Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection

In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL^?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Ionic Conductivity of β‐Cyclodextrin–Polyethylene‐Oxide/Alkali‐Metal‐Salt Complex

Highly conductive, crystalline, polymer electrolytes, β‐cyclodextrin (β‐CD)–polyethylene oxide (PEO)/LiAsF₆ and β‐CD–PEO/NaAsF₆, were prepared through supramolecular self‐assembly of PEO, β‐CD, and LiAsF₆/NaAsF₆. The assembled β‐CDs form nanochannels in which the PEO/X⁺ (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion.     

Charge transport properties of MDMO PPV thin films cast in different solvents

Charge transport properties in thin films of Poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO PPV) cast using either chloroform (CF), toluene (TOL), or chlorobenzene (CB) as solvent were investigated. Hole mobility (μ) in these thin films measured using time‐of‐flight transient photoconductivity showed an increasing trend with respect to the solvent used in the same order, that is, μ_CF (2.4 × 10^?7 cm²/Vs) < μ_TOL (6.9 × 10^?7 cm²/Vs) < μ_CB (2.3 × 10^?6 cm²/Vs). Observed variations in mobilities were attributed to different morphologies of MDMO PPV chains in thin films cast using the aforesaid solvents. Nature of the interchain interactions and aggregate formation were obtained using photoluminescence (PL), Raman spectroscopy, and AFM studies. Ratio of PL peak intensities of 0–0 and 0–1 transitions, which is a direct measure of interchain interaction, was the highest in CB and lowest in CF. Variation in the relative intensities of out‐of‐plane wagging of vinylene group (～963 cm^?1 mode) in Raman spectra suggested different extent of coiling of polymer chains in these thin films. From these observations, it was elicited that aggregate size and interchain interactions are highest in CB and least in CF. AFM‐based topographic images of thin films further supported these variations in the size of aggregates. Variation in the aggregate sizes and interchain interactions explained the corresponding variation in the mobility. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1431–1439     

Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry

Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO₂/N₂ selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557     

Ion transport in polymerized lyotropic liquid crystals containing ionic liquid

In this work, we investigate the effect of morphology and segmental dynamics on ion transport in polymerized lyotropic liquid crystals (polyLLCs) containing 1-butyl-3-methylimidazolium tetrafluoroborate as ionic liquid (IL). We demonstrate that two important factors, which affect ion conduction in polyLLCs, are grain size and chain density at the interface. The polyLLC with large grain size (70 nm) shows significant reduction in ion conductivity (one order of magnitude) compared to its homopolymer/IL mixture. However, the polyLLC with small grain size (20 nm) has little difference in ion conductivity compared to its homopolymer/IL mixture. It is observed that decreasing the chain density enhances the interaction of IL with polymer chains and consequently slows the relaxation of polymer chains. In addition, comparing the dynamics of polymer chains in mixtures of homopolymer/IL and templated LLC mesophases shows that the confinement in LLC structure prolongs the relaxation of polymer chains.     

Spreading of Oil Droplets Containing Surfactants and Pesticides on Water Surface Based on the Marangoni Effect

Oil droplets containing surfactants and pesticides are expected to spread on a water surface, under the Marangoni effect, depending on the surfactant. Pesticides are transported into water through this phenomenon. A high-speed video camera was used to measure the movement of Marangoni ridges. Gas chromatography with an electron capture detector was used to analyze the concentration of the pesticide in water at different times. Oil droplets containing the surfactant and pesticide spread quickly on the water surface by Marangoni flow, forming an oil film and promoting emulsification of the oil–water interface, which enabled even transport of the pesticide into water, where it was then absorbed by weeds. Surfactants can decrease the surface tension of the water subphase after deposition, thereby enhancing the Marangoni effect in pesticide-containing oil droplets. The time and labor required for applying pesticides in rice fields can be greatly reduced by using the Marangoni effect to transport pesticides to the target.     

