Regularized resolvent transform for direct calculation of 45 degrees projections of 2D J spectra

The regularized resolvent transform (RRT) has been applied in a novel way to J-resolved spectra. This involves the direct calculation of the 45 degrees projection without constructing the 2D spectrum. The results show a significant resolution enhancement over that obtained by the 45 degrees projection of a 2D Fourier spectrum, even for much larger signals. In particular, RRT is able to resolve peaks that belong to different overlapping multiplets in a very crowded spectral region, where the conventional technique fails for any signal size. The resolving power of this method along with the significantly shorter signals required, make this method a powerful tool in spectral assignment.     

Nitrogen isotope analysis of ammonium in aqueous solutions using a perfluorosulfonated ionomer membrane for solid-phase microextraction

The use of custom-made solid-phase microextraction (SPME) fibers coated with a perfluorosulfonated ionomer, Nafion, was investigated for nitrogen isotopic analysis of ammonium in aqueous solutions. Aqueous ammonium was converted to ammonia by addition of a base, followed by absorption from the headspace, desorption in the injection port of a gas chromatograph, and analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Fibers coated with a Nafion tubing were chosen due to a higher fiber-gas distribution constant and a higher Nafion thickness than fibers coated with Nafion solution, both leading to a higher amount of ammonia absorbed at equilibrium. The Nafion membrane-coated fiber absorbed approximately 20 times more than a commercial polydimethylsiloxane (PDMS) fiber. The isotopic fractionation between fiber and gas was 1.0117 +/- 0.0009 (standard deviation, SD, of all measurements) at an initial ammonia gas concentration of 21-210 microM. At 390 microM initial gas concentration it was slightly lower. When sampling from liquid samples, an ammonium concentration of 10 mM was needed to obtain a sufficient amount of ammonia absorbed. Modeling of the absorption at different temperatures showed that the absorption was approximately constant in the temperature range suitable for SPME experiments. Absorption at room temperature was therefore used for simplicity. A pilot study was conducted in which absorption was achieved from a single 9 microL droplet of sample. The preliminary results showed that delta(15)N analysis was possible for only 0.4-0.5 micromol of ammonium with a SD of 0.8 per thousand (n = 5).     

Computational evidence that the inverse kinetic isotope effect for reductive elimination of methane from a tungstenocene methyl-hydride complex is associated with the inverse equilibrium isotope effect for formation of a sigma-complex intermediate

Calculations on [H2Si(C5H4)2]W(Me)H demonstrate that the interconversion between [H2Si(C5H4)2]W(Me)H and the sigma-complex [H2Si(C5H4)2]W(sigma-HMe) is characterized by normal kinetic isotope effects for both reductive coupling and oxidative cleavage; the equilibrium isotope effect, however, is inverse and is the origin of the inverse kinetic isotope effect for the overall reductive elimination of methane.     

Trends in exchange coupling for trimethylenemethane-type Bis(semiquinone) biradicals and correlation of magnetic exchange with mixed valency for cross-conjugated systems

A magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling in this series of molecules. Our combined results indicate that the ferromagnetic portion of the exchange couplings occurs via the cross-conjugated pi-systems, while the antiferromagnetic portion occurs through space and is equivalent to incipient bond formation. Thus, molecular conformation controls the relative amounts of ferro- and antiferromagnetic contributions to exchange coupling. In fact, the exchange parameter correlates with average semiquinone ring torsion angles via a Karplus-Conroy-type relation. Because of the natural connection between electron spin exchange coupling and electronic coupling related to electron transfer, we also correlate the exchange parameters in the biradical complexes to mixed valency in the corresponding quinone-semiquinone radical anions. Our results suggest that delocalization in the cross-conjugated, mixed-valent radical anions is proportional to the ferromagnetic contribution to the exchange coupling in the biradical oxidation states.     

Detection of chlorinated methanes by tin oxide gas sensors

Tin oxide thin films prepared by thermal oxidation of Sn films were used for the detection of chlorinated methanes (CH2Cl2, CHCl3 and CCl4). This resulted in better chemical selectivity, sensitivity, response speed and detection limit than seen with previous detectors. The temperature dependence of the sensing of 1% CCl4 gas was studied and the best sensing behavior was observed at 300 degrees C. The films showed different chemical selectivity in both speed and direction of sensing response to each gas and were stable for more than 3 weeks under operating conditions. The films showed rapid gas sensing (<40 s to reach 90% of full response) and low detection limits (< 4 ppm CCl4). The role of oxygen in the detection of chlorinated methanes and in resistance changes without chlorinated methanes was also studied. The changes at the surface of the film after gas sensing were examined using scanning electron microscopy with energy-dispersive X-ray spectrometry.     

Unexpected solute aggregation in water on dilution

Studies on cluster-cluster aggregation phenomena in aqueous solutions of fullerene-cyclodextrin conjugates, beta-cyclodextrin, sodium chloride, sodium guanosine monophosphate, and a DNA oligonucleotide revealed that there are larger aggregates existent in dilute aqueous solutions than in more concentrated solutions.     

Gas diffusion in zeolite beds: PFG NMR evidence for different tortuosity factors in the Knudsen and bulk regimes

We present molecular dynamics simulations in the micro-canonical ensemble of a Lennard-Jones model of nitrogen confined in realistic models for saccharose-based carbons developed in our previous work. We calculate the velocity autocorrelation function and mean-squared displacement, and the self-diffusivities from the latter. We observe that the self-diffusivity increases with temperature and exhibits a maximum with loading or adsorbate density. To the best of our knowledge, a maximum in self-diffusivities has not been observed in molecular dynamics simulations of fluids confined in slit pores.Received: 1 January 2003, Published online: 30 October 2003PACS: 61.43.Gt Powders, porous materials - 68.43.Jk Diffusion of adsorbates, kinetics of coarsening and aggregation - 82.75.Fq Synthesis, structure determination, structure modeling     

Computational and experimental investigation of the fields generated by a 1-3 piezocomposite transducer

Large-scale three-dimensional numerical simulations using the finite-difference time domain technique are used to compute the continuous wave fields associated with a composite transducer. The interior of the transducer is made of a periodic array of square rods. This lattice causes elastic wave Bragg diffraction similar to electrons in a periodic lattice. A low frequency mode shape is assumed for the rods. This prescribed motion includes longitudinal and transverse components. It is shown that the transverse motion in the rod gives rise to shear waves causing standing waves (lateral resonances) in the polymer regions. This is also confirmed by experimental results presented here and other independent analytical and experimental work. The full-scale numerical simulation is performed on a large parallel supercomputer and permits modeling of not only the composite transducer but the radiated pressure from near to far field. In addition, cover plates and edge effects are included, unlike analytical treatments. Although only mechanical effects are included, the wave propagation approach captures many essential features.     

Focusing in microlenses close to a wavelength in diameter

Light focused from air into a spherical microlens is affected by diffraction at the lens surface as its diameter approaches the wavelength of light. Through an extension of Mie theory, we show that a converging wave that is incident upon a Si microlens with a diameter less than approximately 4lambda creates a spot as much as 25% smaller than predicted with vector diffraction theory. Si microlenses only a wavelength in diameter are shown to be virtually insensitive to variations in the maximum illumination angle, and changes in index of refraction are not found to cause the proportional changes in spot size that would be expected from vector diffraction theory.