Liquid crystalline polymers XVI*. Thermotropic liquid crystalline copoly(arylidene-ether)/TiO2 Nanocomposites: synthesis,characterisation and applications

ABSTRACT

Polymer nanocomposites are already a part of many important worldwide businesses. Among many nanocomposite precursors, titanium dioxide (TiO₂) nanopowder is increasingly being investigated due to its special properties. In this work, the feasibility of synthesising a new series of materials, copoly(arylidene-ether)/titanium dioxide nanocomposites, using in-situ copolymerisation technique has been investigated. This can be performed by the interaction of both cyclohexanone and 4-tert-butylcyclohexanone monomers with 4,4′-diformyl-2,2′-dimethoxy-α,ω-diphenoxyalkanes Ia–e, respectively, using different additions of titanium dioxide-P25. The structure of the prepared nanocomposites IIa–e/TiO₂ (0.2–3.0%) was confirmed by elemental analysis (energy dispersive X-ray spectroscopy) and spectral data (Fourier transform-infrared [FT-IR]). FT-IR verified the dispersion of nanofillers in the copolymer. Then, the characterisation and applications of these nanocomposites are extensively discussed depending on the investigation of how the addition of titanium dioxide nanoparticles affected on their properties using various techniques, such as X-ray diffraction, SEM, transmission electron microscopy, Water Contact Angle (WCA), thermogravimetric analysis, differential thermogravimetric, differential thermal analysis (DTA), polarising optical microscope and UV–vis absorption spectroscopy. The nanoparticles affected on the copolymer thermal behaviour in different ways (discrepancy results) depending on how these nanoparticles are dispersed in the copolymer matrix. UV–vis absorption spectra displayed a decrease in the optical band gap of some nanocomposites, which resulted from the addition of titanium dioxide to these copolymers, and this can improve the efficiency of them as organic emitting materials.     

Ionic Aggregates of Lithium Organocuprates

We have used a combination of electrospray ionization mass spectrometry and electrical conductivity measurements to analyze solutions of the Gilman cuprates LiCuR₂?LiX, with R=Ph, Bu and X=Cl, Br, I, in tetrahydrofuran and have compared our findings with previous results on cyanocuprates LiCuR₂?LiCN. Among the various polynuclear organocuprate ions observed, Li₂Cu₃Ph₆^?, LiCu₄Ph₆^?, and Cu₅Ph₆^? are of particular interest because aggregates of the same composition are known from X‐ray crystal structures. Control experiments have indicated that the polynuclear organocuprate anions detected in solution are indeed identical to those formed in the solid state. As abundant ions of the type Li₂Cu₃R₆^? are found in solutions of Gilman cuprates and cyanocuprates alike, their possible involvement in organocuprate reactions should be considered. For comparison, we have also included solutions of LiCu(R)I, LiCuX₂?LiX, LiCuX₂, and CuCN?2 LiX in the present study.     

Studies on Phosphonium Ylides,XXIV: Reactions of Phosphorus Ylides with 1,2,3,4-Tetrahydro1-Naphthylidene-Malononitrile

1,2,3,4-tetrahydro-1-naphthylidene-malononitrile (1) reacts with carbethoxymethylene and carbmethoxymethylene- triphenylphosphoranes (2a, 2b) to give the new phospho-ranylidenecyclopentaylidene products (4a, 4b, and 5), respectively. The treatment of (1) with phosphorus ylide 2c afforded the new phosphonium ylide 6. Moreover, the application of reagent (2d) on (1) renders compound 7. On the other hand, when N-phenyliminotriphenylphosphorane (3) reacts with (1), the corresponding adduct (8) was obtained together with triphenylphosphine. Mechanisms accounting for the formation of new products are discussed, and probable structures of products are presented based on analytical and spectroscopic data.     

