Configurational Lability at Tetrahedral Phosphorus: syn/anti-Isomerization of a P-Stereogenic Phosphiranium Cation by Intramolecular Epimerization at Phosphorus

Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH₂CHPh][OTf] (Mes*=2,4,6-(t-Bu)₃C₆H₂) occurred under mild conditions at 60 °C in CD₂Cl₂, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu₄][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C₆Cl₄O₂)₃) followed by chromatography on silica removed [NBu₄][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH₂CHPh][Δ-TRISPHAT]?x[NBu₄][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P.     

Real-time detection of DNA interactions with long-period fiber-grating-based biosensor

Using an optical biosensor based on a dual-peak long-period fiber grating, we have demonstrated the detection of interactions between biomolecules in real time. Silanization of the grating surface was successfully realized for the covalent immobilization of probe DNA, which was subsequently hybridized with the complementary target DNA sequence. It is interesting to note that the DNA biosensor was reusable after being stripped off the hybridized target DNA from the grating surface, demonstrating a function of multiple usability.     

Fabrication and characterization of TEOS-based silica aerogels prepared using rapid supercritical extraction

Silica aerogels were prepared using the precursor tetraethylorthosilicate (TEOS) via a rapid supercritical extraction (RSCE) method. Multiple consistent batches of monolithic TEOS-based aerogels were fabricated via an 8-h RSCE process. Fabricating TEOS-based aerogels with an RSCE method offers some distinct advantages. One advantage is the relative simplicity of the RSCE approach: liquid precursors are mixed and poured into a metal mold in a hydraulic hot-press, where gelation, aging and extraction of liquid from the pores occur. The precursor recipe employs TEOS, ethanol, water, oxalic acid to catalyze hydrolysis, and ammonia to catalyze the subsequent polycondensation reactions. Another advantage is that reaction of TEOS to form sol gels yields ethanol as a byproduct. A process that releases ethanol, rather than methanol (as in tetramethylorthosilicate (TMOS)-based aerogels) may be more appealing for commercial applications, involving scale-up of the process. The significantly lower cost of TEOS, compared to TMOS, is a considerable advantage. The TEOS-based RSCE aerogels are mesoporous and optically translucent, have bulk densities of 0.099(±0.003) g/cm³ and surface areas of 460(±10) m²/g. Signals observed in infrared and Raman spectra of the aerogels are consistent with Si–O framework bonds. Using scanning electron microscopy imaging, the surface morphology of the aerogel samples was imaged at magnifications up to 150 kX.     

微乳液的热力学性质 I: 芳烃类的侧链链长对微乳液热力学函数影响

本文研究以非离子型表面活性剂-正辛醇-水-芳烃类所组成的微乳液, 探讨醇从油相转移到界面相时的自由能变化, 以及温度对自由能的影响。计算出熵和焓的变化, 发现在实验范围内, 上述热力学函数的对数值与芳烃侧链的碳原子数(n)呈线性关系。这些关系式对微乳液的构成和稳定性的讨论是重要的, 还对几种芳烃异构体所构成的微乳液的热力学函数进行了实验和讨论。     

Control of holding currents in amorphous threshold switches

It is usually assumed that the holding current of an amorphous semiconductor threshold switch is not strongly dependent on the circuit surrounding the switch. This paper shows that the holding current is in fact controlled by both the series resistance and the parallel capacitance, according to two simple inequalities. In order to obtain low holding currents a large series resistor and minimum parallel capacitance are required, and in this way a holding current of 10 μA has been observed. Data are also presented on the effects of device dimensions and temperature on the on-state I-V curves and holding current.     

The use of macroscopic modelling of intermetallic phases in aluminium alloys in the study of ferricyanide accelerated chromate conversion coatings

Chromate conversion coatings are used on aluminium alloys, primarily for their renowned corrosion resistant properties. Although these coatings are in common industrial use, neither the protection mechanisms, nor the coating interation with the intermetallic precipitation phases are fully understood. Macroscopic models have been developed in order to represent the galvanic cells present in aluminium alloys due to the presence of such intermetallic particles. Particles modelled include CuAl₂, FeAl₃ and Cu₂FeAl₇, all know to be cathodic to the aluminium matrix. Variations in deposition, both in composition and thickness, are indicative of the mechanisms of deposition over each phase. Characterisation of the coating deposition was carried out using X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, Auger electron spectroscopy, scanning electron microscopy with X-ray analysis. Depositional characteristics have been determined for each phase. The coating on the intermetallic phases is primarily Al oxide, and is significantly thinner than the coating on the matrix. This coating on the matrix consists mainly of a mixed Cr/Al oxide. The coating on the intermetallic phases was only one tenth the thickness of the matrix coating, and contained higher levels of Fe, Al and O. Matrix coating chemistry predominated with Cr, O, Fe and N, indicative of a chromate conversion coating. The mechanism for reduced rates of deposition over intermetallic phases was found to be affected by fluorine ion attack leading to intermetallic de-alloying and decomposition of Fe(CN)₆²⁻ accelerator into amide groups on the matrix.     

Application of amorphous silicon field effect transistors in addressable liquid crystal display panels

It is shown that thin-film field effect transistors (FETs) made from amorphous (a-) silicon deposited by the glow-discharge technique have considerable potential as switching elements in addressable liquid crystal display panels. The fabrication of the elements and their characteristics with steady and pulsed applied potentials are discussed in some detail. Two important points are stressed: (i) a-Si device arrays can be produced by well-established photolithographic techniques, and (ii) satisfactory operation at applied voltages below 15VV is possible. Small experimental 7×5 transistor panels have been investigated and it is shown that with the present design up to 250-way multiplexing could be achieved. The reproducibility of FET characteristics is good and in tests so far no change has been observed after more than 10⁹ switching operations.     

Bases for rings of coinvariants

We study the multiplicative structure of rings of coinvariants for finite groups. We develop methods that give rise to natural monomial bases for such rings over their ground fields and explicitly determine precisely which monomials are zero in the ring of coinvariants. We apply our methods to the Dickson, upper triangular and symmetric coinvariants. Along the way, we recover theorems of Steinberg [17] and E. Artin [1]. Using these monomial bases we prove that the image of the transfer for a general linear group over a finite field is a principal ideal in the ring of invariants. This research is supported in part by the Natural Sciences and Engineering Research Council of Canada