High Tg nematic thermosets: Synthesis, characterization and thermo-mechanical properties

In this paper the synthesis and characterization of a new family reactive nematic oligomers based on 4-hydroxybenzoic acid (4-HBA) will be presented. We modified the backbone using para- and meta-substituted aromatic monomers such as terephthalic acid (TA), isophthalic acid (IA), hydroquinone (HQ), resorcinol (RS), 4,4′-bisphenol (BP) and 3-hydroxybenzoic acid (3-HBA). All oligomers, with a target M_n of 5000 and 9000 g mol⁻¹, were end-capped with reactive phenylethynyl functionalities and synthesized using standard melt condensation techniques. Curing of the phenylethynyl reactive functionalities proceeds through chain extension and crosslinking, depending upon the temperature and time and can be carried out between 310 and 400 °C. Fully cured nematic thermosets could be obtained with glass-transition temperatures previously not accessible (T_g > 400 °C). The cured polymers exhibit excellent tensile properties, i.e. tensile strength (83 MPa) and elongation at break (9%). This approach allows us to prepare all-aromatic polymers with a combination of useful properties such as ease of processing, high T_g’s, and excellent mechanical properties.     

Synthesis of 5‐(Arylselanyl)‐2‐(arylsulfanyl)benzoates by [3+3] Cyclocondensation of 3‐(Arylsulfanyl)‐1‐(silyloxy)buta‐1,3‐dienes with 2‐(Arylselanyl)‐3‐(silyloxy)alk‐2‐en‐1‐ones

Functionalized 5‐(arylselanyl)‐2‐(arylsulfanyl)benzoates were prepared by [3+3] cyclocondensation of 3‐(arylsulfanyl)‐1‐(silyloxy)buta‐1,3‐dienes with 2‐(arylselanyl)‐3‐(silyloxy)‐alk‐2‐en‐1‐ones.     

Optimization and Validation of RP-LC/UV–VIS Detection Method for Simultaneous Determination of Fat-Soluble Anti-Oxidant Vitamins, all-trans-Retinol and α-Tocopherol in Human Serum: Effect of Experimental Parameters

A versatile isocratic reversed-phase liquid chromatographic/ultraviolet–visible detection method for simultaneous determination of all-trans-retinol and α-tocopherol in human serum was developed and validated after optimization of various chromatographic conditions and other experimental parameters. Analytes were separated on a Kromasil 100 RP₁₈ (150 × 4.6 mm, 5 μm) analytical column protected by a Perkin Elmer RP₁₈ (30 × 4.6 mm, 10 μm) guard cartridge. The mobile phase, methanol–water (96:04 v/v) was pumped at a flow rate of 2.2 mL min^?1 and the column eluents were monitored at the wavelength of 292 nm using retinyl acetate (1.0 μg mL^?1) as the internal standard for both analytes. Sample preparation was based on protein precipitation and stabilization with 2,6-bis(1,1-dimethylethyl)-4-methylphenol/ethanol and a two step extraction process using n-hexane followed by dichloromethane as extraction solvents. Sample size was kept 20 μL and separation of analytes was achieved in less than 7 min. The present method demonstrated acceptable values for specificity/selectivity, linearity within the expected concentration range, recovery, precision, sensitivity, stability of solutions, robustness, and system suitability specifications and tests. The method was used for monitoring all-trans-retinol and α-tocopherol concentrations in human serum samples and could also be applied to other sample matrices such as brain slices and cosmetic products if attention is paid to the extraction procedure.     

Effect on photophysical properties of colloidal ZnS quantum dots by doping with cobalt, copper, and cobalt�Ccopper mixtures

Colloidal ZnS quantum dots (QDs) are prepared by passing H₂S gas through a solution of Zn(CH₃COO)₂ in acetonitrile. Photophysical properties are investigated using UV?CVisible and photoluminescence (PL) spectroscopy. The spectrum shows an absorption shoulder at 271 nm representing a band gap of 4.6 eV. The doping of ZnS QDs with Co, Cu, and a mixture of Co and Cu not only increased the band gap to 0.2 eV but also turns these otherwise colorless QDs to blue in color due to cobalt, and green due to Cu. The observed emission in the visible region suggests that the dopants may have induced additional excited states to the ZnS QDs. This absorbance in the visible region can be utilized in the optoelectronic applications.     

Spectrophotometric Quantitation of Fluoxetine Hydrochloride Using Benzoyl Peroxide and Potassium Iodide

 Fluoxetine hydrochloride reacts with benzoyl peroxide and potassium iodide, after heating for 1 min at 30 °C, to give a blue colour having maximum absorbance at 570 nm. The reaction is selective for fluoxetine with 0.01 mg/mL as visual limit of quantitation and provides a basis for a new spectrophotometric determination. The colour reaction obeys Beer’s law from 0.1 mg/10 mL to 2.0 mg/10 mL of fluoxetine and the relative standard deviation is 0.68%. The qualitative assessment of tolerable amounts of other drugs is also studied. Received September 21, 1998. Revision September 10, 1999.     

