Isophthalamides and 2,6-dicarboxamidopyridines with pendant indole groups: a 'twisted' binding mode for selective fluoride recognition

Two cleft-like anion receptors have been synthesised that contain indole hydrogen-bond donors and show fluoride selectively in a DMSO-water solution with crystallographic studies showing a 'twisted' binding mode for fluoride in the solid state.     

Acridinone-based anion receptors and sensors

The interaction of a variety of acridinone derivatives containing hydrogen-bond donor groups in the 4- and 5-positions with anions demonstrate the potential of this new scaffold in anion receptor and sensor design.     

A low-cost, disposable card for rapid polymerase chain reaction

A low-cost, disposable card for rapid polymerase chain reaction (PCR) was developed in this work. Commercially available, adhesive-coated aluminum foils and polypropylene films were laminated with structured polycarbonate films to form microreactors in a card format. Ice valves [1] were employed to seal the reaction chambers during thermal cycling and a Peltier-based thermal cycler was configured for rapid thermal cycling and ice valve actuation. Numerical modeling was conducted to optimize the design of the PCR reactor and investigate the thermal gradient in the reaction chamber in the direction of sample thickness. The PCR reactor was experimentally characterized by using thin foil thermocouples and validated by a successful amplification of 10 copy of E. coli tuf gene in 27 min.     

On Genericity and Ershov's Hierarchy

It is natural to wish to study miniaturisations of Cohen forcing suitable to sets of low arithmetic complexity. We consider extensions of the work of Schaeffer [9] and Jockusch and Posner [6] by looking at genericity notions within the Δ₂ sets. Different equivalent characterisations of 1‐genericity suggest different ways in which the definition might be generalised. There are two natural ways of casting the notion of 1‐genericity: in terms of sets of strings and in terms of density functions, as we will see here. While these definitions coincide at the first level of the difference hierarchy, they turn out to differ at other levels. Furthermore, these differences remain when the remainder of the Δ⁰₂ sets are considered. While the string characterization of 1‐genericity collapses at the second level of the difference hierarchy to 2‐genericity, the density function definition gives a very interesting hierarchy at level w and above. Both of these results point towards the deep similarities exhibited by the n‐c.e. degrees for n ≥ 2.     

Acid-base catalysis in zeolites from first principles

Zeolite materials are microporous aluminosilicates with various uses, including acting as important catalysts in many processes. One such process is the methanol to gasoline reaction, used widely in industry. This reaction is known to be associated with Brønsted acid sites in the zeolite, formed when Si is substituted by Al in the framework, with an associated H⁺ being bound nearby to maintain charge neutrality. However, it is not clear exactly what role the proton plays in this reaction. Because of the large unit cell (generally 50-300 atoms, depending on the particular zeolite) of such structures, most ab initio calculations of these materials have focused on studying small clusters representing just a portion of the framework. However, by choosing the chabazite zeolite structure, which has only 36 atoms in the primitive unit cell, we have been able to perform a full periodic ab initio calculation. This has used density functional theory with a generalized gradient approximation for the exchange-correlation energy, a plane-wave basis set, and norm-conserving optimized pseudopotentials. Using these methods we have examined the geometry and electronic structure of a zeolite acid site and considered one way in which a methanol molecule may bind to such a site. © 1997 John Wiley & Sons, Inc.     

Capillary Hysteresis in Neutrally Wettable Fibrous Media: A Pore Network Study of a Fuel Cell Electrode

Hysteresis in the saturation versus capillary pressure curves of neutrally wettable fibrous media was simulated with a random pore network model using a Voronoi diagram approach. The network was calibrated to fit experimental air-water capillary pressure data collected for carbon fibre paper commonly used as a gas diffusion layer in fuel cells. These materials exhibit unusually strong capillary hysteresis, to the extent that water injection and withdrawal occur at positive and negative capillary pressures, respectively. Without the need to invoke contact angle hysteresis, this capillary behaviour is re-produced when using a pore-scale model based on the curvature of a meniscus passing through the centre of a toroid. The classic Washburn relation was shown to produce erroneous results, and its use is not recommended when modelling fibrous media. The important effect of saturation distribution on the effective diffusivity of the medium was also investigated for both water injection and withdrawal cases. The findings have bearing on the understanding of both capillarity in fibrous media and fuel cell design.     

Dual-color operation of a femtosecond optical parametric oscillator exhibiting stable relative carrier-envelope phase-slip frequencies

A femtosecond optical parametric oscillator is demonstrated that can operate in a regime where two signal pulses with well-separated center wavelengths are simultaneously resonant. Measurements show that the oscillator output contains a stable modulation at a frequency corresponding to the difference in the carrier-envelope phase-slip frequencies of the co-resonant pulses. The physical origin of this internal beat signal is attributed to second-order mixing effects, and its frequency is shown to be consistent with theory.     

Oligoether-strapped calix[4]pyrrole: an ion-pair receptor displaying cation-dependent chloride anion transport

A ditopic ion-pair receptor (1), which has tunable cation- and anion-binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([1·F](-) and [1·Cl](-)) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li(+), Na(+), K(+), Cs(+), as their perchlorate salts), ion-dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [1·F](-), no appreciable interaction with the K(+) ion was seen. On the other hand, when this complex was treated with Li(+) or Na(+) ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li(+), Na(+), K(+), treating [1·F](-) with Cs(+) ions gave rise to a stable, host-separated ion-pair complex, [F·1·Cs], which contains the Cs(+) ion bound in the cup-like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [1·Cl](-). Here, no appreciable interaction was observed with Na(+) or K(+). In contrast, treating with Li(+) produces a tight ion-pair complex, [1·Li·Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [1·F](-), treatment of [1·Cl](-) with Cs(+) ions gives rise to a host-separated ion-pair complex, [Cl·1·Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co-transport) and antiport (nitrate-for-chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate-for-chloride anion exchange mechanism.