Synthesis and Electrophilic Cyclization Reactions of Diphenyl 3-Methylpenta-1,2,4-trienyl Phosphine Oxide

Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide can be readily prepared via an atom-economical [2,3]-sigmatropic rearrangement of the mediated alkenynyl phosphinite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with diphenylchlorophosphine. Electrophilic cyclization reactions of the vinylallenyl phosphine oxide prepared were investigated as it was established that the reactions proceeded with formation of various heterocyclic or highly unsaturated compounds with participation of the allenic and/or 1,3-dienic part of the vinylallenic system with neighboring group participation of phosphoryl and/or vinylic group.

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Determination of glutathione in single HepG2 cells by capillary electrophoresis with reduced graphene oxide modified microelectrode

Determination of intracellular bioactive species will afford beneficial information related to cell metabolism, signal transduction, cell function, and disease treatment. In this study, the electrochemically reduced graphene oxide modified carbon fiber microdisk electrode (ER‐GOME) was used as a detector of CZE‐electrochemical detection and developed to detect glutathione (GSH). The electrocatalytic activity of the modified microelectrode was characterized by cyclic voltammetry. Under optimized experimental conditions, the concentration linear range of GSH was from 1 to 60 μM. When the S/N ratio was 3, the concentration detection limit was 1 μM. Compared with the unmodified carbon fiber microdisk electrode, the sensitivity was enhanced more than five times. With the use of this method, the average contents of GSH in single HepG2 cells were found to be 7.13 ± 1.11 fmol (n = 10). Compared with gold/mercury amalgam microelectrode, which was usually used in determining GSH, the electrochemically reduced graphene oxide modified carbon fiber microdisk electrode was friendly to environment for free mercury. Furthermore, there were several merits of the novel electrochemical detector coupled with CE, such as comparative repeatability, easy fabrication, and high sensitivity, hold great potential for the single‐cell assay.     

Chiral Monolithic Absorbent Constructed by Optically Active Helical‐Substituted Polyacetylene and Graphene Oxide: Preparation and Chiral Absorption Capacity

Chiral monolithic absorbent is successfully constructed for the first time by using optically active helical‐substituted polyacetylene and graphene oxide (GO). The preparative strategy is facile and straightforward, in which chiral‐substituted acetylene monomer (Ma), cross‐linker (Mb), and alkynylated GO (Mc) undergo copolymerization to form the desired monolithic absorbent in quantitative yield. The resulting monoliths are characterized by circular dichroism, UV–vis absorption, scanning electron microscopy (SEM), FT‐IR, Raman, energy‐dispersive spectrometer (EDS), X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET), XPS, and thermogravimetric analysis (TGA) techniques. The polymer chains derived from Ma form chiral helical structures and thus provide optical activity to the monoliths, while GO sheets contribute to the formation of porous structures. The porous structure enables the monolithic absorbents to demonstrate a large swelling ratio in organic solvents, and more remarkably, the helical polymer chains provide optical activity and further enantio‐differentiating absorption ability. The present study establishes an efficient and versatile methodology for preparing novel functional materials, in particular monolithic chiral materials based on substituted polyacetylene and GO.

     

Well‐Defined High Molecular Weight Polystyrene with High Rates and High Livingness Synthesized via Two‐Stage RAFT Emulsion Polymerization

A highly living polymer with over 100 kg mol⁻¹ molecular weight is very difficult to achieve by controlled radical polymerization since the unavoidable side reactions of irreversible radical termination and radical chain transfer to monomer reaction become significant. It is reported that over 500 kg mol⁻¹ polystyrene with high livingness and low dispersity could be synthesized by a facile two‐stage reversible addition–fragmentation transfer emulsion polymerization. The monomer conversion reaches 90% within 10 h. High livingness of the product is ascribed to the extremely low initiator concentration and the chain transfer constant for monomer unexpectedly much lower than the well‐accepted values in the conventional radical polymerization. The two‐stage monomer feeding policy much decreases the dispersity of the product.

     

Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage

Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca_xV₂O₅-H₂O (CVO), was probed at the V-K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn-ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near-neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn-ion influence on the V-K absorption edge is visualized using a difference technique called Δμ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn-ion electrochemical cell.     