Cobalt(II) Complex Catalysed Epoxidation with Molecular Oxygen

Cobalt(II) complexes 1 or 2, catalyses the epoxidation of alkenes in the presence of molecular oxygen and 2-methylpropanal in high yields.     

Electrochemical behavior of anthraquinone in aqueous solution in presence of a non-ionic surfactant

Cyclic voltammetric behavior of anthraquinone in aqueous medium has been studied in presence of a non-ionic surfactant, Triton X-100 (TX-100) using sodium salt of anthraquinone-2-sulphonic acid (AQS) as the electro-active species. When cathodic potential is applied, the anthraquinone (AQ) group of AQS is reduced to its dianion. In the reverse scan, the oxidation of AQ²⁻ gives AQ. The electrochemical behavior shows a profound influence from the dissolved state of TX-100 in aqueous media. Spectrophotometric results indicate interaction between AQ and TX-100. A CEC (chemical–electrochemical–chemical) mechanism with the electrochemical reaction coupled with preceding interaction of AQS with TX-100 and following protonation reaction of reduced AQ has been proposed.     

A study on melt grafting of maleic anhydride onto low‐density polyethylene and its blend with polyamide 6

Graft copolymerization of low‐density polyethylene (LDPE) with a maleic anhydride (MAH) was performed using intermeshing corotating twin‐screw extruder in the presence of benzoyl peroxide (BPO). The LDPE/polyamide 6 (PA6) and LDPE‐g‐MAH/PA6 blends were prepared in a corotating twin‐screw extruder. The melt viscosity of the grafted LDPE was measured by a capillary rheometer. The grafted copolymer was characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microcopy (SEM). The influence of the variation in temperature, BPO and MAH concentration, and temperature on the grafting degree and on the melt viscosity was studied. The grafting degree increased appreciably up to about 0.45 phr and then decreased continuously with an increasing BPO concentration. According to the FTIR analysis, it was found that the amount of grafted MAH on the LDPE chains was ～5.1%. Thermal analysis showed that melting temperature of the graft copolymers decreases with increasing grafting degree. In addition to this, loss modulus (E″) of the copolymers first increased little with increasing grafting and then obviously decreased with increasing grafting degree. Furthermore, the results revealed that the tensile strength of the blends increased linearly with increasing PA6 content. The results of SEM and mechanical test showed that the blends have good interfacial adhesion and good stability of the phase structure, which is reflected in the mechanical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 267–275, 2010     

High‐performance liquid chromatography/mass spectrometric and proton nuclear magnetic resonance spectroscopic studies of the transacylation and hydrolysis of the acyl glucuronides of a series of phenylacetic acids in buffer and human plasma

The use of high‐performance liquid chromatography/mass spectrometry (HPLC/MS) and proton nuclear magnetic resonance (¹H NMR) spectroscopy for the kinetic analysis of acyl glucuronide (AG) isomerisation and hydrolysis of the 1‐β‐O‐acyl glucuronides (1‐β‐O‐AG) of phenylacetic acid, (R)‐ and (S)‐α‐methylphenylacetic acid and α,α‐dimethylphenylacetic acid is described and compared. Each AG was incubated in both aqueous buffer, at pH 7.4, and control human plasma at 37°C. Aliquots of these incubations, taken throughout the reaction time‐course, were analysed by HPLC/MS and ¹H NMR spectroscopy. In buffer, transacylation reactions predominated, with relatively little hydrolysis to the free aglycone observed. In human plasma incubations the calculated rates of reaction were much faster than for buffer and, in contrast to the observations in buffer, hydrolysis to the free aglycone was a significant contributor to the overall reaction. A diagnostic analytical methodology based on differential mass spectrometric fragmentation of 1‐β‐O‐AGs compared to the 2‐, 3‐ and 4‐positional isomers, which enables selective determination of the former, was confirmed and applied. These findings show that HPLC/MS offers a viable alternative to the more commonly used NMR spectroscopic approach for the determination of the transacylation and hydrolysis reactions of these AGs, with the major advantage of having the capability to do so in a complex biological matrix such as plasma. Copyright © 2010 John Wiley & Sons, Ltd.     

A new type of electrohydrodynamic instability in nematic liquid crystals with positive dielectric anisotropy

A new type of electrohydrodynamic instability originally reported in nematic liquid crystal mixtures with positive dielectric anisotropy and as moderately thick samples is further studied. The ability of homogeneously aligned nematics with positive dielectric anisotropy, in the presence of a magnetic field, to exhibit Williams domains as a threshold effect is numerically investigated. The variation of the threshold voltage for domain formation and dielectric alignment with dielectric anisotropy is calculated theoretically and compared with the experimental results as moderately thick and thin samples.