Real‐time measurement of peroxyacetyl nitrate using selected ion flow tube mass spectrometry

The on‐line detection of gaseous peroxyacetyl nitrate (PAN) using selected ion flow tube mass spectrometry (SIFT‐MS) has been investigated using a synthetic sample of PAN in air at a humidity of ～30%. Using the H₃O⁺ reagent ion, signals due to PAN at m/z 122, 77 and 95 have been identified. These correspond to protonated PAN, protonated peractetic acid and its water cluster, respectively. These products and their energetics have been probed through quantum mechanical calculations. The rate coefficient of H₃O⁺ has been estimated to be 4.5 × 10^?9 cm³ s^?1, leading to a PAN sensitivity of 138 cps/ppbv. This gives a limit of detection of 20 pptv in 10 s using the [M+H]⁺ ion of PAN at m/z 122. Copyright © 2010 John Wiley & Sons, Ltd.     

In situ lift-out using a FIB-SEM system

An in situ 'lift-out' technique for preparing transmission electron microscopy specimens, which is performed using secondary electron imaging within the chamber of a focused ion beam-SEM system is presented. The main advantage of this in situ approach, relative to the ex situ lift-out technique, is that secondary electron imaging enables higher magnifications to be used than is possible with optical microscopy. This makes the lift-out procedure more controllable and thus increases the overall success rate especially for inexperienced users. The technique is also compared with another in situ lift-out approach, the 'wedge' technique.     

Reorientation Response of Magnetic Microspheres Attached to Gold Electrodes Under an Applied Magnetic Field

In this work, we report the mechanical reorientation of thiolated ferromagnetic microspheres bridging a pair of gold electrodes under an external magnetic field. When an external magnetic field (7 kG) is applied during the measurement of the current–voltage characteristics of a carboxyl ferromagnetic microsphere (4 μm diameter) attached to two gold electrodes by self-assembled monolayers (SAMs) of octane dithiol (C₈H₁₈S₂), the current signal is distorted. Rather than due to magnetoresistance, this effect is caused by a mechanical reorientation of the ferromagnetic sphere, which alters the number of SAMs between the sphere and the electrodes and therefore affects conduction. To study the physical reorientation of the ferromagnetic particles, we measure their hysteresis loops while suspended in a liquid solution.     

Normal form for generalized Hopf bifurcation with non-semisimple 1 ∶ 1 resonance

The primary result of this research is the derivation of an explicit formula for the Poincaré-Birkhoff normal form of the generalized Hopf bifurcation with non-semisimple 1:1 resonance. The classical nonuniqueness of the normal form is resolved by the choice of complementary space which yields a unique equivariant normal form. The 4 leading complex constants in the normal form are calculated in terms of the original coefficients of both the quadratic and cubic nonlinearities by two different algorithms. In addition, the universal unfolding of the degenerate linear operator is explicitly determined. The dominant normal forms are then obtained by rescaling the variables. Finally, the methods of averaging and normal forms are compared. It is shown that the dominant terms of the equivariant normal form are, indeed, the same as those of the averaged equations with a particular choice for the constant of integration.Partially supported by NSF through grant MSS 90-57437, AFOSR through grant 91-0041 and NSERC of Canada.     

Scanning-induced growth on single crystal calcite with an atomic force microscope

We report observations of localized growth on the (1014) surface of single-crystal CaCO3 in supersaturated solutions while scanning with the tip of an atomic force microscope (AFM). At low contact forces, AFM scanning strongly enhances deposition along preexisting steps. This enhancement increases rapidly with increasing solution supersaturation, and is capable of filling in multilayer etch pits to produce defect-free surfaces at the resolution of the AFM. Attempts to achieve similar deposition rates in the absence of scanning require high supersaturations that produce three-dimensional crystal nuclei, which are important defects. Localized deposition produced by drawing the AFM tip back and forth across step edges can produce monolayer deposits extending well over a micron from the scanned area. These tip-induced deposits provide convincing evidence for the importance of ledge diffusion in calcite crystal growth.     

Unusual solid-state behavior in a neutral [2]catenane bearing a hydrolyzable component

A template-directed strategy to forming a bis(diimide) macrocycle through an intermediate asymmetric [2]catenane is reported. Saponification of the ester linkages within the crown ether component is much slower in the mechanically interlocked structure when compared to the free crown. The predominance of a single translational isomer leads to a dimeric structure, resulting in the generation of infinite channels within the crystal lattice. [structure: see text]     

Characterization of an LED based photoreactor to degrade 4-chlorophenol in an aqueous medium using coumarin (C-343) sensitized TiO2

A detailed performance evaluation of a simple high intensity LED based photoreactor exploiting a narrow wavelength range of the LED to match the spectrum of a dye in a photocatalysis system is reported. A dye sensitized (coumarin-343, lambda max = 446 nm) TiO 2 photocatalyst was used for the degradation of 4-chlorophenol (4-CP) in an aqueous medium using the 436 nm LED based photoreactor. The LED reactor performed competitively with a conventional multilamp reactor and sunlight in the degradation of 4-CP. Light intensities entering the reaction vessel were measured by conventional ferrioxalate actinometry. The results can be fitted by approximate first order kinetic behavior in this system. Hydroxyl radicals were detected by spin trapping EPR, and effects of OH radical quenchers on kinetics suggest that the reaction is initiated by these radicals or their equivalents. LEDs operating at competitive intensities offer a number of advantages to the photochemist or the environmental engineer via long life, efficient current to light conversion, narrow bandwidth, forward directed output, and direct current power for remote operation. Matching light source spectrum to chromophore is a key.