N-Isocyaniminotriphenylphosphorane as an Efficient Reagent for the Synthesis of Disubstituted 1,3,4-Oxadiazoles Via In-Situ Generation of Sterically Congested Iminophosphorane Derivatives

Abstract

Reaction of N-isocyaniminotriphenylphosphorane with benzaldehyde derivatives in the presence of 3-phenyl-2-propynoic acid and secondary amines proceeds smoothly at room temperature and under neutral conditions to afford sterically congested 1,3,4-oxadiazole derivatives in high yields. The reaction proceeds smoothly and cleanly under mild conditions and no side reactions are observed.     

Preparation and Characterization of Carbon Nanotubes Supported Ni2P for Hydrodesulfurization (HDS) of Naphtha

Abstract

Ni₂P nanoparticles supported by functionalized carbon nanotubes (CNTs) were prepared for the first time. Nickel (II) dihydrogenphosphite as a source of nickel, with different loadings on the functionalized CNTs, were used. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) techniques. Surface areas of the samples were measured by using Brunauer, Emmett and Teller (BET) method. The catalytic activity of the prepared samples was studied in hydrodesulfurization (HDS) of naphtha. The results showed that the CNTs were

functionalized and Ni₂P particles were dispersed on the functionalized CNTs. It was also indicated that the pores size of Ni₂P particles were less than 20 nm. The catalytic study of the prepared samples confirmed that these compounds were stable and active in the process. Removal of sulfur from the desired naphtha in presence of the samples depended on the nickel loadings and increased with temperature in all cases.     

Synthesis of Bis(indolyl)methanes using a Catalytic Amount of ZnO under Solvent‐Free Conditions

Efficient electrophilic substitution reactions of indoles with various aromatic aldehydes were carried out using a catalytic amount of ZnO under solvent‐free conditions to afford the corresponding bis(indolyl)methanes in excellent yields. Among the various methods published for the synthesis of bis(indolyl)methane, ZnO is a very cheap, environmentally friendly, and reusable catalyst that can be used for synthesis of a new range of bis(indolyl)methane derivatives.     

Trace determination of vardenafil hydrochloride in commercial formulation and human serum by adsorptive anodic stripping voltammetry at a carbon paste electrode

The electrochemical behavior of vardenafil HCl (VRL) at a carbon paste electrode (CPE) was investigated by cyclic voltammetry, and the mechanism of its oxidation was suggested and discussed. A simple Nujol-based CPE in combination with a sensitive square-wave adsorption anodic stripping voltammetry method was described for trace determination of VRL. The described method showed excellent performance for trace determination of VRL in its formulation “Levitra® tablets” without interference from excipients. The results were statistically compared with those obtained with an established HPLC method; nonsignificant differences were found between the described voltammetric and HPLC methods. The described stripping voltammetric method is highly sensitive (limit of detection?=?3?×?10^?10?mol?L^?1 and limit of quantitation?=?1?×?10^?9?mol?L^?1). It was successfully applied for the determination of VRL in spiked human serum without the necessity for pretreatment and/or time-consuming extraction steps prior to the analysis.     

Formation mechanisms of gold-zinc oxide hexagonal nanopyramids by heterogeneous nucleation using microwave synthesis

This work reports the development of a fast and simple "one-pot" route for the synthesis of hybrid Au-ZnO hexagonal nanopyramids by sequential homogeneous-heterogeneous nucleation steps involving both Au and Zn ions using microwave irradiation (MWI). The rapid decomposition of zinc acetate by MWI in the presence of a mixture of oleic acid (OAc) and oleylamine (OAm) results in the formation of hexagonal ZnO nanopyramids. In the presence of Au ions, the initially formed Au nanocrystals act as heterogeneous nuclei for the nucleation and growth of the ZnO nanopyramids. The Au nanoparticles promote the heterogeneous nucleation of ZnO and the formation of the hexagonal base of the ZnO nanopyramids. Using preformed Au nanoparticles instead of Au ions results in a narrow size distribution of uniform Au-ZnO nanopyramids, each consisting of a gold nanoparticle embedded in the center of the hexagonal base of the ZnO nanopyramid. We study the factors that control the nucleation and growth of these complex structures, and provide new insights into the stepwise homogeneous-heterogeneous mechanism and the conventional heterogeneous nucleation on preformed Au nanoparticles. The formation of the hetero nanostructures Au-ZnO nanopyramids is strongly dependent on the molar ratios of OAc to OAm. The presence of OAc with a considerable dipole moment results in strong electrostatic interaction with the polar surfaces of the growing ZnO nanocrystals thus resulting in slowing the growth rate of the polar planes and allowing the formation of well-developed facets. In the absence of Au nanoparticles, a high concentration of zinc acetate and longer MWI times are required for the production of the nanopyramids. The gold nanoparticles could provide the metallic contact points within the hybrid nanopyramids which could facilitate the bottom-up assembly of Au-ZnO devices. Furthermore, the Au-ZnO nanopyramids could have improved performance in solar energy conversion and photocatalysis.     