The green synthesis of exceptional braided,helical carbon nanotubes and nanospiral platelets made directly from CO2

Helical carbon nanotubes currently cost ~15,000–19,000 USD/kg commercially and are ~10–15 times the price of straight carbon nanotubes of similar dimensions. They have not previously been made from the greenhouse gas CO₂ nor had new variants of the helical morphology been demonstrated. In this study, a novel, inexpensive electrosynthesis of these helical nanocarbon materials from CO₂ is presented. This material may be produced by molten carbon growth conditions that (1) maximize torsional stresses, such as those that may occur during rapid, nucleated carbon reduction, (2) enhance defects that cause formation of heptagonal, rather than the conventional hexagonal building blocks of graphene cylindrical walls, and (3) uniformly control those enhanced defects to repeatedly induce a uniform spiral conformation. These conditions are achieved with at least two of the following experimental conditions: (i) high electrolysis current density, (ii) sp³ defect-inducing agents, such as added oxide, and (iii) controlled concentration of iron added to the electrolyte or cathode. Here, it is shown with SEM, TEM, EDX, XRF, and Raman spectroscopy that a molten controlled electrolyte carbonate synthesis to induce defect formation, and a high rate of electrolysis (0.6 A/cm²) leads to a high yield of helical nanotubes, helical nanofibers, or helical nanoplatelet carbon morphologies.     

Impact of Imine Bond Orientations on the Geometric and Electronic Structures of Imine-based Covalent Organic Frameworks

Many efforts are currently devoted to improving the stability and crystallinity of imine-based two-dimensional (2D) covalent organic frameworks (COFs) given their wide range of potential applications. The variation in the relative orientations of the imine bonds has been found to be a critical factor that impacts the stacking of the 2D COF layers, leads to the formation of isomer structures, and influences the crystallinity of the final product. Most investigations to date have focused only on the structural properties, while the role of the imine orientations on the electronic properties has not been studied systematically. Here, we explore this effect by examining how the electronic band structures, electronic couplings, and effective masses evolve when considering four isomeric structures of an imine-linked tetraphenyl-pyrene naphthalene-diimide COF. Our results provide an understanding of the impact of the imine orientations and how they need to be controlled to realize COF inter-layer stackings that can lead to efficient cross-plane electron transport. They can be used to guide the design and synthesis of imine-based COFs for applications where charge transport needs to be optimized.     

Role of anti-inflammatory interventions in high-fat-diet-induced obesity

Lipotoxicity is defined as deposition of excess fat associated with an inflammatory response. Metabolomic analysis of fatty acids (FAs) can be a marker of silent inflammation. ω3-Enriched diet, celecoxib, and safranal may have a protective anti-inflammatory role. In this work, total FAs extracted from red blood cells and arachidonic acid-to-eicosapentaenoic acid (AA-to-EPA) ratios were assessed using GC–MS assay in single-ion monitoring mode. The study was conducted on 64 male rats divided into eight groups: I, controls; II, rats received high-fat diet (HFD), III, rats received ω-6-enriched HFD; IV, rats received ω-3-enriched HFD; V, rats received celecoxib with HFD; VI, rats received safranal with HFD; VII and VIII, rats received celecoxib and safranal with ω-3 HFD, respectively. GC–MS Gas chromatography Mass spectrometry was performed for analysis of fatty acid methyl ester. Enzyme-linked immunosorbent assay was used to analyze serum interleukin-6 (IL-6) and transforming growth factor-beta 1 (TGF-β1) concentrations. A statistically significant decrease of AA-to-EPA ratio was observed in group VII when compared with the groups receiving HFDs. This group also showed the lowest serum IL-6 level and highest TGF-β1 level. In conclusion, ω3-enriched diet along with drugs (e.g. celecoxib) and herbal medications (e.g. safranal) may have an anti-inflammatory effect in lipotoxicity. GC–MS with single-ion monitoring is valid for the analysis of FAs.