Submicron carbon-based hybrid nano-pour-point depressant with outstanding pour point depressant and excellent viscosity depressant

We have investigated the effective utilization potential of carbon nanomaterials in the field of pour point depressants, and reported three kind of carbon-based hybrid nano-pour-point depressants with different dimensions. In this paper, poly-α-olefins-acrylate high-carbon ester pour point depressant (PAA-18) was prepared by esterification and polymerization as the basic pour point depressant. Then, the basic pour point depressant PAA18 was modified by solvothermal method with graphene oxide (GO), carbon nanospheres (Cna) and carbon nanotubes (OCNTs). The morphology and structure of the composites were analyzed by SEM, FTIR and XRD. The results showed that PAA18 was successfully in situ polymerized on GO, Cna and OCNTs. We took the simulated oil as the experimental object, and evaluated its pour point, rheological properties and wax crystal morphology, and achieved excellent results. In the three carbon-based hybrid nano-pour-point depressants with different carbon contents, the oxidation carbon nanotubes composite pour point depressant (PAA18-1 % OCNTs) with carbon content of 1 % had the best pour point and viscosity reduction effect when the dosage was 1250 ppm, which could make the pour point of the simulated oil containing wax decrease by 16 °C. PAA18-1 % OCNTs reduced the pour point by 5 °C more than PAA18. This paper provides reference for the application of carbon nanomaterials in the field of pour point depressant.     

Electro‐optic switching with liquid crystal graphene

Graphene oxide (GO) particles in aqueous dispersions can form liquid crystal (LC) phases at extremely low concentrations due to the extremely high aspect ratio of the flakes and noticeably, they possess an extremely large Kerr coefficient attractive for low power consumption electro‐optic devices. Reduced graphene does not easily form LC phases in water due to its hydrophobic nature but here we show that stable dispersions of reduced graphene oxide can be realized with surfactants and that they exhibit birefringence upon shearing as well as under application of electric fields. The performance of the system is largely superior to GO LC possessing longer time stability and drastically improved electro‐optic properties with an induced birefringence twice as large at the same field strength thanks to the almost recovery of graphene properties upon reduction. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

High pressure inactivation of Clostridium botulinum type E endospores in model emulsion systems

Clostridium botulinum type E is a cold-tolerant, neurotoxigenic, endospore-forming organism, primarily associated with aquatic environments. High pressure thermal (HPT) processing presents a promising tool to enhance food safety and stability. The effect of fat on HPT inactivation of C. botulinum type E spores was investigated using an emulsion model system. The distribution of spores in oil-in-water (O/W) emulsions and their HPT (300–750?MPa, 45–75?°C, 10?min) inactivation was determined as a function of emulsion fat content (30–70% (v/v) soybean oil in buffer). Approximately 26% and 74% of the spores were located at the oil–buffer interface and the continuous phase, respectively. Spore inactivation in emulsion systems decreased with increasing oil contents, which suggests that the fat content of food plays an important role in the protection of C. botulinum type E endospores against HPT treatments. These results can be helpful for future safety considerations.     

Effects of high hydrostatic pressure on secondary structure and emulsifying behavior of sweet potato protein

In this study, secondary structures of sweet potato protein (SPP) after high hydrostatic pressure (HHP) treatment (200–600?MPa) were evaluated and emulsifying properties of emulsions with HHP-treated SPP solutions in different pH values (3, 6, and 9) were investigated. Circular dichroism analysis confirmed the modification of the SPP secondary structure. Surface hydrophobicity increased at pH 3 and decreased at 6 and 9. Emulsifying activity index at pH 6 increased with an increase in pressure, whereas emulsifying stability index increased at pH 6 and 9. Oil droplet sizes decreased, while volume frequency distribution of the smaller droplets increased at pH 3 and 6 with the HHP treatment. Emulsion viscosity increased at pH 6 and 9 and pseudo-plastic flow behaviors were not altered for all emulsions produced with HHP-treated SPP. These results suggested that HHP could modify the SPP structure for better emulsifying properties, which could increase the use of SPP emulsion in the food industry.