Optimisation of supercritical fluid extraction of polynuclear aromatic hydrocarbons from spiked soil and marine sediment standard reference material

 For the determination of 16 PAHs in soils and sediment samples by GC/FID and GC/MS, the dynamic off-line supercritical fluid extraction with both pure and modified carbon dioxide has been evaluated. The optimisation of extraction parameters was performed for four individual groups of PAHs according to their number of aromatic rings (2–3 rings, 4 rings, 5 rings and 6 rings) by varying pressure (200–510 bar), temperature (50–150 °C), extraction fluid volume (10–50 ml), and the methanol modifier concentration (0–10%). Using a five level spherical factorial experimental design the number of experiments required for optimisation was 45. In spiked soil samples extraction efficiencies of 80–100% were achieved for the individual groups of PAHs. At the optimal set of conditions 10–30% lower recoveries of PAHs were obtained for the standard reference material NIST SRM 1941a (marine sediment). The largest differences between extraction recoveries of native and spiked PAHs occurred at high molecular weight PAHs. Using SFE efficiency data for the standard reference material, cluster analysis proved that dividing the 16 PAHs into four groups according to their number of aromatic rings was appropriate and correct. Received: 2 February 1996/Revised: 26 November 1996/Accepted: 30 November 1996     

Synthesis,characterization, and antimicrobial evaluation of a small library of ferrocene-containing acetoacetates and phenyl analogs: the discovery of a potent anticandidal agent

A library of 16 2-substituted methyl acetoacetates containing ferrocenyl or phenyl units was designed to disclose differences in the antimicrobial activity of ferrocene-containing compounds and their phenyl analogs. Two methyl acetoacetates, whose structures do not contain an aromatic nucleus, were also included in order to probe the inherent activity of the scaffold itself. The acetoacetates were synthesized (low-to-good yields) and fully characterized by spectral (MS, IR, UV–Vis, 1D and 2D NMR) and electrochemical (cyclic voltammetry) techniques. Single-crystal X-ray analysis has been performed for methyl 2-acetyl-2-(ferrocenylmethyl)-5-methylhex-4-enoate. All compounds have demonstrated in vitro antimicrobial activity against six bacterial (three Gram-positive and three Gram-negative) and two fungal strains with minimal inhibitory concentration values of 0.0050–20.6  \(\upmu \hbox {mol mL}^{-1}\) . The most active compound was 2-acetyl-2-(ferrocenylmethyl)-4-methylpent-4-enoate whose activity was comparable to that of nystatin against the yeast Candida albicans. Agglomerative hierarchical clustering statistical analysis of the antimicrobial assay data demonstrated that ferrocene-containing compounds have statistically different and greater antimicrobial activity when compared to their phenyl analogs.     

Discrete Charges on a Two Dimensional Conductor

We investigate the electrostatic equilibria of N discrete charges of size 1/N on a two dimensional conductor (domain). We study the distribution of the charges on symmetric domains including the ellipse, the hypotrochoid and various regular polygons, with an emphasis on understanding the distributions of the charges, as the shape of the underlying conductor becomes singular. We find that there are two regimes of behavior, a symmetric regime for smooth conductors, and a symmetry broken regime for “singular” domains. For smooth conductors, the locations of the charges can be determined, to within $O\left( {\sqrt {\log {N \mathord{\left/ {\vphantom {N {N^2 }}} \right. \kern-0em} {N^2 }}} } \right)$ by an integral equation due to Pommerenke [ Math. Ann., 179: 212–218, (1969)]. We present a derivation of a related (but different) integral equation, which has the same solutions. We also solve the equation to obtain (asymptotic) solutions which show universal behavior in the distribution of the charges in conductors with somewhat smooth cusps. Conductors with sharp cusps and singularities show qualitatively different behavior, where the symmetry of the problem is broken, and the distribution of the discrete charges does not respect the symmetry of the underlying domain. We investigate the symmetry breaking both theoretically, and numerically, and find good agreement between our theory and the numerics. We also find that the universality in the distribution of the charges near the cusps persists in the symmetry broken regime, although this distribution is very different from the one given by the integral equation.     

Twist elasticity and anchoring in a lamellar nematic phase

Electro-optic measurements were performed on a lamellar nematic phase in which the mesogenic moieties lie in lamellae that are separated by partially perfluorinated side groups. The twist elastic constant K22, viscosity gamma(1), and the quadratic and quartic anchoring strength coefficients are reported. K22 and gamma(1) are found to be considerably smaller than that of typical three-dimensional nematics. The small K22 is due to the greatly weakened interactions between the spatially separated lamellae.     

Image reconstruction in diffuse optical tomography using the coupled radiative transport-diffusion model

The coupled radiative transport-diffusion model can be used as light transport model in situations in which the diffusion equation is not a valid approximation everywhere in the domain. In the coupled model, light propagation is modelled with the radiative transport equation in sub-domains in which the approximations of the diffusion equation are not valid, such as within low-scattering regions, and the diffusion approximation is used elsewhere in the domain. In this paper, an image reconstruction method for diffuse optical tomography based on using the coupled radiative transport-diffusion model is developed. In the approach, absorption and scattering distributions are estimated by minimising a regularised least-squares error between the measured data and solution of the coupled model. The approach is tested with simulations. Reconstructions from different cases including domains with low-scattering regions are shown. The results show that the coupled radiative transport-diffusion model can be utilised in image reconstruction problem of diffuse optical tomography and that it produces as good quality reconstructions as the full radiative transport equation also in the presence of low-scattering regions.     

Investigating Possible Dipole-Bound States of Cyanopolyynes: the Case for the C5N− Anion Detected in Interstellar Space

We present results of quantum structure calculations aimed at demonstrating the possible existence of dipole-bound states (DBS) for the anion , a species already detected in the Interstellar medium (ISM). The positive demonstration of DBS existence using ab initio studies is an important step toward elucidating possible pathways for the formation of the more tightly bound valence bound states (VBS) in environments where free electrons from starlight ionization processes are known to be available to interact with the radical partner of the title molecule. Our current calculations show that such excited DBS states can exist in , in agreement with what we had previously found for the smallercyanopolyyne in the series: the anion. This system has a very weakly bound anion with binding energies of about 3 and 9 cm⁻¹ for the and DBS, respectively.