energy needed for calcination process as well as increasing the porosity and active surface area, enhancing physical and electrochemical properties in SOFC anode.     

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Rh^III‐catalyzed N‐nitroso‐directed C?H addition to ethyl 2‐oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N‐nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C?H functionalization‐based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tricyclic‐fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.