Monitoring cellular responses upon fatty acid exposure by Fourier transform infrared spectroscopy and Raman spectroscopy

We investigated the applicability of FTIR-spectroscopy as a high throughput screening method for detection of biochemical changes in intact liver cells in bulk upon fatty acid exposure. HepG2 cells adapted to serum free (HepG2-SF) growth were exposed to four different fatty acids, three octadecenoic acids, differing in cis/trans-configuration or double bond position (oleic acid, elaidic acid and vaccenic acid) as well as palmitic acid in three days. High throughput FTIR spectroscopic measurements on dried films of intact cells showed spectra with high signal-to-noise ratio and great reproducibility. When applying principal component analysis (PCA) a clear discrimination between fatty acid exposures was observed. Higher levels of triacylglycerides were accumulated in cells exposed to elaidic acid than when exposed to the other fatty acids; the least accumulation appeared to be in cells exposed to palmitic acid. An increased absorption at ~966 cm(-1) corresponding to trans-double bond was detected upon elaidic acid exposure but not upon vaccenic acid exposure. Instead, upon vaccenic acid exposure two new absorption bands were observed at 981 and 946 cm(-1) due to the presence of double bond conjugation. Raman spectroscopy on single cells, with and without treatment by vaccenic acid, confirmed the presence of conjugation. By fatty acid composition analysis, the conjugation was further specified to be conjugated linoleic acid (CLA) isomers. Thus, instead of being preserved as a monounsaturated fatty acid, vaccenic acid was converted into CLA in HepG2 cells. The results demonstrate the applicability of high-throughput FTIR spectroscopy as an explorative method in in vitro systems from which biologically relevant hypotheses can be generated and further investigated.     

Nanoemulsions of Jasminum humile L. and Jasminum grandiflorum L. Essential Oils: An Approach to Enhance Their Cytotoxic and Antiviral Effects

Unprecedented nanoemulsion formulations (NE) of Jasminum humile and Jasminum grandiflorum essential oils (EO) were prepared, and examined for their cytotoxic and antiviral activities. NE characterization and stability examination tests were performed to ensure formula stability. The antiviral activity was determined against hepatitis A (HAV) and herpes simplex type-1 (HSV-1) viruses using MTT assay, while the cytotoxic potential was determined against liver (HepG-2), breast (MCF-7), leukemia (THP-1) cancer cell lines and normal Vero cells. Statistical significance was determined in comparison with doxorubicin as cytotoxic and acyclovir as antiviral standard drugs. GC-MS analysis indicated twenty four compounds in the EO of J. humile and seventeen compounds in the EO of J. grandiflorum. Biological investigations of pure EOs revealed weak cytotoxic and antiviral effects. Nevertheless, their NE formulations exhibited high biological value as cytotoxic and antiviral agents. NE formulations also showed feasible selectivity index for the viral-infected and cancer cells (especially HepG-2) than normal Vero cells. Both nanoemulsions showed lower IC₅₀ than standard doxorubicin against HepG-2 (26.65 and 22.58 vs. 33.96 μg/mL) and MCF-7 (36.09 and 36.19 vs. 52.73 μg/mL), respectively. The study results showed the dramatic effect of nanoemulsion preparation on the biological activity of EOs and other liposoluble phytopharmaceuticals.