Preparation of phosphinated bisphenol from acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane and its application in high‐performance cyanate esters

We reveal a route for the preparation of phosphinated bisphenol, 1,1‐bis(4‐hydroxyphenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (2) , via a one‐pot reaction of 1,1,1‐tris(4‐hydroxyphenyl)ethane and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) in the catalysis of p‐toluenesulfonic acid. A two‐step reaction mechanism, acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane followed by nucleophilic addition of DOPO, is proposed for the synthesis. Based on (2) , a dicyanate ester derivative, 1,1‐bis(4‐cyanatophenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (3) was prepared and co‐cured with a commercially available dicyanate ester, the dicyanate ester of bisphenol A (BACY). Experimental data show that incorporating (3) into BACY enhances the flame retardancy and dielectric properties with little penalty to the thermal properties. A thermoset with T_g 274 °C, coefficient of thermal expansion (CTE) 49 ppm/°C, D_k 3.04 (1 GHz), T_d (5%,) N₂: 435 °C, air: 424 °C, and UL‐94 V‐0 rating can be achieved via this approach. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Experimental and theoretical investigation of galloping of transversely inclined slender prisms

Galloping is characterized by large and periodical oscillations which may lead to collapse of slender structures. This study is the first attempt of a comprehensive experimental and theoretical investigation of galloping of transversely inclined prisms. A modified quasi-steady model is proposed with a constant term to estimate the galloping of a transversely inclined prism, which is later experimentally investigated by conducting a static Synchronous Multi-Pressure Sensing System (SMPSS) test and an aeroelastic test in a boundary layer wind tunnel. The galloping responses of the prisms were measured in the aeroelastic test, while the aerodynamic force coefficients were determined from the SMPSS test. These experimental results were subsequently utilized to validate the quasi-steady model. Based on the proposed model, the galloping responses of the prisms were predicted and compared with the experimental results. The experimentally measured and theoretically predicted galloping responses are discussed with respect to aerodynamic damping ratios, onset galloping wind speeds, distributed pressure coefficients, point pressure spectra and vortex shedding frequencies. Interesting findings are summarized.     

Coherent photogalvanic valley Hall effect

The theory of the coherent photogalvanic valley Hall effect in two-dimensional systems with the Dirac spectrum of charge carriers is formulated. The study deals with a two-dimensional sample irradiated by two electromagnetic waves, at the fundamental and doubled frequencies. Both frequencies exceed the band gap of the material, whereas the wave with the fundamental frequency having circular polarization and a high intensity is taken into account in a nonperturbative manner. The wave at the doubled frequency is linearly polarized and the electrical conductivity of the two-dimensional system is calculated with respect to it. The effect under study manifests itself as the dc Hall current in the direction orthogonal to the electric field of the weak electromagnetic wave. It is assumed that, in equilibrium, the sample is in the insulating state with the completely occupied valence band and empty conduction band. The strong electromagnetic wave induces a nonequilibrium filling of the bands and the system passes to a strongly nonequilibrium steady state. The behavior of the Hall current in the case of nonequilibrium distribution functions is analyzed both including and disregarding the intraband relaxation and interband recombination.     

Control of Schottky barrier heights on high-K gate dielectrics for future complementary metal-oxide semiconductor devices

The calculated Schottky barrier heights of polar and nonpolar interfaces of many metals on HfO2 high dielectric constant gate oxide have been found to vary strongly with the metal work function and also with oxide termination, with relatively little Fermi level pinning. This indicates that the choice of metal gate materials will not limit the continued scaling of metal-oxide semiconductor devices.     

HPLC Determination of Lansoprazole and Method Application for the Formulation Development of Enteric‐coated Lansoprazole Pellets

The aim of this study was to develop a validated HPLC method for the determination of lansoprazole in dissolution medium and pellets. For the formulation development, we investigated the role of 2‐hydroxypropyl‐β‐cyclodextrin (HPβCD) on the dissolution of enteric‐coated pellets of lansoprazole prepared by the solution layering technique using a fluid bed coater. Dissolution results demonstrated the coating using Acryl‐Eze protected the formulations from releasing lansoprazole in acid medium for the first 2 h, and the addition of HPβCD improved the dissolution performance by 189%, compared with the group without HPβCD. The DSC analysis displaced an absence of the endothermic peak for the lyophilized products lansoprazole and HPβCD, and FTIR analysis demonstrated the band broadening, shifting or disappearance compared to the spectra of the physical mixture, which indicated the formation of the inclusion complex between lansoprazole and HPβCD. This study has developed a validated HPLC method to measure lansoprazole in test media and pellets, which was applied successfully to the formula tion development of enteric‐coated pellets.     

Strategies in quantitative LC-MS/MS analysis of unstable small molecules in biological matrices

Stability is an important pre-analytical variable for quantitative LC-MS/MS analysis of drug molecules and/or their metabolites in biological matrices. Instability of an analyte in any stage of the bioanalytical process, including sample collection, processing, storage, extraction and LC-MS/MS analysis, can result in under-/over-estimation if an adequate preventive procedure is not in place. In the current review on practical strategies in quantitative LC-MS/MS bioanalysis of unstable small molecules, the common causes of analyte instability were examined. The instability of some analytes is readily predictable because of the presence of certain chemically or biologically labile moieties in the molecules or because the compounds are in an inter-convertible form, e.g. lactone vs hydroxyl carboxylic acid. However, the instability of many other analytes is not readily predictable. Necessary evaluation needs to be conducted to identify the possible instability issues. The current review highlighted some general considerations and specific approaches for developing a robust LC-MS/MS method. In particular, incurred samples should be used as part of routine short-term stability assessment of any unstable analyte during the early stages of method development and validation. This can help unveil any 'hidden' instability issues that, if left unaddressed, could lead to the invalidation of a 'validated' method.